WO2008020925A1 - Plasticized hetero-phase polyolefin blends - Google Patents

Plasticized hetero-phase polyolefin blends Download PDF

Info

Publication number
WO2008020925A1
WO2008020925A1 PCT/US2007/015486 US2007015486W WO2008020925A1 WO 2008020925 A1 WO2008020925 A1 WO 2008020925A1 US 2007015486 W US2007015486 W US 2007015486W WO 2008020925 A1 WO2008020925 A1 WO 2008020925A1
Authority
WO
WIPO (PCT)
Prior art keywords
composition
less
cst
nfp
polypropylene
Prior art date
Application number
PCT/US2007/015486
Other languages
French (fr)
Inventor
Bryan R. Chapman
Jeffrey Valentage
Jared M. Hill
Bruce R. Lundmark
Original Assignee
Exxonmobil Chemical Patents Inc.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Exxonmobil Chemical Patents Inc. filed Critical Exxonmobil Chemical Patents Inc.
Priority to BRPI0715067-9A priority Critical patent/BRPI0715067A2/en
Priority to AU2007285017A priority patent/AU2007285017C1/en
Priority to CN200780033057XA priority patent/CN101511929B/en
Priority to EP07810207A priority patent/EP2052028A1/en
Priority to MX2009001661A priority patent/MX2009001661A/en
Priority to JP2009524596A priority patent/JP5140670B2/en
Priority to CA002660532A priority patent/CA2660532A1/en
Priority to KR1020097002949A priority patent/KR101161914B1/en
Publication of WO2008020925A1 publication Critical patent/WO2008020925A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/02—Heterophasic composition
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0807—Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815—Copolymers of ethene with aliphatic 1-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L91/00—Compositions of oils, fats or waxes; Compositions of derivatives thereof
    • C08L91/005—Drying oils

Definitions

  • This invention relates to hetero-phase polyolefin compositions, such as 5 polypropylene-based thermoplastic polyolefin compositions, for use in the manufacture of automotive components, among other uses, and for articles made from such compositions.
  • Multi-phase polyolefin compositions often consisting of a "plastic” matrix phase and a “rubber” dispersed phase - are used in many applications that require a material that is
  • polyolefins in particular semi-crystalline polyolefins (see WO 01/18109 Al and Chemical Additives for the Plastics Industry, Radian Corp., 1987, p. 107-116). Indeed, such compounds are often detrimental to semicrystalline polypropylene, in that they migrate to the surface causing, parts to become oily (except at very low concentrations), or they degrade mechanical properties because they fail to depress the glass transition temperature effectively.
  • the plasticizers 0 described herein overcome these limitations.
  • WO 04/014998 discloses blends of polyolefins with non-functionalized plasticizers.
  • Tables 8, 11, and 21a to 22f describe blends of certain impact copolymers with certain liquids and/or plasticizers
  • Tables 23a to 23f describe blends of a certain thermoplastic polyolefin composition with certain liquids and/or plasticizers.
  • Plasticized polyolefin compositions and their applications are also described in WO 04/014997 and US 2004/260001. Additional references of interest include: US 4132698, US 4536537, US 4774277, JP 09-208761, WO 98/44041, WO 03/48252, and US 2004/034148.
  • TPOs including compositions that comprise polypropylene and or filler, are described in POLYPROPYLENE HANDBOOK, 2 ND ED., N. Pasquini, Ed. (Hanser, 2005), p. 314-330; POLYMER BLENDS, D.R. Paul and CB. Bucknall, Eds. (Wiley-Interscience. 2000), Vol.
  • This invention relates to the use of certain of hydrocarbon liquids as plasticizers for hetero-phase polyolefin compositions based on polypropylene.
  • Such compositions are especially useful in automotive components and other applications that demand high stiffness, excellent impact toughness at low temperatures, and good processibility during fabrication.
  • this invention relates to a hetero-phase polyolefin composition
  • a hetero-phase polyolefin composition comprising: a) 30 to 99.7 wt% of a polypropylene-based TPO comprising at least 50 wt% propylene and at least 10 wt% ethylene, and b) 0.1 to 20 wt% of one or more non-functionalized plasticizer(s), and c) 0.2 to 50 wt% of one or more filler(s); based upon the weight of the composition, and having: i) a melt flow rate, 230 0 C, 2.16kg, (MFR) of 5 dg/min or more, and ii) a flexural modulus of 500 MPa or more, and iii) a notched Charpy impact strength at -30 0 C of 1 kJ/m 2 or more, or a notched Izod impact strength at -18°C of 50 J/m or more.
  • the olefin present in the polymer or oligomer is the polymerized or oligomerized form of the olefin, respectively.
  • polymer is meant to encompass homopolymers and copolymers.
  • copolymer includes any polymer having two or more different monomers in the same chain, and encompasses random copolymers, statistical copolymers, interpolymers, and (true) block copolymers.
  • a polymer blend is said to comprise a certain percentage of a monomer, that percentage of monomer is based on the total amount of monomer units in all the polymer components of the blend. For example if a blend comprises 50 wt% of polymer A, which has 20 wt % monomer X, and 50 wt% of a polymer B, which has 10 wt% monomer X, the blend comprises 15 wt% of monomer X.
  • a "polymer” has a number-average molecular weight (M n ) of 20 kg/mol or more, while an “oligomer” has a M n of less than 20 kg/mol.
  • hetero-phase refers to the presence of two or more morphological phases in a blend of two or more polymers, where each phase comprises a different ratio of the polymers as a result of partial or complete immiscibiliry (i.e., thermodynamic incompatibility).
  • a common example is a morphology consisting of a "matrix” (continuous) phase and at least one "dispersed” (discontinuous) phase.
  • the dispersed phase takes the form of discrete domains (particles) distributed within the matrix (or within other phase domains, if there are more than two phases).
  • Another example is a co-continuous morphology, where two phases are observed but it is unclear which is the continuous phase and which is the discontinuous phase.
  • microscopy techniques e.g., optical microscopy, scanning electron microscopy (SEM) 5 or atomic force microscopy (AFM); or by the presence of two glass transition peaks in a dynamic mechanical analysis (DMA) experiment; in the event of disagreement among these methods, the AFM determination shall be used.
  • SEM scanning electron microscopy
  • AFM atomic force microscopy
  • a “liquid” is defined to be a material that flows at room temperature, having a pour point of less than +20 0 C and a kinematic viscosity at 25°C of 30,000 cSt or less.
  • the term "paraffin” refers to saturated hydrocarbons, including normal paraffins, branched paraffins, isoparaffms, cycloparaffins, and blends thereof, and may be derived synthetically or from refined crude oil by means known in the art.
  • isoparaffins are branched chain-type saturated hydrocarbons (i.e., branched alkanes, having at least one tertiary or quaternary carbon atom), which possess at least one Ci to Cis (more commonly Ci to C 10 ) alkyl branch along at least a portion of each chain;
  • normally paraffins are un-branched chain-type saturated hydrocarbons (i.e., normal alkanes);
  • cycloparaffins also known as "naphthenes” are cyclic (mono-ring and/or multi-ring) saturated hydrocarbons and branched cyclic saturated hydrocarbons.
  • Unsaturated hydrocarbons include alkenes (olefins, diolefins, etc.), alkynes, and "aromatics" (unsaturated mono-ring and/or multi-ring cyclic moieties, including branched cyclic unsaturated hydrocarbons).
  • mineral oil includes any hydrocarbon liquid of lubricating viscosity (i.e., a kinematic viscosity at 100 0 C of 1 cSt or more) derived from petroleum crude oil and subjected to one or more refining and/or hydroprocessing steps (such as fractionation, hydrocracking, dewaxing, isomerization, and hydrofinishing) to purify and chemically modify the components to achieve a final set of properties.
  • refining and/or hydroprocessing steps such as fractionation, hydrocracking, dewaxing, isomerization, and hydrofinishing
  • Such “refined” oils are in contrast to “synthetic” oils, which are manufactured by combining monomer units using catalysts and/or heat.
  • refined “basestocks” which are mineral oils
  • basestocks which are mineral oils
  • Group I ⁇ 90 wt% and/or > 0.03 wt% and 80 - 119
  • a "Group HI Mineral Oil” is defined to be a mineral oil having a viscosity index of 120 or more, whereas a “Group m basestock” is defined according to the above table; therefore, any Group HI basestock will also be a Group HI Mineral Oil, but the opposite is not necessarily true.
  • mineral oils are often called ' ⁇ process oils” (or “extender oils”).
  • a common classification system for process oils is to identify them as either “paraffmic”, “naphthenic”, or “aromatic” mineral (or process or extender) oils based on the relative content of paraffinic, naphthenic, and aromatic moieties (see Typical in the table below).
  • the three common classes are defined based on the compositions described under Definitions in the table below:
  • Cp, C N , and C ⁇ indicate the percentage of carbons in paraffinic chain-like (i.e., isoparaffinic and normal paraffinic) structures, naphthenic (i.e., saturated ring) structures, and aromatic (i.e., unsaturated ring) structures, respectively.
  • substantially absent means that the compounds in question are not added deliberately to the compositions and, if present, are present at less than 1 wt%, based upon the total weight of the composition. Preferably, the compounds in question are present at less than
  • 0.5 wt% (preferably less than 0.1 wt%, preferably less than 0.05 wt%, preferably less than 0.01 wt%, preferably less than 0.001 wt%), based upon the total weight of the composition.
  • This invention relates to plasticized hetero-phase polyolefin compositions comprising a polypropylene-based TPO, one or more non-functionalized plasticizers, and one or more filler.
  • the non-functionalized plasticizer (NFP) compounds of the present invention are hydrocarbon liquids with certain characteristics as described herein. We discovered that addition of one or more NFP improves the overall performance of polypropylene-based TPO compositions that meet the stringent array of mechanical property requirements for automotive (and other) applications. In particular, these compositions exhibit better processibility than can be achieved using previous formulation approaches.
  • the compositions comprise a polypropylene- based TPO 5 an NFP, and a filler, and optionally additives.
  • this invention relates to a hetero-phase polyolefin composition
  • a hetero-phase polyolefin composition comprising: a) 30 to 99.7 wt% of a polypropylene-based TPO comprising at least 50 wt% propylene and at least 10 wt% ethylene, and b) 0.1 to 20 wt% of one or more non-functionalized plasticizer, and c) 0.2 to 50 wt% of one or more filler; based upon the weight of the composition, and having: i) an MFR of 5 dg/min or more, and ii) a flexural modulus of 500 MPa or more, and iii) a notched Charpy impact strength at -30 0 C of 1 kJ/m 2 or more, and/or a notched Izod impact strength at -18°C of 50 J/m or more.
  • the polypropylene-based TPO may be an impact copolymer (especially an in-situ ICP), or it may be a physical blend of an ICP with a plastomer and/or ethylene-propylene rubber (EP Rubber), or it may be a physical blend of a propylene polymer (especially a homopolymer polypropylene (hPP) or a random copolymer polypropylene (RCP)) with a plastomer and/or EP Rubber.
  • an impact copolymer especially an in-situ ICP
  • ICP plastomer and/or ethylene-propylene rubber
  • EP Rubber ethylene-propylene rubber
  • propylene polymer especially a homopolymer polypropylene (hPP) or a random copolymer polypropylene (RCP)
  • the polypropylene-based TPO comprises a matrix having a melting point (T m ) of 110°C or more (preferably 120 0 C or more, preferably 125°C or more, preferably 130 0 C or more, preferably 140 0 C or more, preferably 150 0 C or more, preferably 160 0 C or more), hi another preferred embodiment, the polypropylene-based TPO comprises a dispersed phase having a glass transition temperature (Tg) of -20 0 C or less (preferably -25°C or less, preferably -30 0 C or less, preferably -35°C or less, preferably -40 0 C or less, preferably -45°C or less, preferably -50 0 C or less, preferably -55°C or less).
  • Tg glass transition temperature
  • the non-functional plasticizer may be a PAO oligomer, or it may be a Group IH Mineral Oil, or it may be a GTL basestock, or it may be an Exceptional Paraffinic Process Oil.
  • the NFP has a kinematic viscosity at 100 0 C of 5 cSt or more, a viscosity index of 100 or more, a pour point of -20 0 C or less, a specific gravity less than 0.86, and a flash point greater than 200 0 C. Preferred NFPs are described more fully below.
  • the filler may be inorganic mineral particulates, inorganic fibers, or engineering thermoplastic fibers. Preferred fillers are described more fully below.
  • this invention relates to a hetero-phase polyolefm composition
  • a hetero-phase polyolefm composition comprising: a) 30 to 99.7 wt% (preferably 35 to 95 wt%, preferably 40 to 90 wt%, preferably 45 to 85 wt%) of a polypropylene-based TPO, b) 0.1 to 20 wt% (preferably 0.5 to 15 wt%, preferably 1 to 10 wt%, preferably 1.5 to 5 wt%) of one or more NFP(s), and c) 0.2 to 50 wt% (preferably 0.5 to 40 Wt 0 Zo, preferably 1 to 30 wt%, preferably 5 to 20 wt%) of one or more filler(s), based upon the weight of the composition; and having i) a melt flow rate of 5 dg/min or more (preferably 10 dg/min or more, preferably 15 to 400 dg/min, preferably 20 to 300 dg/min, preferably 30 to 200
  • 3500 MPa preferably 1000 to 3000 MPa, preferably 1100 to 2500 MPa
  • the polypropylene-based TPO may comprise one or more ICP(s); or one or more propylene polymer and one or more ethylene copolymer and/or EP Rubber; or one or more ICP and one or more propylene polymer and one or more ethylene copolymer and/or EP Rubber.
  • the ICP(s) preferably at least one of the ICP(s) is an in-situ ICP; more preferably all the ICP(s) are in-sini ICP(s).
  • the combination of ICP(s) comprises two in-situ ICPs; alternately, the composition comprises only one in-situ ICP.
  • the propylene polymer of the combination of propylene polymer(s) has a melting point of at least 110 0 C (preferably at least 120 0 C, preferably at least 130 0 C, preferably at least 140 0 C. preferably at least 150 0 C 5 preferably at least 160 0 C, preferably at least 165°C).
  • the ethylene copolymer or the combination of ethylene copolymers has a density of less than 0.90 g/cm 3 (preferably less than 0.89 g/cm 3 , preferably less than 0.88 g/cm 3 , preferably less than 0.87 g/cm 3 ).
  • EP Rubber Preferably the EP Rubber or the combination of EP Rubber(s) has density of less than 0.87 g/cm 3 (preferably less than 0.86 g/cm 3 ).
  • NFP has a kinematic viscosity at
  • 100 0 C of 4 cSt or more (preferably 6 cSt or more, preferably 8 cSt or more, preferably 10 cSt or more), a viscosity index of 100 or more (preferably 110 or more, preferably 120 or more, preferably 130 or more), a pour point of -15°C or less (preferably -20 0 C or less, preferably -25°C or less, preferably -30 0 C or less), a flash point of 200 0 C or more (preferably 220 0 C or more, preferably 240 0 C or more, preferably 260 0 C or more), and a specific gravity of 0.88 or less
  • the filler is an inorganic mineral filler with a median particle diameter of less than 50 microns.
  • any hetero-phase polyolefin composition of the present invention has: a) melt flow rate (MFR) of 10 to 500 dg/min (preferably 15 to 200 dg/min, preferably 20 to 100 dg/min, preferably 25-80 dg/min), and b) flexural modulus of 900 to 3500 MPa (preferably 1000 to 3000 MPa, preferably 1100 to 2800 MPa); and one or both of the following properties : c) notched Charpy impact strength at -30 0 C of 1.5 to 15 kJ/m 2 (preferably 2 to 12 kJ/m 2 , preferably 2.5 tolO kJ/m 2 ), and/or d) notched Izod impact strength at -18°C of 60 to 500 J/m (preferably 70 to 400 J/m, preferably 80 to 350 J/m, preferably 90 to 300 J/m, preferably 100 to 250 J/m); and optionally one or more of the following properties: e) notched
  • the hetero-phase polyolefin composition in the absence of any optional additives has a fogging number (SAE Jl 756) of 80 or more (preferably 90 or more, preferably 95 or more, preferably 98 or more).
  • compositions of the present invention can be characterized in that the glass transition temperature (Tg) of at least one polymer component in the composition is depressed by at least 2 0 C (preferably at least 4°C, preferably at least 6°C, preferably at least 8°C, preferably at least 8°C, preferably at least 10 0 C) for every 1 wt% of NFP present in the composition, while the peak melting temperature of the highest melting component remains within 5 0 C (preferably within 4°C, preferably within 3°C, preferably within 2°C) of its value for the same composition absent the NFP.
  • Tg glass transition temperature
  • compositions of the present invention can be characterized in that the glass transition temperature (Tg) of at least one component in the composition is depressed at least 2°C (preferably at least 4°C, preferably at least 6°C, preferably at least 8°C, preferably at least 10°C, preferably at least 12°C, preferably at least 15°C, preferably at least 20 0 C) relative to its value for the same composition absent the NFP, while the peak melting temperature of the highest melting component remains within 5°C (preferably within 4°C, preferably within 3°C, preferably within 2°C) of its value for the same composition absent the NFP.
  • Tg glass transition temperature
  • compositions of the present invention can be characterized in that the weight loss of the composition containing the NFP is less than 3% (preferably less than 2%, preferably less than 1%) when permanence of the NFP is determined as described in the Experimental Methods section. Weight loss here refers to the reduction in weight in excess of that measured for the same composition without the NFP under the same test conditions.
  • Preferred compositions of the present invention can be characterized in that the melt flow rate (MFR) of the composition increases by at least 2% (preferably at least 4%, preferably at least 6%, preferably at least 8%, preferably at least 10%, preferably at least 12%, preferably at least 15%, preferably at least 20%) for every 1 wt% of NFP present in the composition as compared to the same composition absent the NFP.
  • MFR melt flow rate
  • the hetero-phase polyolefin composition exhibits reduced flow marks, either in severity (visibility rating) or tendency (onset distance from gate) as compared to the same hetero-phase polyolefin composition without NFP (i.e., where the ratio of the remaining component weight fractions is the unchanged).
  • the compositions of this invention have a flow mark visibility rating of 3 or less (preferably 2 or less, preferably 1 or less, preferably 0).
  • the distance from the gate to the first visible flow mark is 5 in or more (preferably 7 in or more, preferably 9 in or more, preferably 11 in or more,' preferably 13 in or more).
  • no flow marks are detected. Flow marks are evaluated following the protocol outlined in the Experimental Methods section.
  • the hetero-phase polyolefin composition exhibits an equal or better scratch resistance rating as compared the same hetero-phase polyolefin composition without NFP (i.e., where the ratio of the remaining component weight fractions is the unchanged).
  • the compositions of this invention have a scratch resistance rating of 3 N or more (preferably 5 N or more, preferably 7 N or more, preferably 10 N or more, preferably 12 N or more). The scratch resistance rating is determined following the protocol outlined in the Experimental Methods section.
  • the hetero-phase polyolefin compositions of the present invention include one or more matrix phase component(s), comprised of polypropylene impact copolymer (ICP) and/or propylene homopolymer or copolymer, as well as one or more dispersed phase component(s), comprised of ethylene copolymer and/or EP Rubber.
  • matrix phase component(s) comprised of polypropylene impact copolymer (ICP) and/or propylene homopolymer or copolymer
  • dispersed phase component(s) comprised of ethylene copolymer and/or EP Rubber.
  • the classes of materials described herein that are useful for the matrix phase can be utilized alone or admixed to obtain desired properties.
  • the classes of materials described herein that are useful for the dispersed phase can be utilized alone or admixed to obtain desired properties.
  • Any polymeric component useful in the present invention may be described by any number of, or any combination of, parameters described herein.
  • the ICP comprises a polypropylene component (A) of hPP or RCP, and a rubber component (B) of propylene copolymer.
  • the morphology is such that the matrix phase is comprised primarily of (A) while the dispersed phase is comprised primarily of (B).
  • Preferred ICPs useful in this invention include those having one or more of the following properties:
  • total comonomer content of 1 to 35 wt% (preferably 2 to 30 wt%, preferably 3 to 25 wt%, preferably 5 to 20 wt%) based on the weight of the ICP; and/or
  • ratio of the intrinsic viscosity (IV) of the rubber component to the IV of the polypropylene component of 0.5 to 15 (preferably 0.75 to 12, preferably 1 to 8); and/or 6) propylene meso diads in the polypropylene component of 90% or more (preferably 92% or more, preferably 94% or more, preferably 96% or more); and/or
  • M w of 20 to 2,000 kg/mol preferably 50 to 1,000 kg/mol, preferably 90 to 500 kg/mol
  • melting point (T m , second heat, peak) of 100 0 C or more (preferably 110 0 C or more, preferably 120 0 C or more, preferably 130 0 C or more, preferably 140 0 C or more, preferably 150 0 C or more, preferably 155°C or more, preferably 160°C or more); and/or
  • heat of fusion of 60 J/g or more (preferably 70 J/g or more, preferably 80 J/g or more, preferably 90 J/g or more, preferably 95 J/g or more, preferably 100 J/g or more); and/or
  • glass transition temperature (Tg) of the rubber component of -30 0 C or less (preferably -40 0 C or less, preferably -50 0 C or less); and/or
  • glass transition temperature (T g ) of the polypropylene component of-10°C or more (preferably -5°C or more, preferably 0 0 C or more);
  • flexural modulus of 300 to 3000 MPa preferably 500 to 2500 MPa, preferably 700 to 2000 MPa, preferably 900 to 1500 MPa
  • HDT heat deflection temperature
  • Comonomers used in conjunction with propylene to make an ICP are chosen from ethylene and C 4 to Cs 1 -olefins, preferably from ethylene and 1-butene.
  • the comonomer is ethylene and is present in the ICP at 1 to 50 wt% (preferably 2 to 40 wt%, preferably 3 to 30 wt%, preferably 5 to 20 wt%) based on the weight of the ICP.
  • the rubber component of the ICP comprises 20 to 75 wt% (preferably 25 to 70 wt%, preferably 30 to 65 wt%, preferably less than 60 wt%) ethylene, and the balance propylene, based on the weight of the rubber component.
  • More than one comonomer may also be employed, preferable selected from ethylene and C 4 to Cs 1 -olefins, such as ethylene and butene-1 or ethylene and hexene-1, such that the rubber component comprises a propylene terpolymer.
  • the polypropylene (A) and rubber (B) components may be made using any appropriate polymerization process, including gas-phase, solution, slurry, and high-pressure polymerization processes.
  • (A) is made in a solution or slurry process
  • (B) is made in a gas-phase process.
  • the in- situ ICP is made using a slurry reactor to produce an hPP (A) component, and a gas-phase reactor to produce an EP Rubber (B) component.
  • the in-situ ICP polymerization processes may employ any appropriate polymerization catalyst or combination of catalysts, including Ziegler-Natta and/or single-site (e.g., metallocene) polymerization catalysts, which may be supported (for use in heterogeneous catalysis processes) or not (for use in homogeneous catalysis processes).
  • (A) and (B) are made using a common supported Ziegler-Natta or single-site catalyst.
  • the rubber component comprises a propylene copolymer with a weight-average molecular weight (M w ) of at least 50 kg/mol (preferably 100 kg/mol, preferably 150 kg/mol, preferably 200 kg/mol); a molecular weight distribution (M w /M n ) of less than 3.5 (preferably less than 3.0, preferably 1.8 to 2.5); and a CDBI of greater than 60% (preferably greater than 65%, preferably greater than 70%, preferably greater than 75%, preferably greater than 80%, preferably greater than 85%).
  • CDBI is a measure of the composition distribution of monomer within the polymer chains.
  • In-situ ICPs useful in the present invention are commercially available from many manufacturers, including ExxonMobil Chemical, Borealis, Dow Chemical (including INSPIRETM grades), Sunoco Chemical, and Total Petrochemicals. Suitable examples include: ExxonMobil Chemical in-situ ICPs
  • Suitable ICPs are also commercially available from Basell Polyolefins, including "Advanced Polyolefins" grades made using their CATALLOYTM polymerization process, some of which are commercially available under the ADFLEXTM tradename. Basell also sells ICPs under the HIFAXTM and PROF AXTM tradenames.
  • Useful in-situ-impact copolymers may be prepared by the process described in US 4,379,759; US 6,342,566; and US 6,384,142. A general description of in-situ ICPs can be found in POLYPROPYLENE HANDBOOK, E.P. Moore, Ed. (Hanser-Verlag, 1996).
  • Preferred propylene polymers (homopolymers and copolymers) useful in this invention include those having one or more of the following properties: 1) propylene content of at least 85 wt% (preferably at least 90 wt%, preferably at least 95 wt%, preferably at least 97 wt%, preferably 100 wt%); and/or
  • M w of 30 to 2,000 kg/mol preferably 50 to 1 ,000 kg/mol, preferably 90 to 500 kg/mol
  • M w /M n of 1 to 40 (preferably 1.4 to 20, preferably 1.6 to 10, preferably 1.8 to 3.5 , preferably 1.8 to 2.5);
  • branching index (g ? ) of 0.2 to 2.0 preferably 0.5 to 1.5, preferably 0.7 to 1.3, preferably 0.9 to 1.1
  • melt flow rate of 1 to 300 dg/min (preferably 5 to 150 dg/min, preferably 10 to 100 dg/min, preferably 20 to 60 dg/min); and/or 6) melting point (T m , peak second melt) of at least 100 0 C (preferably at least 110 0 C, preferably at least 120 0 C, preferably at least 130 0 C, preferably at least 140 0 C, preferably at least 150 0 C, preferably at least 160 0 C, preferably at least 165°C); and/or
  • T 0 crystallization temperature (T 0 , peak) of at least 70 0 C (preferably at least 90 0 C, preferably at least 110 0 C, preferably at least 130 0 C); and/or
  • H f heat of fusion
  • crystallinity of 5 to 80% (preferably 10 to 75%, preferably 20 to 70%, preferably 30 to 65%, preferably 40 to 60%);
  • propylene meso diads of 90% or more (preferably 92% or more, preferably 94% or more, preferably 96% or more); and/or 11) heat deflection temperature (HDT) of 45 to 14O 0 C (preferably 60 to 135°C, preferably 75 to 125°C); and/or
  • flexural modulus of 300 to 3000 MPa preferably 600 to 2500 MPa, preferably 800 to 2000 MPa, preferably 1000 to 1500 MPa.
  • the propylene polymer is selected from polypropylene homopolymer, polypropylene copolymers, and blends thereof.
  • the homopolymer may be atactic polypropylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, and blends thereof.
  • the copolymer can be a random copolymer, a statistical copolymer, a block copolymer, and blends thereof.
  • the method of making the polypropylene is not critical, as it can be made by slurry, solution, gas-phase, high-pressure, or other suitable processes, through the use of catalyst systems appropriate for the polymerization of polyolefms, such as Ziegler-Natta-type catalysts, metallocene-type catalysts, other appropriate catalyst systems or combinations thereof.
  • the propylene polymers are made by the catalysts, activators and processes described in US 6,342,566, US 6,384,142, WO 03/040201, WO 97/19991 and US 5741563.
  • Such catalysts are well known in the art, and are described in, for example, ZIEGLER CATALYSTS (Gerhard Fink, Rolf M ⁇ lhaupt and Hans H. Brintzinger, eds., Springer- Verlag 1995); Resconi et al., Selectivity in Propene Polymerization with Metallocene Catalysts, 100 CHEM. REV. 1253- 1345 (2000); and I, H METALLOCENE-BASED POLYOLEFINS (Wiley & Sons 2000).
  • Polypropylene homopolymers or copolymers useful in the present invention may have some level of isotacticity or syndiotacticity.
  • the polypropylene is isotactic polypropylene, and in another embodiment, the polypropylene is highly isotactic polypropylene.
  • the polypropylene is a polypropylene homopolymer having at least 85% (preferably at least 90%) isotactic pentads.
  • the polypropylene is a polypropylene homopolymer having at least 85% (preferably at least 90%) syndiotactic pentads.
  • the propylene polymers useful herein are produced by a metallocene catalyst system, and have a M w /M n of 1.5 to 3 (preferably 1.8 to 2.5) and a CDBI of 80 wt% or more (preferably 90 wt% or more).
  • the propylene polymer is a random copolymer, also known as an "RCP," comprising propylene and up to 20 mole % of ethylene or a C4 to C20 olefin, preferably up to 20 mole % ethylene, preferably from 1 to 10 mole % ethylene.
  • RCP random copolymer
  • Propylene polymers that are useful in this invention include hPP and RCP grades commercially available from many manufacturers, including ExxonMobil Chemical (including hPP grades sold under the ACHIEVETM tradename), Basell Polyolefins, Borealis, Dow Chemical, Sunoco Chemical, and Total Petrochemicals.
  • Ethylene Copolymers [0057] Preferred ethylene copolymers useful in this invention include those having one or more of the following properties:
  • ethylene content of 60 to 90 wt% (preferably 65 to 85 wt%, preferably 65 to 80 wt%, preferably 65 to 75 wt%); and/or
  • butene-1 content of 15 wt% or more (preferably 20 wt% or more, preferably 25 wt% or more);
  • hexene-1 content of 20 wt% or more (preferably 25 wt% or more, preferably 30 wt% or more);
  • octene-1 content of 25 wt% or more (preferably 30 wt% or more, preferably 35 wt% or more);
  • H f heat of fusion (H f ) of 90 J/g or less (preferably 70 J/g or less, preferably 50 J/g or less, preferably 30 J/g or less, preferably 10 to 70 J/g, preferably 10 to 50 J/g, preferably 10 to 30 J/g); and/or
  • crystallinity of 40% or less (preferably 30% or less, preferably 20% or less, preferably at least 5%, preferably 5 to 30%, preferably 5 to 20%); and/or 10) melting point (T m , peak first melt) of 100 0 C or less (preferably 90 0 C or less, preferably 80 0 C or less, preferably 70 0 C or less, preferably 60 0 C or less, preferably 50 0 C or less); and/or
  • crystallization temperature (T c , peak) of 90 0 C or less (preferably 80 0 C or less, preferably 70 0 C or less, preferably 60 0 C or less, preferably 5O 0 C or less, preferably 40 0 C or less); and/or
  • glass transition temperature (Tg) of -20 0 C or less (preferably -30 0 C or less, preferably -40 0 C or less);
  • Mw of 30 to 2,000 kg/mol preferably 50 to 1 ,000 kg/mol, preferably 90 to 500 kg/mol
  • M w /M n of 1 to 40 (preferably 1.4 to 20, preferably 1.6 to 10, preferably 1.8 to 3.5, preferably 1.8 to 2.5); and/or 15) branching index (g 1 ) of 0.9 or greater (preferably 0.95 or greater, preferably 0.99 or greater); and/or
  • melt index (MT) of 0.1 to 100 dg/min (preferably 0.3 to 60 dg/min, preferably 0.5 to 40 dg/min, preferably 0.7 to 20 dg/min); and/or
  • CDBI of at least 60 wt% (preferably at least 70 wt%, preferably at least 80 wt%, preferably at least 90 wt%, preferably at least 95 wt%).
  • the ethylene copolymer is an ethylene-based plastomer with a density of 0.86 to 0.91 g/cm 3 (preferably 0.86 to 0.90 g/cm 3 , preferably 0.86 to 0.89 g/cm 3 , preferably 0.86 to 0.88 g/cm 3 , preferably 0.86 to 0.87 g/cm 3 ).
  • Preferred plastomers comprise less than 85 wt% (preferably less than 75 wt%) ethylene and up to 50 wt% (preferably 20 to 40 wt%) of one or more olefin comonomers selected from propylene and C 4 -C 2O olefins (preferably 1- butene, 1-hexene, and/or 1-octene).
  • the ethylene copolymer is an ethylene elastomer with a density of less than 0.86 g/cm 3 , comprised of ethylene and at least 30 wt% of one or more C4-C20 olefin comonomers (preferably 1-butene, 1-hexane, and/or 1-octene).
  • the ethylene copolymer can be a random copolymer, a statistical copolymer, a block copolymer, and blends thereof.
  • the method of making the ethylene copolymer is not critical, as it can be made by slurry, solution, gas-phase, high-pressure, or other suitable processes, through the use of catalyst systems appropriate for the polymerization of polyolefins, such as Ziegler-Natta catalysts, metallocene catalysts, other appropriate catalyst systems or combinations thereof.
  • the ethylene copolymers useful herein are produced using a metallocene catalyst system, i.e., a mono- or bis-cyclopentadienyl transition metal catalysts in combination with an activator of alumoxane and/or a non-coordinating anion in solution, slurry, high-pressure, or gas-phase.
  • the catalyst and activator may be supported or unsupported and the cyclopentadienyl rings by may substituted or unsubstituted.
  • WO 94/26816 WO 94/03506
  • EPA 277,003 EPA 277,004
  • U.S. Pat. No. 5,153,157 U.S. Pat. No. 5,198,401
  • U.S. Pat. No. 5,240,894 U.S. Pat. No. 5,017,714; CA 1,268,753; U.S. Pat. No. 5,324,800; EPA 129,368; U.S. Pat. No.
  • preferred plastomers are produced using a single-site catalyst, whether a metallocene catalyst or not, and have a M w /M n of 1.5 to 3 (preferably 1.8 to 2.5) and a CDBI of 70% or more (preferably 80% or more, preferably 90% or more).
  • Plastomers that are useful in this invention include those available from ExxonMobil Chemical (sold under the EXACTTM tradename), Dow Chemical (sold under the AFFINITYTM, ENGAGETM, and FLEXOMERTM tradenames), and Mitsui Chemicals (sold under the TAFMERTM tradename). Examples include: ExxonMobil Chemical EXACTTM Plastomers
  • Preferred EP Rubbers useful in this invention include those having one or more of the following properties:
  • ethylene content of 25 to 80 wt% (preferably 30 to 75 wt%, preferably 35 to 70 wt%, preferably 40 to 65 wt%); and/or
  • diene content of 15 wt% or less (preferably 12 wt% or less, preferably 9 wt% or less, preferably 6 wt% or less, preferably 3 wt% or less, preferably 0 wt%); and/or
  • Tg glass transition temperature
  • M w /M n of 1.5 to 40 (preferably 1.6 to 30, preferably 1.7 to 20, preferably 1.8 to 10, preferably 1.8 to 5, preferably 1.8 to 3, preferably 1.8 to 2.5);
  • Particularly preferred EP Rubbers for use herein contain no diene (i.e., an ethylene- propylene copolymers). If diene is present (i.e., an ethylene-propylene-diene terpolymer), preferably the diene is a norbornene-derived diene such as ethylidene norbornene (ENB) or vinylidene norbornene (VNB). Diene content is measured by ASTM D-6047.
  • the method of making the EP Rubber is not critical, as it can be made by slurry, solution, gas-phase, high-pressure, or other suitable processes, through the use of catalyst systems appropriate for the polymerization of polyolefins, such as Ziegler-Natta catalysts, metallocene catalysts, other appropriate catalyst systems or combinations thereof.
  • the EP Rubbers useful herein are produced using a vanadium-based catalyst system in a solution or slurry process.
  • the EP Rubbers useful herein are produced using a metallocene-based catalyst system in a solution or slurry process.
  • the EP Rubbers useful herein are produced using any single-sited catalyst system in a solution or slurry process.
  • the EP Rubbers made by a vanadium, metallocene, or other single-sited catalyst system has a molecular weight distribution (M w /M n ) of 1.8 to 2.5.
  • EP Rubbers that are useful in this invention include those available from ExxonMobil Chemical (sold under the VistalonTM tradename), including: ExxonMobil Chemical VistalonTM EP Rubbers
  • NDP Non-Functionalized Plasticizer
  • the hetero-phase polyolefin compositions of the present invention include at least one non-fimctionalized plasticizer ("NFP").
  • NFP non-fimctionalized plasticizer
  • the classes of materials described herein that are useful as non-functionalized plasticizers can be utilized alone or admixed other NFPs described herein to obtain desired properties. Any NFP useful in the present invention may also be described by any number of, or any combination of, parameters described herein.
  • An NFP is defined to be a hydrocarbon liquid compound comprising carbon and hydrogen, having functional groups selected from hydroxide, aryls, substituted aryls, halogens, alkoxys, carboxylates, esters, carbon unsaturation, acrylates, oxygen, nitrogen, and carboxyl present to an unappreciable extent.
  • unappreciable extent it is meant that these groups and compounds comprising these groups are not deliberately added to the NFP, and if present at all for any reason, are present at less than 5 wt%.
  • the these groups and compounds are present at less than 4 wt%, preferably less than 3 wt%, preferably less than 2 wt%, preferably less than 1 wt%, preferably less than 0.7 wt%, preferably less than 0.5 wt%, preferably less than 0.3 wt%, preferably less than 0.1 wt%, preferably less than 0.05 wt%, preferably less than 0.01 wt%, preferably less than 0.001 wt%), based upon the weight of the NFP.
  • aromatic moieties including compounds whose molecules have the ring structure characteristic of benzene, naphthalene, phenanthrene, anthracene, etc.
  • naphthenic moieties including compounds whose molecules have a saturated ring structure such as would be produced by hydrogenating benzene, naphthalene, phenanthrene, anthracene, etc.
  • the NFP is a hydrocarbon that contains olefinic unsaturation to an unappreciable extent.
  • unappreciable extent of olefinic unsaturation it is meant that the carbons involved in olefinic bonds account for less than 10% (preferably less than 8%, preferably less than 6%, preferably less than 4%, preferably less than 2%, preferably less than 1%, preferably less than 0.7%, preferably less than 0.5%, preferably less than 0.3%, preferably less than 0.1%, preferably less than 0.05%, preferably less than 0.01%, preferably less than 0.001%) of the total number of carbons.
  • the percent of carbons of the NFP involved in olefinic bonds is between 0.001 and 10% of the total number of carbon atoms in the NFP (preferably between 0.01 and 5%, preferably between 0.1 and 2%, preferably less than 1%).
  • the NFP comprises Ce to C 2 oo paraffins, and Cg to Cioo paraffins in another embodiment.
  • the NFP consists essentially of Ce to C 200 paraffins, or essentially of C 8 to Cioo paraffins in another embodiment.
  • the NFP comprises C 2 o to C 1 S 0 O paraffins, preferably C25 to C500 paraffins, preferably C25 to C500 paraffins, preferably C 3 o to C50 0 paraffins, preferably C 40 to C500 paraffins, preferably C40 to C250 paraffins, preferably C30 to C150 paraffins, preferably C20 to Cioo paraffins.
  • the NFP comprises oligomers of C 5 to C 24 olefins.
  • NFPs include a) isoparaffins, b) PAOs, c) Group IQ Mineral Oils, d) high purity hydrocarbon fluids derived from a so-called Gas-To-Liquids processes, and e) mineral oils; with a viscosity index greater than 100 (preferably greater than 120), pour point less than -15°C (preferably less than -20 0 C), specific gravity less than 0.86 (preferably less than 0.855), and flash point greater than 200 0 C (preferably greater than 230 0 C).
  • the NFP is an isoparaffin-rich hydrocarbon liquid with a pour point of -50 0 C or less (preferably -6O 0 C or less) and a specific gravity of 0.84 or less (preferably 0.83 or less).
  • isoparaffin-rich is meant that the NFP comprises at least 50 wt% (preferably at least 60 wt%, preferably at least 70 wt%, preferably at least 80 wt%, preferably at least 90 wt%, preferably 100 wt%) of C 6 to Q 5 O (preferably C 6 to Cioo, preferably C 6 to C25, preferably Cs to C2 0 ) isoparaffms.
  • the paraffin chains possess C 1 to C 1O alkyl branching along at least a portion of each paraffin chain, where any combination of regio and stereo placement of the alkyl branches may be involved.
  • Isoparaffin liquids may also include a minor amount of (less than 50 wt%, preferably less than 30 wt%, preferably less than 10 wt%) of cycloparafflns with isoparaff ⁇ nic branched side chains.
  • Isoparaffms may include any combination of regio and stereo placement of the alkyl branches.
  • the number-average molecular weight of the isoparaffin-rich fluid is in the range of 100 to 1000 (preferably 120 to 500, preferably 150 to 300) g/mol.
  • the isoparaffin-rich NFP has a kinematic viscosity at 40 0 C of l to 15 cSt (preferably 2 to 10 cSt).
  • the isoparaffin-rich NFP has a kinematic viscosity at 25°C of 1 to 30 cSt (preferably 2 to 25 cSt, preferably 3 to 20 cSt, preferably 5 to 15 cSt) and a glass transition temperature (Tg) that cannot be determined by ASTM E 1356 or if it can be determined then it is less than 0 0 C (preferably less than -10 0 C, preferably less than -20 0 C, preferably less than -3O 0 C).
  • the isoparaffin-rich NFP has one or more of the following properties:
  • a pour point of -40 0 C or less (preferably -50 0 C or less, preferably -6O 0 C or less); and/or 2.
  • a kinematic viscosity at 25 0 C of from 1 to 30 cSt; and/or 4. a number average molecular weight (M n ) between 2,000 and 100 g/mol (preferably between 1500 and 150 g/mol, preferably between 1000 and 200 g/mol); and/or
  • a specific gravity (15.6/15.6°C) of less than 0.85 preferably less than 0.84, preferably less than 0.83, preferably from 0.65 to 0.85, preferably from 0.70 to 0.84, preferably from 0.75 to 0.83, preferably from 0.800 to 0.840; and/or
  • a distillation range having a difference between the upper and lower temperatures of 40 0 C or less (preferably 30 0 C or less, preferably 20 0 C or less, preferably 10 0 C or less, preferably between 6 and 4O 0 C); and/or 9. a final boiling point of from 115 to 500 0 C (preferably from 200 to 450 0 C, preferably from 250 to 400 0 C).
  • Suitable isoparaffin-rich hydrocarbon liquids are described in, for example US 3818105, US 3439088 and US 6197285, and are commercially available under the tradename ISOP ARTM (ExxonMobil Chemical), some of which are summarized in the table below.
  • Other suitable isoparaffin-rich hydrocarbon liquids are commercial available under the trade names SHELLSOLTM (Royal Dutch/Shell), SOLTROLTM (Chevron Phillips) and SASOLTM (Sasol Limited). The percentage of carbons in chain-type paraffinic structures (Cp) in such liquids is close to 100% (95% or more).
  • the isoparaffin-rich NFP is a mixture of branched and normal paraffins having 6 to 50 (preferably 8 to 40, preferably 10 to 30) carbon atoms in the molecule.
  • the isoparaffin composition has a ratio of branch paraffin to n-paraffin of 1:1 to 100:1 (preferably 1 :1 to 10:1).
  • the distribution of branches in the isoparaffms of the mixture is such that at least 50% (preferably at least 70%) are methyl branches, with less than 50% (preferably less than 30%) of branches with carbon number greater than 1 (for example, ethyl, propyl, butyl or the like).
  • the isoparaffinic mixture boils within a range of from 100 to 350 0 C (preferably from 110 to 320 0 C) and with a narrow boiling range (preferably 35 0 C or less).
  • branch paraffin/n-paraffm blends are described in, for example, US 5906727.
  • the NFP comprises a polyalphaolefin (PAO) liquid with a pour point of -10 0 C or less and a kinematic viscosity at 100 0 C of 3 cSt or more.
  • PAO liquid comprises hydrocarbon oligomers manufactured by catalytic oligomerization of alpha-olefins, preferably linear alpha-olefins.
  • a PAO may be characterized by any type of tacticity, including isotactic or syndiotactic and/or atactic, and by any degree of tacticity, including isotactic-rich or syndiotactic-rich or fully atactic.
  • PAO liquids are described in, for example, US 3149178; US 4827064; US 4S27073; US 5171908; and US 5783531 and in SYNTHETIC LUBRICANTS AND HIGH-PERPORMANCE FUNCTIONAL FLUIDS, Leslie R. Rudnick & Ronald L. Shubkin, eds. (Marcel Dekker, 1999), p. 3-52.
  • a PAO is not a polymer.
  • PAO liquids may be conveniently prepared by the oligomerization of an ⁇ -olefin in the presence of a polymerization catalyst, such as a Friedel-Crafts catalyst (including, for example, AlCl 3 , BF 3 , and complexes of BF 3 with water, alcohols, carboxylic acids, or esters), a coordination complex catalyst (including, for example, the ethylaluminum sesquichloride + TiCl 4 system), or a homogeneous or heterogeneous (supported) catalyst more commonly used to make polyethylene and/or polypropylene (including, for example, Ziegler-Natta catalysts, metallocene or other single-site catalysts, and chromium catalysts).
  • a polymerization catalyst such as a Friedel-Crafts catalyst (including, for example, AlCl 3 , BF 3 , and complexes of BF 3 with water, alcohols, carboxylic acids, or esters), a coordination complex catalyst (including, for example
  • the PAO comprises C1 5 to C 1SO o (preferably C 2 o to C 1 OOO * preferably C30 to CSOO J preferably C35 to C 4 oo 5 most preferably C40 to C250) oligomers of alpha- olefins. These oligomers are dimers, trimers, tetramers, pentamers, etc.
  • the PAO comprises C 3 to C 24 (preferably C 5 to C 18 , preferably C 6 to C 14 , even preferably Cs to C12, most preferably C10) branched or linear alpha-olefins, provided that C3 and C 4 alpha-olefins are present at 10 wt% or less.
  • the PAO comprises C 3 to C 24 (preferably C5 to C 1S , preferably C 6 to Ci 4 , most preferably C 8 to C 12 ) linear alpha-olefins (LAOs), provided that C3 and C 4 LAOs are present at 10 wt% or less.
  • Suitable olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, and blends thereof.
  • Oligomers of LAOs with only even carbon numbers between 6 and 18 (inclusive) are particularly preferred.
  • a single LAO is used to prepare the oligomers.
  • a preferred embodiment involves the oligomerization of 1-decene, and the PAO is a mixture of oligomers (including, for example, dimers, trimers, tetramers, pentamers, and higher) of 1- decene.
  • the PAO comprises oligomers of two or more C 3 to Ci 8 LAOs (preferably C 5 to C 1S LAOs), to make 'bipolymer' or 'terpolymer' or higher-order copolymer combinations, provided that C 3 and C 4 LAOs are present at 10 wt% or less.
  • a preferred embodiment involves the oligomerization of a mixture of 1-octene, 1-decene, and 1- dodecene
  • the PAO is a mixture of oligomers (for example, dimers, trimers, tetramers, pentamers, and higher) of 1-octene/l-decene/l-dodecene 'terpolymer'.
  • the PAO comprises oligomers of a single alpha-olefin species having a carbon number of 5 to 24 (preferably 6 to 18, preferably 8 to 12, most preferably 10).
  • the NFP comprises oligomers of mixed alpha-olefins (i.e., involving two or more alpha-olefin species), each alpha-olefin having a carbon number of 3 to 24 (preferably 5 to 24, preferably 6 to 18, most preferably 8 to 12), provided that alpha-olefins having a carbon number of 3 or 4 are present at 10 wt% or less.
  • the PAO comprises oligomers of mixed alpha-olefins (i.e., involving two or more alpha-olefin species) where the weighted average carbon number for the alpha-olefin mixture is 6 to 14 (preferably 8 to 12, preferably 9 to 11).
  • the PAO comprises oligomers of one or more ⁇ -olefin with repeat unit formulas of: -[CHR-CH 2 ]- where R is a C 3 to Ci 8 saturated hydrocarbon branch.
  • R is constant for all oligomers.
  • R is linear, i.e., R is (CH 2 )zCH 3 , where z is 2 to 17 (preferably 3 to 11, preferably 4 to 9).
  • R may contain one methyl or ethyl branch, i.e.,
  • R is (CH 2 ) m [CH(CH 3 )](CH 2 ) n CH 3 or (CH 2 ) ⁇ [CH(CH 2 CH 3 )](CH 2 ) y CH 3 , where (m + n) is 1 to 15 (preferably 1 to 9, preferably 3 to 7) and (x ⁇ + ⁇ y) is 1 to 14 (preferably 1 to 8, preferably 2 to 6).
  • m > n Preferably m is 0 to 15 (preferably 2 to 15, preferably 3 to 12, preferably 4 to 9) and n is 0 to 10 (preferably 1 to 8, preferably 1 to 6, preferably 1 to 4).
  • x > y is
  • x is 0 to 14 (preferably 1 to 14, preferably 2 to 11, preferably 3 to 8) and y is 0 to 10 (preferably 1 to 8, preferably 1 to 6, preferably 1 to 4.)
  • the repeat units are arranged in a head-to-tail fashion with minimal heat-to-head connections.
  • the PAO may be atactic, isotactic, or syndiotactic.
  • the PAO has essentially the same population of meso [m] and racem ⁇ c [r] dyads (preferably neither [m] nor [r] greater than 60%, preferably neither greater than 55%) as measured by 13 C-NMR, making it atactic.
  • the PAO has more than 60% (preferably more than 70%, preferably more than 80%, preferably more than 90%) meso dyads [m]. In another embodiment, the PAO has more than 60% (preferably more than 70%, preferably more than 80%, preferably more than 90%) racemic dyads [r]. In one embodiment, [m]/[r] determined by 13 C-NMR is between 0.9 and 1.1 in one embodiment, [m]/[r] is greater than 1 in another embodiment, and [m]/[r] is less than 1 in yet another embodiment.
  • Preferred PAOs have a "branching ratio" as defined in US 4827064 and measured according to the method described therein, of 0.20 or less (preferably 0.19 or less, preferably 0.18 or less, preferably 0.17 or less, preferably 0.15 or less, preferably 0.12 or less, preferably 0.10 or less).
  • the PAO has a number average molecular weight of from 100 to 20,000 g/mol (preferably 300 to 15,000 g/mol, preferably 400 to 10,000 g/mol, preferably 500 to 5,000 g/mol, preferably 600 to 3,000 g/mol, preferably 600 to 1,500 g/mol).
  • the PAO has a kinematic viscosity at 100 0 C of 3 cSt or more (preferably 5 cSt or more, preferably 6 cSt or more, preferably 8 cSt or more, preferably 10 cSt or more, preferably 20 cSt or more, preferably 30 cSt or more, preferably 40 cSt or more, preferably 100 or more, preferably 150 cSt or more).
  • the PAO has a kinematic viscosity at 100 0 C of 300 cSt or less (preferably 100 cSt or less).
  • the PAO has a kinematic viscosity at 100 0 C of 3 to 3,000 cSt (preferably 4 to 1,000 cSt, preferably 6 to 300 cSt, preferably 8 to 150 cSt, preferably 8 to 100 cSt, preferably 8 to 40 cSt). In another embodiment, the PAO has a kinematic viscosity at 100 0 C of 10 to 1000 cSt (preferably 10 to 300 cSt, preferably 10 to 100 cSt). In yet another embodiment, the PAO has a kinematic viscosity at 100 0 C of about 4 to 8 cSt. In yet another embodiment, the PAO has a kinematic viscosity at 100 0 C of 1 to 3 cSt.
  • the PAO has a Viscosity Index of 120 or more (preferably 130 or more, preferably 140 or more, preferably 150 or more, preferably 170 or more, preferably 190 or more, preferably 200 or more, preferably 250 or more, preferably 300 or more).
  • the PAO or blend of PAOs has a viscosity Index of 120 to 350 (preferably 130 to 250).
  • the PAO has a pour point of -1O 0 C or less (preferably -20 0 C or less, preferably -25°C or less, preferably -30 0 C or less, preferably -35°C or less, preferably -40 0 C or less, preferably -50 0 C or less).
  • the PAO or blend of PAOs has a pour point of -15 to -70 0 C (preferably -25 to -60 0 C).
  • the PAO has a glass transition temperature (Tg) of -40 0 C or less (preferably -50 0 C or less, preferably -6O 0 C or less, preferably -70 0 C or less, preferably -80 0 C or less).
  • Tg glass transition temperature
  • the PAO or blend of PAOs has a T g of -50 to -120 0 C (preferably -60 to -100 0 C, preferably -70 to -90 0 C).
  • the PAO has a flash point of 200 0 C or more (preferably 210 0 C or more, preferably 220 0 C or more, preferably 230 0 C or more), preferably between 240°C and 290 0 C.
  • the PAO has a specific gravity (15.6/15.6°C) of 0.86 or less (preferably 0.855 or less, preferably 0.85 or less, preferably 0.84 or less).
  • Particularly preferred PAOs are those having A) a flash point of 200 0 C or more (preferably 210 0 C or more, preferably 220 0 C or more, preferably 230°C or more); and B) a pour point less than -20 0 C (preferably less than -25 0 C, preferably less than -30 0 C, preferably less than -35°, preferably less than -40 0 C) and/or a kinematic viscosity at 100 0 C of 10 cSt or more (preferably 35 cSt or more, preferably 40 cSt or more, preferably 50 cSt or more).
  • Further preferred PAOs have a kinematic viscosity at 100 0 C of at least 3 cSt (preferably at least 6 cSt, preferably at least 8 cSt, most preferably at least 10 cSt); a viscosity index of at least 120 (preferably at least 130, preferably at least 140, most preferably at least 150); a pour point of -10 0 C or less (preferably -20 0 C or less, preferably -30 0 C or less, most preferably -40 0 C or less); and a specific gravity (15.6/15.6°C) of 0.86 or less (preferably 0.855 or less, preferably 0.85 or less, most preferably 0.84 or less).
  • the PAO may be comprised of one or more distinct PAO components.
  • the NFP is a blend of one or more PAOs with different compositions (e.g., different ⁇ -olefin(s) were used to make the oligomers) and/or different physical properties (e.g., kinematic viscosity, pour point, viscosity index, and/or glass transition temperature).
  • Desirable PAOs are available as SpectraSynTM and SpectraSyn UltraTM from ExxonMobil Chemical in Houston, Texas (previously sold under the SHF and SuperSynTM tradenames by ExxonMobil Chemical Company), some of which are summarized in the table below.
  • Other useful PAOs include SynfluidTM available from ChevronPhillips Chemical Company (Pasedena, Texas), DurasynTM available from Innovene (Chicago, Illinois), NexbaseTM available from Neste Oil (Keilaniemi, Finland), and SyntonTM available from Chemtura Corporation (Middlebury, Connecticut).
  • the percentage of carbons in chain-type paraff ⁇ nic structures (C P ) is close to 100% (typically greater than 98% or even 99%) for PAOs.
  • This invention also relates to hetero-phase polyolefm compositions comprising one or more polyolefins, preferably polypropylene, and one or more non-functionalized plasticizers where the non-functionalized plasticizer comprises a polyalphaolefin comprising oligomers of C 5 to C 18 olefins (preferably Ce to C 14 , preferably C 8 to C 12 , preferably Qo); having a kinematic viscosity at 100 0 C of 5 cSt or more (preferably 8 cSt or more, preferably 10 cSt or more); a viscosity index of 120 or more (preferably 130 or more); and a pour point of -10 0 C or less (preferably -20 0 C or less, preferably -30 0 C or less).
  • the non-functionalized plasticizer comprises a polyalphaolefin comprising oligomers of C 5 to C 18 olefins (preferably Ce to C 14 , preferably C 8 to C 12 , preferably
  • This invention also relates to polyolefm compositions comprising a polypropylene- based TPO and one or more non-functionalized plasticizers where the non-functionalized plasticizer comprises oligomers of linear olefins having 5 to 18 carbon atoms (preferably 6 to 14 carbon atoms, preferably 8 to 12 carbon atoms, preferably 10 carbon atoms); a kinematic viscosity at 100 0 C of 5 to 300 cSt (preferably 8 to 150 cSt, preferably 10 to 100 cSt); a viscosity index of 120 or more (preferably 130 or more, preferably 140 or more); and a pour point of -20 0 C or less (preferably -30 0 C or less, preferably -40 0 C or less).
  • the non-functionalized plasticizer comprises oligomers of linear olefins having 5 to 18 carbon atoms (preferably 6 to 14 carbon atoms, preferably 8 to 12 carbon atoms, preferably 10 carbon atoms); a
  • the NFP comprises oligomers of C 4 olefins (including 1-butene, 2-butene, isobutylene, and butadiene, and mixtures thereof) and up to 10 wt% other olefins, often referred to as a "polybutenes" liquid when the oligomers comprise primarily isobutylene and 1-butene.
  • polybutenes also includes homopolymer oligomers of isobutylene or 1-butene, copolymer oligomers of a C 4 raff ⁇ nate stream, and copolymer oligomers of C 4 olefins with ethylene and/or propylene and/or Cs olefins.
  • Such liquids are commonly used as additives for polyolefins; e.g. to introduce tack or as a processing aid.
  • the ratio of C 4 olefin isomers can vary by manufacturer and by grade, and the material may or may not be hydrogenated after synthesis.
  • Polybutenes are described in, for example, SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS (Leslie R. Rudnick & Ronald L. Shubkin, ed., Marcel Dekker 1999), p. 357-392.
  • Preferred polybutenes include those in which isobutylene derived units comprise 40 to 100 wt% (preferably 40 to 99 wt%, preferably 40 to 96 wt%) of the polymer; and/or the 1-butene derived units comprise 0 to 40 wt% (preferably 2 to 40 wt%) of the copolymer; and/or the 2- butene derived units comprise 0 to 40 wt% (preferably 0 to 30 wt%, preferably 2 to 20 wt%) of the polymer.
  • Suitable polybutenes may have a kinematic viscosity at 100 0 C of 3 to 50,000 cSt (more commonly 5 to 3000 cSt), a pour point of -60 to 10 0 C (more commonly -40 to 0 0 C), and a number-average molecular weight of 300 to 10,000 g/mol (more commonly 500 to 2,000 g/mol). Note that, at the same kinematic viscosity or molecular weight, a polybutenes liquid has a higher specific gravity and lower flash point than a PAO liquid.
  • Desirable polybutenes liquids are commercially available from a variety of sources including Innovene (IndopolTM grades) and Infineum (C-Series grades). When the C 4 olefin is exclusively isobutylene, the material is referred to as "polyisobutylene" or PIB. Commercial sources of PIB include Texas Petrochemical (TPC Enhanced PIB grades). When the C 4 olefin is exclusively 1-butene, the material is referred to as "poly-n-butene” or PNB. [0105] Properties of some polybutenes liquids made from C 4 olefin(s) are summarized in the table below.
  • grades with a flash point of 200 0 C or more also have a pour point greater than -10 0 C and/or a VI less than 120.
  • the percentage of carbons in chain-type parafQnic structures (C P ) is close to 100% (typically greater than 98% or even 99%) for polybutenes.
  • TPC 1160 (PIB) 660 190 +3 0.903 230
  • the NFP is not an oligomer of C 4 olefins (i.e., 1-bute ⁇ e, 2-butene, isobutylene, butadiene, and mixtures thereof), including polybutenes and/or PIB and/or PNB.
  • the NFP contains less than 90 wt% (preferably less than 80 wt%, preferably less than 70 wt%, preferably less than 60 wt%, preferably less than 50 wt%, preferably less than 40 wt %, preferably less than 30 wt%, preferably less than 20 wt%, preferably less than 10 wt %, preferably less than 5 wt%, preferably less than 2 wt%, preferably less than 1 wt%, preferably 0 wt %) of C 4 olefins, in particular 1- butene and isobutylene.
  • oligomers of C 4 olefins may also be present in the composition.
  • the composition comprises less than 50 wt% (preferably less than 40%, preferably less than 30 wt%, preferably less than 20 wt%, preferably less than 10 wt%, preferably less than 5 wt%, preferably less than 1 wt%, preferably 0 wt%) of oligomers of C 4 olefins, including polybutenes and/or PIB and/or PNB.
  • the NFP is a high purity hydrocarbon fluid of lubricating viscosity comprising a mixture of C20 to C 12 O paraffins, 50 wt% or more being isoparaff ⁇ nic hydrocarbons and less than 50 wt% being hydrocarbons that contain naphthenic and/or aromatic structures.
  • the mixture of paraffins comprises a wax isomerate lubricant basestock or oil, which includes:
  • hydroisomerized natural and refined waxes such as slack waxes, deoiled waxes, normal alpha-olefin waxes, microcrystalline waxes, and waxy stocks derived from gas oils, fuels hydrocracker bottoms, hydrocarbon raffinates, hydrocracked hydrocarbons, lubricating oils, mineral oils, polyalphaolefms, or other linear or branched hydrocarbon compounds with carbon number of about 20 or more;
  • hydroisomerized synthetic waxes such as Fischer-Tropsch waxes (i.e., the high boiling point residues of Fischer-Tropsch synthesis, including waxy hydrocarbons); or mixtures thereof.
  • Fischer-Tropsch waxes i.e., the high boiling point residues of Fischer-Tropsch synthesis, including waxy hydrocarbons
  • lubricant basestocks or oils derived from hydrocarbons synthesized in a Fischer-Tropsch process as part of an overall Gas-to-Liquids (GTL) process.
  • GTL Gas-to-Liquids
  • the mixture of paraffins has two or more of the following properties:
  • a naphthenic content of less than 40 wt% (preferably less than 30 wt%, preferably less than 20 wt%, preferably less than 15 wt%, preferably less than 10 wt%, preferably less than 5 wt%, preferably less than 2 wt%, preferably less than 1 wt%) based on the total weight of the hydrocarbon mixture; and/or
  • a normal paraffins content of less than 5 wt% (preferably less than 4 wt%, preferably less than 3 wt%, preferably less than 1 wt%) based on the total weight of the hydrocarbon mixture; and/or
  • a saturates level of 90 wt% or higher (preferably 95 wt% or higher, preferably 98 wt% or higher, preferably 99 wt% or higher); and/or 5. the percentage of carbons in chain-type paraffinic structures (Cp) of 80% or more (preferably 90% or more, preferably 95% or more, preferably 98% or more); and/or 6. a branched paraffin:normal paraffin ratio greater than about 10:1 (preferably greater than 20:1, preferably greater than 50:1, preferably greater than 100:1, preferably greater than 500:1, preferably greater than 1000:1); and/or 7. sidechains with 4 or more carbons making up less than 10% of all sidechains (preferably less than 5%, preferably less than 1%); and/or
  • sidechains with 1 or 2 carbons making up at least 50% of all sidechains (preferably at least 60%, preferably at least 70%, preferably at least 80%, preferably at least 90%, preferably at least 95%, preferably at least 98%); and/or 9. a sulfur content of 300 ppm or less (preferably 100 ppm or less, preferably 50 ppm or less, preferably 10 ppm or less) where ppm is on a weight basis; and/or
  • a nitrogen content of 300 ppm or less (preferably 100 ppm or less, preferably 50 ppm or less, preferably 10 ppm or less) where ppm is on a weight basis; and/or
  • a number-average molecular weight of 300 to 1800 g/mol (preferably 400 to 1500 g/mol, preferably 500 to 1200 g/mol, preferably 600 to 900 g/mol); and/or
  • a kinematic viscosity at 4O 0 C 10 cSt or more (preferably 25 cSt or more, preferably between about 50 and 400 cSt); and/or
  • a kinematic viscosity at 100°C ranging from 2 to 50 cSt (preferably 3 to 30 cSt, preferably 5 to 25 cSt, preferably 6 to 20 cSt, preferably 8 to 16 cSt); and/or 14.
  • a viscosity index (VI) of 80 or greater preferably 100 or greater, preferably 120 or greater, preferably 130 or greater, preferably 140 or greater, preferably 150 or greater, preferably 160 or greater, preferably 180 or greater; and/or
  • a pour point of -5°C or lower (preferably -10 0 C or lower, preferably -15°C or lower, preferably -20 0 C or lower, preferably -25°C or lower, preferably -30 0 C or lower); and/or 16.
  • a flash point of 200 0 C or more (preferably 220 0 C or more, preferably 240 0 C or more, preferably 260 0 C or more); and/or
  • the mixture of paraffins comprises a GTL basestock or oil.
  • GTL basestocks and oils are fluids of lubricating viscosity that are generally derived from waxy synthesized hydrocarbons, that are themselves derived via one or more synthesis, combination, transformation, and/or rearrangement processes from gaseous carbon-containing compounds and hydrogen-containing compounds as feedstocks, such as: hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes, and butynes.
  • the feedstock is "syngas” (synthesis gas, essentially CO and H 2 ) derived from a suitable source, such as natural gas and/or coal.
  • GTL basestocks and oils include wax isomerates, comprising, for example, hydroisomerized synthesized waxes, hydroisomerized Fischer-Tropsch (F-T) waxes (including waxy hydrocarbons and possible analogous oxygenates), or mixtures thereof.
  • GTL basestocks and oils may further comprise other hydroisomerized basestocks and base oils.
  • Particularly preferred GTL basestocks or oils are those comprising mostly hydroisomerized F-T waxes and/or other liquid hydrocarbons obtained by a F-T synthesis process.
  • the synthesis of hydrocarbons, including waxy hydrocarbons, by F-T may involve any suitable process known in the art, including those involving a slurry, a fixed-bed, or a fluidized- bed of catalyst particles in a hydrocarbon liquid.
  • the catalyst may be an amorphous catalyst, for example based on a Group VHI metal such as Fe, Ni, Co, Ru, and Re on a suitable inorganic support material, or a crystalline catalyst, for example a zeolitic catalyst.
  • the process of making a lubricant basestock or oil from a waxy stock is characterized as a hydrodewaxing process.
  • a hydrotreating step while typically not required for F-T waxes, can be performed prior to hydrodewaxing if desired. Some F-T waxes may benefit from removal of oxygenates while others may benefit from oxygenates treatment prior to hydrodewaxing.
  • the hydrodewaxing process is typically conducted over a catalyst or combination of catalysts at high temperatures and pressures in the presence of hydrogen.
  • the catalyst may be an amorphous catalyst, for example based on Co, Mo, W, etc. on a suitable oxide support material, or a crystalline catalyst, for example a zeolitic catalyst such as ZSM-23 and ZSM-48 and others disclosed in US patents 4906350, often used in conjunction with a Group VDI metal such as Pd or Pt.
  • Solvent dewaxing involves the physical fractionation of waxy components from the hydroisomerate.
  • Catalytic dewaxing converts a portion of the hydroisomerate to lower boiling hydrocarbons; it often involves a shape-selective molecular sieve, such as a zeolite or silicoaluminophosphate material, in combination with a catalytic metal component, such as Pt, in a fixed-bed, fluidized-bed, or slurry type process at high temperatures and pressures in the presence of hydrogen.
  • Desirable GTL-derived fluids are expected to become broadly available from several sources, including Chevron, ConocoPhillips, ExxonMobil, Sasol, SasolChevron, Shell, Statoil, and Syntroleum.
  • This invention also relates to plasticized polyolefm compositions comprising one or more polyolefins and one or more non-functionalized plasticizers, where one or more NFP is a high purity hydrocarbon fluid derived from a GTL process comprising a mixture of paraffins of carbon number ranging from about C2 0 to Ci 00 , a molar ratio of isoparaffinsrn-paraffms greater than about 50:1, the percentage of carbons in paraffinic structures (Cp) of 98% or more, a pour point ranging from about -20 to -6O 0 C, and a kinematic viscosity at 100 0 C ranging from about 6 to 20 cSt.
  • NFP is a high purity hydrocarbon fluid derived from a GTL process comprising a mixture of paraffins of carbon number ranging from about C2 0 to Ci 00 , a molar ratio of isoparaffinsrn-paraffms greater than about 50:1, the percentage of carbons in
  • hydroisomerized describes a catalytic process in which normal paraffins and/or slightly branched isoparaffms are converted by rearrangement into more branched isoparaffins (also known as “isodewaxing”);
  • wax is a hydrocarbonaceous material existing as a solid at or near room temperature, with a melting point of 0 0 C or above, and consisting predominantly of paraffinic molecules, most of which are normal paraffins;
  • slack wax is the wax recovered from petroleum oils such as by solvent dewaxing, and may be further hydrotreated to remove heteroatoms.
  • the NFP comprises a Group IH Mineral Oil.
  • the NFP has a saturates levels of 90% or more (preferably 92% or more, preferably 94% or more, ' preferably 95% or more, preferably 98% or more); a sulfur content of less than 0.03% (preferably between 0.001 and 0.01%); and a VI of 120 or more (preferably 130 or more, preferably 140 or more).
  • the Group HI Mineral Oil has a kinematic viscosity at 100 0 C of 3 to 50, preferably 4 to 40 cSt, preferably 6 to 30 cSt, preferably 8 to 20; and/or a number average molecular weight of 300 to 5,000 g/mol, preferably 400 to 2,000 g/mol, preferably 500 to 1,000 g/mol.
  • the Group HI Mineral Oil has a pour point of -10 0 C or less, a flash point of 200 0 C or more, and a specific gravity (15.6°C/15.6°C) of 0.86 or less.
  • the Group m Mineral Oil is a Group m basestock. Desirable Group IH basestocks are commercially available from a number of sources and include those described in the table below. The percentage of carbons in chain-type paraffinic structures (Cp) in such liquids is greater than 80%.
  • VHVI 4 5 4.6 128 -21 0.826
  • the NFP is an Exceptional Paraffinic Process Oil, which is a paraffinic process oil with
  • a pour point of -15°C or less (preferably -18°C or less, preferably -20 0 C or less, preferably -25°C or less, preferably -30 0 C or less, preferably -35°C or less).
  • paraffinic process oils are described in the tables below; each has a viscosity index less than 120, so none are Group El Mineral Oils. Furthermore, all have less than 80% carbons in paraffinic chain-like structures (Cp ⁇ 80%), meaning they also all have more than 20% carbons in aromatic and/or naphthenic ring-like structures (C A + C N )- Conventional Paraffinic Process Oils, as shown in the first table, are low viscosity and/or have relatively high pour points.
  • the Exceptional Paraffinic Process Oils in the second table are examples from a very select subcategory of paraffinic process oils that have a kinematic viscosity at 40 0 C of 80 cSt or more (indicating the potential for high permanence) and a pour point of -15°C or less (indicating the potential for high plasticization efficiency).
  • the NFP is not a naphthenic mineral oil (also called a naphthenic process oil or a naphthenic extender oil), nor is it an aromatic mineral oil (also called an aromatic process
  • naphthenic and aromatic mineral oils are substantially absent from the compositions of the present invention.
  • paraffinic mineral oils with a kinematic viscosity at 40°C of less than 80 cSt and a pour point of greater than -15°C are substantially absent from the compositions of the present invention.
  • the NFP has a kinematic viscosity at 100 0 C (KV 1 Oo) of 3 cSt or more, preferably 4 cSt or more, preferably 5 cSt or more, preferably 6 cSt or more, preferably 8 cSt or more, preferably 10 cSt or more, preferably 20 cSt or more, preferably 40 cSt or more, preferably 6 to 5000 cSt, preferably 8 to 3000 cSt, preferably 10 to 1000 cSt, preferably
  • the NFP has a pour point of -10°C or less, preferably -20 0 C or less, preferably -30 0 C or less, preferably -40 0 C or less, preferably -45°C or less, preferably -50 0 C or less, preferably -10 to -100 0 C, preferably -15 to -80 0 C, preferably -15 to -75°C, preferably -20 to -70 0 C, preferably -25 to -65°C, preferably greater than -120 0 C, wherein a desirable range may be any combination of any lower pour point limit with any upper pour point limit described herein.
  • the NFP has a pour point of less than -30 0 C when the kinematic viscosity at 40 0 C is from 20 to 600 cSt (preferably 30 to 400 cSt, preferably 40 to 300 cSt).
  • the NFP has a glass transition temperature (Tg) of -40 0 C or less, preferably -50 0 C or less, preferably -60 0 C or less, preferably -70 0 C or less, preferably -80 0 C or less, preferably -45 to -120 0 C, preferably -65 to -90 0 C, wherein a desirable range may be any combination of any lower T g limit with any upper T g limit described herein.
  • Tg glass transition temperature
  • the NFP has a Viscosity Index (VI) of 100 or more, preferably 110 or more, preferably 120 or more, preferably 130 or more, preferably 115 to 350, preferably 135 to 300, preferably 140 to 250, preferably 150 to 200, preferably 125 to 180, wherein a desirable range may be any combination of any lower VI limit with any upper VI limit described herein.
  • VI Viscosity Index
  • the NFP has a flash point of 200 0 C or greater, preferably 210° or greater, preferably 230 0 C or greater, preferably 200 to 350 0 C, preferably 210 to 300 0 C, preferably 215 to 290°C, preferably 220 to 280 0 C, preferably 240 to 280 0 C, wherein a desirable range may be any combination of any lower flash point limit with any upper flash point limit described herein.
  • the NFP has a specific gravity of 0.86 or less, preferably 0.855 or less, preferably 0.84 or less, preferably 0.78 to 0.86, preferably 0.79 to 0.855, preferably 0.80 to 0.85, preferably 0.81 to 0.845, preferably 0.82 to 0.84, wherein a desirable range may be any combination of any lower specific gravity limit with any upper specific gravity limit described herein.
  • the NFP has a number-average molecular weight (M n ) of 250 g/mol or more, preferably 300 g/mol or more, preferably 500 g/mol or more, preferably 300 to 21,000 g/mol, preferably 300 to 10,000 g/mol, preferably 400 to 5,000 g/mol, preferably 500 to 3,000 g/mol, preferably 10 kg/mol or less, preferably 5 kg/mol or less, preferably 3 kg/mol or less, preferably 2 kg/mol or less, preferably 1 kg/mol or less, wherein a desirable range may be any combination of any lower M n limit with any upper M n limit described herein.
  • M n number-average molecular weight
  • the NFP has a low degree of color, such as typically identified as “water white”, “prime white”, “standard white”, or “bright and clear,” preferably an APHA color of 100 or less (preferably 80 or less, preferably 60 or less, preferably 40 or less, preferably 20 or less).
  • any NFP may have an initial boiling point of from 300 to 600 0 C (preferably 350 to 500 0 C, preferably greater than 400 0 C).
  • the NFP for use in the present invention may be described by any embodiment described herein, or any combination of the embodiments described herein.
  • the NFP is a Cg to C 200 paraffin having a pour point of less than -25°C.
  • the NFP comprises an aliphatic hydrocarbon having a kinematic viscosity of from 0.1 to 1000 cSt at 100 0 C.
  • the NFP is selected from isoparaffins and PAOs and blends thereof having from 8 to 25 carbon atoms.
  • the NFP of the present invention comprises C25 to C 1 50 0 paraffins, and C 30 to C5 0 0 paraffins in another embodiment, and has a flash point of 200 0 C or more and a pour point of -10 0 C or less and a viscosity index of 120 or more.
  • the NFP comprises C 25 to paraffins, preferably C 30 to C 50 0 paraffins, and has a flash point of 200 0 C or more and a pour point of -2O 0 C or less.
  • the NFP comprises C 25 to C 1SO o paraffins, preferably C 30 to C 500 paraffins, and has a flash point of 200 0 C or more and a kinematic viscosity at 100 0 C of 35 cSt or more.
  • the NFP consists essentially of C 35 to C 300 paraffins, preferably the NFP consists essentially of C 40 to C 2 so paraffins, and has a flash point of 200 0 C or more and a pour point of -1O 0 C or less and a viscosity index of 120 or more.
  • the NFP consists essentially of C35 to C 3 00 paraffins, preferably C 4 o to C2 5 0 paraffins, and has a flash point of 200 0 C or more and a pour point of -20 0 C or less.
  • the NFP consists essentially of C35 to C 3 00 paraffins, preferably C4 0 to C 250 paraffins, and has a flash point of 200 0 C or more and a kinematic viscosity at 100 0 C of 35 cSt or more.
  • the NFP has a flash point of 200 0 C or more and a pour point of -20 0 C or less.
  • the NFP has a flash point of 200 0 C or more and a kinematic viscosity at 100 0 C of 35 cSt or more.
  • any NFP described herein has a flash point of 200 0 C or more (preferably 210 0 C or more) and a pour point of -20 0 C or less (preferably -25°C or less, preferably -30 0 C or less, preferably -35°C or less, preferably -45°C or less, preferably -50 0 C or less).
  • the NFP has a flash point of 220 0 C or more (preferably 23O 0 C or more) and a pour point of -10 0 C or less (preferably -25°C or less, preferably -3O 0 C or less, preferably -35°C or less, preferably -45°C or less, preferably -50°C or less).
  • the NFP has a kinematic viscosity at 100 0 C of 35 cSt or more (preferably 40 cSt or more, preferably 50 cSt or more, preferably 60 cSt or more) and.
  • the NFP has a) a flash point of 200 0 C or more; b) a specific gravity of 0.86 or less; and cl) a pour point of -1O 0 C or less and a viscosity index of 120 or more, or c2) a pour point of -20 0 C or less, or c3) a kinematic viscosity at 100 0 C of 35 cSt or more.
  • the NFP has a) a specific gravity (15.6/15.6°C) of 0.85 or less (preferably between 0.80 and 0.85); and bl) a kinematic viscosity at 100 0 C of 3 cSt or more (preferably 4 or more, preferably 5 cSt or more, preferably 8 cSt or more, preferably 10 cSt or more, preferably 15 cSt or more, preferably 20 cSt or more) and/or b2) a number-average molecular weight (M n ) of at least 280 g/mol.
  • M n number-average molecular weight
  • the NFP has a) a specific gravity (15.6/15.6°C) of 0.86 or less (preferably between 0.81 and 0.855, preferably between 0.82 and 0.85); and bl) a kinematic viscosity at 100 0 C of 5 cSt or more (preferably 6 or more, preferably 8 cSt or more, preferably 10 cSt or more, preferably 12 cSt or more, preferably 15 cSt or more, preferably 20 cSt or more) and/or b2) a number-average molecular weight (M n ) of at least 420 g/mol (preferably at least 450 g/mol, preferably at least 480 g/mol, preferably at least 500 g/mol).
  • M n number-average molecular weight
  • the NFP has a) a specific gravity (15.6/15.6°C) of 0.87 or less (preferably between 0.82 and 0.87); and bl) a kinematic viscosity at 100 0 C of 10 cSt or more (preferably 12 cSt or more, preferably 15 cSt or more, preferably 20 cSt or more, preferably 30 cSt or more, preferably 40 cSt or more) and/or b2) a number-average molecular weight (M n ) of at least 700 g/mol (preferably at least 800 g/mol, preferably at least 900 g/mol, preferably at least 1000 g/mol).
  • M n number-average molecular weight
  • the NFP has a) a specific gravity (15.6/15.6°C) of 0.88 or less (preferably 0.87 or less, preferably between 0.82 and 0.87); and bl) a kinematic viscosity at 100 0 C of 15 cSt or more (preferably 20 cSt or more, preferably 25 cSt or more, preferably 30 cSt or more, preferably 40 cSt or more) and/or b2) a number-average molecular weight (M n ) of at least 840 g/mol (preferably at least 900 g/mol).
  • M n number-average molecular weight
  • the NFP has a kinematic viscosity at 100 0 C of 3 to 3000 cSt (preferably 6 to 300 cSt. preferably 8 to 100 cSt); and a number average molecular weight (M n ) of 300 to 21,000 g/mol (preferably 500 to 5,000 g/mol, preferably 600 to 3,000 g/mol).
  • the NFP has a kinematic viscosity at 100 0 C of 3 to 500 cSt (preferably 6 to 200 cSt, preferably 8 to 100 cSt, preferably 8 to 25 cSt); and a number average molecular weight (M n ) of 300 to 10,000 g/mol (preferably 400 to 5,000 g/mol, preferably 500 to 2,500 g/mol, preferably 300 to 1,200 g/mol).
  • Li another preferred embodiment the NFP has a kinematic viscosity at 100°C of 3 to 100 cSt (preferably 4 to 50 cSt, preferably 6 to 25 cSt, preferably 6 to 15 cSt); and a number average molecular weight (M n ) of 300 to 3,000 g/mol (preferably 350 to 2,000 g/mol, preferably 400 to 1,000 g/mol, preferably 300 to 800 g/mol).
  • the NFP has a pour point of -25°C or less (preferably between -30 0 C and -90 0 C), and a kinematic viscosity in the range of from 20 to 5000 cSt at 40 0 C.
  • the NFP has a pour point of -25°C or less and a Mn of 400 g/mol or greater.
  • Most mineral oils, which typically include functional groups, have a pour point of from 10 0 C to -25°C at the same viscosity and molecular weight ranges.
  • the NFP has kinematic viscosity at 100 0 C of 3 cSt or greater (preferably 6 cSt or greater, preferably 8 cSt or greater) and one or more of the following properties:
  • a pour point of -10 0 C or less (preferably -20°C or less, preferably -30 0 C or less, preferably -40 0 C or less); and/or,
  • a low degree of color such as typically identified as “water white”, “prime white”, “standard white”, or “bright and clear,” preferably an APHA color of 100 or less, preferably 80 or less, preferably 60 or less, preferably 40 or less, preferably 20 or less (preferably 15 or less); and/or 4. a flash point of 200 0 C or more (preferably 220 0 C or more, preferably 240 0 C or more); and/or
  • the NFP has a Viscosity Index of 120 or more and one or more of the following properties:
  • a pour point of -10 0 C or less (preferably -20 0 C or less, preferably -30 0 C or less, preferably -40 0 C or less); and/or,
  • a kinematic viscosity at 100 0 C of 3 cSt or greater preferably 6 cSt or greater, preferably 8 cSt or greater, preferably 10 cSt or greater
  • a low degree of color such as typically identified as “water white”, “prime white”, “standard white”, or “bright and clear,” preferably an APHA color of 100 or less (preferably 80 or less, preferably 60 or less, preferably 40 or less, preferably 20 or less, preferably 15 or less); and/or
  • a flash point of 200 0 C or more (preferably 220 0 C or more, preferably 240 0 C or more);
  • the NFP has a pour point of -20 0 C or less, preferably -30 0 C or less, and one or more of the following properties:
  • a kinematic viscosity at 100 0 C of 3 cSt or greater (preferably 6 cSt or greater, preferably 8 cSt or greater, preferably 10 cSt or more); and/or,
  • Viscosity Index 120 or greater (preferably 130 or greater); and/or,
  • a low degree of color such as typically identified as “water white”, “prime white”, “standard white”, or “bright and clear,” preferably APHA color of 100 or less (preferably 80 or less, preferably 60 or less, preferably 40 or less, preferably 20 or less, preferably 15 or less); and/or 4. a flash point of 200 0 C or more (preferably 220 0 C or more, preferably 240 0 C or more); and/or
  • Most mineral oils have a kinematic viscosity at 100 0 C of less than 6 cSt, or an APHA color of greater than 20, or a flash point less than 200 0 C when their pour point is less than -20 0 C.
  • the NFP has a glass transition temperature (Tg) that cannot be determined by ASTM E 1356 or, if it can be determined, then the T g according to
  • ASTM E 1356 is less than -20 0 C (preferably less than -30 0 C, preferably less than -40 0 C), and has one or more of the following properties:
  • a pour point of -10 0 C or less (preferably -15°C or less, preferably -25°C or less, preferably
  • M w weight average molecular weight
  • M n a number average molecular weight between 10,000 and 400 g/mol (preferably between 5,000 and 500 g/mol, preferably between 2,000 and 600 g/mol); and/or
  • a final boiling point of from 300 0 C to 800 0 C (preferably from 400 0 C to 700 0 C, preferably greater than 500 0 C).
  • the NFP has a specific gravity of 0.86 or less (preferably 0.855 or less, preferably 0.85 or less), and one or more of the following: a) a VI of 120 or more (preferably 135 or more, preferably 140 or more), and/or b) a flash point of 200 0 C or more (preferably 220 0 C or more, preferably 240 0 C or more).
  • the NFP has a pour point of -10 0 C or less (preferably -15°C or less, preferably -20°C or less, preferably -25 0 C or less), a VI of 120 or more (preferably 135 or more, preferably 140 or more), and optionally a flash point of 200 0 C or more (preferably 220 0 C or more, preferably 240 0 C or more).
  • the NFP has a pour point of -20 0 C or less (preferably -25°C or less, preferably -30 0 C or less, preferably -40 0 C or less) and one or more of the following: a) a flash point of 200 0 C or more (preferably 220 0 C or more, preferably 240 0 C or more), and/or b) a VI of 120 or more (preferably 135 or more, preferably 140 or more), and/or c) a KVlOO of 4 cSt or more (preferably 6 cSt or more, preferably 8 cSt or more, preferably 10 cSt or more), and/or d) a specific gravity of 0.86 or less (preferably 0.855 or less, preferably 0.85 or less).
  • the NFP has a KVlOO of 4 cSt or more (preferably 5 cSt or more, preferably 6 cSt or more, preferably 8 cSt or more, preferably 10 cSt or more), a specific gravity of 0.86 or less (preferably 0.855 or less, preferably 0.85 cSt or less), and a flash point of 200 0 C or more (preferably 220 0 C or more, preferably 240 0 C or more).
  • the NFP has a flash point of 200 0 C or more (preferably 220 0 C or more, preferably 240 0 C or more), a pour point of -10 0 C or less (preferably -15°C or less, preferably -20 0 C or less, preferably -25°C or less), a specific gravity of 0.86 or less (preferably 0.855 or less, preferably 0.85 or less), a KVlOO of 4 cSt or more (preferably 5 cSt or more, preferably 6 cSt or more, preferably 8 cSt or more, preferably 10 cSt or more), and optionally a VI of 100 or more (preferably 120 or more, preferably 135 or more).
  • the NFP has a KVlOO of 35 cSt or more (preferably 40 or more) and a specific gravity of 0.86 or less (preferably 0.855 or less), and optionally one or more of the following: a) a flash point of 200 0 C or more (preferably 220 0 C or more, preferably 240 0 C or more), and/or b) a pour point of -10 0 C or less (preferably -15°C or less, preferably -20 0 C or less, preferably -25°C or less).
  • the NFP has a flash point of 200 0 C or more (preferably 210 0 C or more, preferably 220 0 C or more), a pour point of -10 0 C or less (preferably -20 0 C or less, preferably -30 0 C or less), and a KVlOO of 6 cSt or more (preferably 8 cSt or more, preferably 10 cSt or more, preferably 15 cSt or more).
  • the NFP has a pour point of -40 0 C or less (preferably -50 0 C or less) and a specific gravity of 0.84 or less (preferably 0.83 or less).
  • the percentage of carbons in chain-type paraffins (Cp) for any NFP is at least 80% (preferably at least 85%, preferably at least 90%, even preferably at least 95%, even preferably at least 98%, most preferably at least 99%).
  • Preferred NFPs of this invention are characterized in that, when blended with the polyolefin(s) to form a plasticized composition, the NFP is miscible with the polyolefin(s) as indicated by no change in the number of tan-delta peaks in the Dynamic Mechanical Analysis trace (DMA Tan-Delta vs temperature) as compared to the same composition without the NFP added. Lack of miscibility is indicated by an increase in the number of tan-delta peaks in DMA trace over those in the composition absent the NFP.
  • DMA Tan-Delta vs temperature Dynamic Mechanical Analysis trace
  • the hetero-phase polyolefm compositions of the present invention include at least one filler.
  • the classes of materials described herein that are useful as fillers can be utilized alone or admixed to obtain desired properties.
  • filler may be present at 0.1 to 50 wt% (preferably 1 to 40 wt%, preferably 2 to 30 wt%, preferably 5 to 20 wt%) based on the weight of the total composition. Filler content is equated with the wt% ash content as determined by the ISO 3451-1 (A) test method.
  • Desirable fillers include but not limited to: mineral aggregates (natural or synthetic), fibers, carbon black, graphite, wollastonite, natural and synthetic clays including nanoclays and organoclays, sand, glass beads, and the like, and any other porous or nonporous fillers and supports known in the art.
  • the filler has a median particle diameter of 0.1-100 microns (preferably 0.5-50 microns, preferably 1 to 20 microns).
  • the filler has a filler shape that is needle-like or plate-like, with an aspect ratio greater than 1.2 (preferably greater than 2, preferably greater than 3, preferably greater than 5, preferably greater than 10, preferably from 2 to 20, preferably from 3-10), where the aspect ratio is the ratio of the longest dimension to the shortest dimension of the particles, on average, and is typically reported by filler manufacturers.
  • the filler has an aspect ratio of essentially 1 (0.9 to 1.1); i.e., it is not needle-like or plate-like but is essentially spherical.
  • the filler is pulverized.
  • Useful fillers have a specific surface area of 10 to 300 m 2 /cm 3 .
  • the NFP or some portion of the NFP is blended with a filler, desirably a porous filler.
  • the NFP and filler may be blended by, for example, a tumbler or other wet blending apparatus, for a time suitable to form a homogenous composition of NFP and filler, desirably from 1 minute to 5 hours.
  • a filler may be pre-contacted or pre-absorbed with the NFP or some portion of the NFP prior to contacting the filler with the pqlyolefin.
  • the filler, polyolefm, and NFP are contacted simultaneously (or in the same blending apparatus).
  • Preferred natural or synthetic mineral fillers include talc, mica, wollastonite, titanium dioxide, silicon carbide, silica, silicon dioxide and other oxides of silica (precipitated or not), calcium silicate, calcium and barium sulfates, calcium carbonate (calcite), lead carbonate, magnesium silicate, magnesium oxysulfates, antimony oxide, zinc white, lithopone, zircon, corundum, spinel, apatite, Barytes powder, magnesiter, dolomite, zinc borate, hydrotalcite compounds of the ions Mg, Ca, or Zn with Al, Cr or Fe and CO 3 and/or HPO 4 (hydrated or not), quartz powder, hydrochloric magnesium carbonate, alumina, chrome, phosphorous and brominated flame retardants, antimony trioxide, silicone, other metal oxides, other metal carbonates, other metal hydroxides, and blends thereof.
  • Fibers include glass fibers (long or short), carbon fibers, and
  • Preferred clays include nanoclays or organoclays to produce a nanocomposite. These clays may comprise one or more of ammonium, primary alkylammonium, secondary alkylammonium, tertiary alkylammonium, quaternary alkylammonium, phosphonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines or sulfides or sulfonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines or sulfides.
  • the organoclay may be selected from one or more of montmorillonite, sodium montmorillonite, calcium montmorillonite, magnesium montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, sobockite, svindordite, stevensite, vermiculite, halloysite, aluminate oxides, hydrotalcite, illite, rectorite, tarosovite, ledikite, and/or florine mica.
  • the filler is a nano-clay with mean particle diameter of less than 1 micron.
  • Additives such as antioxidants and stabilizers (including UV stabilizers and other UV absorbers, such as chain-breaking antioxidants), nucleating agents, slip agents, block, antiblock, pigments, dyes, color masterbatches, waxes, processing aids (including pine or coal tars or resins and asphalts), neutralizers (such as hydro talcite), adjuvants, oils, lubricants, low molecular weight resins, surfactants, acid scavengers, anticorrosion agents, cavitating agents, blowing agents, quenchers, antistatic agents, cure or cross linking agents or systems (such as elemental sulfur, organo-sulfur compounds, and organic peroxides), fire retardants, coupling agents (such as silane).
  • additives used in polypropylene and polypropylene blends are described in POLYPROPYLENE HANDBOOK 2 ND ED., N. Pasquini, ed. (Hanser Publishers, 2005).
  • the additives may be present in the typically effective amounts well known in the art, preferably at 0.001 to 50 wt% (preferably 0.01 to 20 wt%, preferably 0.1 to 10 wt%, preferably 0.1 to 1 wt%), based upon the weight of the composition.
  • Pigments, dyes, and other colorants may be present from 0.01 to 10 wt% (preferably 0.1 to 6 wt%).
  • Antioxidants and stabilizers include organic phosphites, hindered amines (including high and low molecular weight hindered amine light stabilizers, or "HALS”), and phenolic antioxidants may be present in the thermoplastic polyolefin compositions of the invention from 0.001 to 2 wt% (preferably from 0.01 to 0.8 wt%, preferably from 0.02 to 0.5 wt%).
  • HALS high and low molecular weight hindered amine light stabilizers
  • phenolic antioxidants may be present in the thermoplastic polyolefin compositions of the invention from 0.001 to 2 wt% (preferably from 0.01 to 0.8 wt%, preferably from 0.02 to 0.5 wt%).
  • Non-limiting examples of organic phosphites that are suitable are tris(2,4-di-tert- butylphenyl)phosphite (IRGAFOS 168) and di(2,4-di-tert-butylphenyl)pentaerithritol diphosphite (ULTRANOX 626).
  • Non-limiting examples of hindered amines include poly[2-N,N'-di(2,2,6,6- teframethyl-4-piperidinyl)-hexanediamine-4-(l-amino-l,l,3,3-tetramethylbutane)sym-triazine] (CHJMASORB 944); bis(l,2,2,6,6-pentamethyl-4-piperidyl)sebacate (TINUVIN 770).
  • Non- limiting examples of phenolic antioxidants include pentaerythrityl tetrakis(3,5-di-tert-butyl-4- hydroxyphenyl) propionate (IRGANOX 1010); and l,3,5-Tri(3,5-di-tert-butyl-4-hydroxybenzyl- isocyanurate (IRGANOX 3114).
  • Preferred antioxidants include phenolic antioxidants, such as Lrganox 1010, Irganox, 1076 both available from Ciba-Geigy.
  • the polymer concentrate may comprise one or more phenolic antioxidants.
  • Slip Agent
  • the polyolefin compositions of the present invention may include a slip agent.
  • the slip agent is preferably a fast bloom slip agent, and can be a hydrocarbon having one or more functional groups selected from hydroxide, aryls and substituted aryls, halogens, alkoxys, carboxylates, esters, carbon unsaturation, acrylates, oxygen, nitrogen, carboxyl, sulfate and phosphate.
  • the slip agent is an ionic compound.
  • Ionic slip agents include salt derivatives of aromatic or aliphatic hydrocarbon oils, notably metal salts of fatty acids, including metal salts of carboxylic, sulfuric, and phosphoric aliphatic saturated or unsaturated acid having a chain length of 7 to 26 carbon atoms, preferably 10 to 22 carbon atoms.
  • Suitable fatty acids include the monocarboxylic acids lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, erucic acid, and the like, and the corresponding sulfuric and phosphoric acids.
  • Suitable metals include Li, Na, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb and so forth.
  • Suitable salts include magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate, zinc oleate, magnesium oleate, and so on, as well as the corresponding metal higher alkyl sulfates and metal esters of higher alkyl phosphoric acids.
  • fatty acid metal salts are substantially absent from the polyolefm compositions of the present invention.
  • the slip agent is a non-ionic fiinctionalized compound. Suitable functionalized compounds include: (a) esters, amides, alcohols and acids of oils including aromatic or aliphatic hydrocarbon oils, for example, mineral oils, naphthenic oils, paraffinic oils; natural oils such as castor, corn, cottonseed, olive, rapeseed, soybean, sunflower, other vegetable and animal oils, and so on.
  • oils include, for example, polyol esters of monocarboxylic acids such as glycerol monostearate, pentaerythritol monooleate, and the like, saturated and unsaturated fatty acid amides or ethylenebis(amides), such as oleamide, erucamide, linoleamide, and mixtures thereof, glycols, polyether polyols like Carbowax, and adipic acid, sebacic acid, and the like; (b) waxes, such as carnauba wax, microcrystalline wax, polyolefin waxes, e.g.
  • polyethylene waxes such as polyethylene waxes; (c) fluoro-containing polymers such as polytetrafluoroethylene, fluorine oils, fluorine waxes and so forth; and (d) silicon compounds such as silanes and silicone polymers, including silicone oils, polydimethylsiloxane, amino-modified polydimethylsiloxane, and so on.
  • the fatty amides useful in the present invention are represented by the formula: R 1 C(O)NHR 2 where R 1 is a saturated or unsaturated alkyl group having of from 7 to 26 carbon atoms, preferably 10 to 22 carbon atoms, and R 2 is independently hydrogen or a saturated or unsaturated alkyl group having from 7 to 26 carbon atoms, preferably 10 to 22 carbon atoms.
  • R 1 is a saturated or unsaturated alkyl group having of from 7 to 26 carbon atoms, preferably 10 to 22 carbon atoms
  • R 2 is independently hydrogen or a saturated or unsaturated alkyl group having from 7 to 26 carbon atoms, preferably 10 to 22 carbon atoms.
  • Compounds according to this structure include for example, palmitamide, stearamide, arachidamide, behenamide, oleamide, erucamide, linoleamide, stearyl stearamide, palmityl palmitamide, stearyl arachidamide and mixtures thereof.
  • ethylenebis(amides) useful in the present invention are represented by the formula: RC(O)NHCH 2 CH 2 NHC(O)R where each R is independently is a saturated or unsaturated alkyl group having of from 7 to 26 carbon atoms, preferably 10 to 22 carbon atoms.
  • Compounds according to this structure include for example, stearamidoethylstearamide, stearamidoethylpalmitamide, pahnitamido-ethylstearamide, ethylenebisstearamide, ethylenebisoleamide, stearylerucamide, erucamidoethylerucamide, oleamidoethyloleamide, erucamidoethyloleamide, oleamidoethylerucamide, stearamidoethylerucamide, erucamidoethylpalmitamide, palmitamidoethyloleamide and mixtures thereof.
  • fatty amides include Ampacet 10061 which comprises 5% of a 50:50 mixture of the primary amides of erucic and stearic acids in polyethylene; Elvax 3170 which comprises a similar blend of the amides of erucic and stearic acids in a blend of 18% vinyl acetate resin and 82% polyethylene. These slip agents are available from DuPont.
  • Slip agents also are available from Croda Universal, including Crodamide OR (an oleamide), Crodamide SR (a stearamide), Crodamide ER (an erucamide), and Crodamide BR (a behenamide); and from Crompton, including Kemamide S (a stearamide), Kemamide B (a behenamide), Kemamide O (an oleamide), Kemamide E (an erucamide), and Kemamide (an N.N'-ethylenebisstearamide).
  • Other commercially available slip agents include Erucamid ER erucamide.
  • concentrations of the slip agent are in the range of from about 0.001% to about 0.5% by weight of the composition, preferably of from about 0.01% to about 0.4% by weight and most preferably of from about 0.1 parts to about 0.3% by weight based on the weight of the composition.
  • the polyolefin composition described herein may also include the addition of at least one nucleating agent.
  • nucleating agents increase the rate of crystallization (isothermal and/or non-isothermal) of the polyolefin.
  • clarifying agents typically reduces the size of crystallites, thereby improving the transparency and clarity of articles made from the polyolefin.
  • Suitable nucleating agents for use herein are disclosed in Plastics Additive Handbook, 5 th Ed.; H. Zweifel, Ed.; Hanser-Gardner Publications, (2001); Chapter 18, p. 949-972. Suitable nucleating agents for use herein are also disclosed by H.N. Beck in Heterogeneous Nucleating Agents for Polypropylene Crystallization, J. APPLIED POLY. SCI. Vol. 11, p. 673-685 (1967) and in Heterogeneous Nucleation Studies on Polypropylene, J. POLY. SCI.: POLY. LETTERS, Vol. 21, p. 347-351 (1983).
  • Useful nucleating agents can be either homogeneous nucleating agents (i.e., melt-soluble, meaning dissolved into the polyolefin) and heterogeneous nucleating agents (i.e., melt-insoluble, meaning suspended or dispersed in the polyolefin).
  • Typical nucleating agents promote at least one crystal polymorph for the polyolefin.
  • known crystal forms include the so-called alpha, beta, and gamma polymorphs; useful nucleating agents therefore include those that promote alpha crystals in iPP, those that promote beta crystals in iPP, and those that promote gamma crystals in iPP.
  • Suitable nucleating agents also include those that promote crystallization in syndiotactic polypropylene (sPP).
  • Suitable nucleating agents preferably improve one or more performance parameters of the polyolefin, such as increased clarity, reduced haze, increased stiffness, increased impact toughness, increased heat deflection temperature; and/or processing parameters, such as reduced cycle time or increased line speed.
  • Suitable nucleating agents can be organic, inorganic, or polymeric, and may include combinations of one or more nucleating agent.
  • the appearance and mechanical properties of the compositions of the present invention can be controlled to some extent by the type of nucleating agent used.
  • the nucleating agent(s) are typically present in the composition of this invention at 0.01 to 1 wt% (100 to 10,000 ppm), preferably 0.02 to 0.5 wt% (200 to 5,000 ppm), preferably 0.03 to 0.3 wt% (300 to 3,000 ppm), preferably 0.05 to 0.25 wt% (500 to 2,500 ppm), based upon the weight of the composition (where ppm is parts-per-million by weight).
  • the polyolefin composition may further comprise a crosslinking agent.
  • crosslinking agents include those having functional groups that can react with functional groups present on the polyolefin, including alcohols, multiols, amines, diamines and/or triamines.
  • Particular examples of crosslinking agents useful in this invention include polyamines such as ethylene-diamine, diethylene-triamine, hexamethylene-diamme, diethylaniinopropyl-amine, and menthane-diamine.
  • conventional mineral oils may be present in the composition of this invention, such as paraff ⁇ nic or naphthenic mineral oils, white oils, technical white oils, bright stocks, Group I or Group II basestocks, vegetable oils, or the like.
  • functionalized oils other than amide slip agents are substantially absent from the polyolefin composition.
  • naphthenic and aromatic mineral oils are substantially absent from the compositions of the present invention, preferably present at 0 wt%.
  • aromatic moieties and carbon-carbon unsaturation are substantially absent from the non-functionalized plasticizers used in the present invention.
  • Aromatic moieties include a compound whose molecules have the ring structure characteristic of benzene, naphthalene, phenanthrene, anthracene, etc.
  • tackif ⁇ ers may be blended with the polyolefin composition of this invention.
  • useful tackifiers include, but are not limited to, aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpens phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, and hydrogenated rosin esters.
  • the tackif ⁇ er is hydrogenated. In other embodiments the tackif ⁇ er is non-polar. (Non-polar meaning that the polar groups are substantially absent from the tackif ⁇ er, or preferably polar groups are not present.) In some embodiments the tackifier has a softening point (Ring and Ball, ASTM E 28) of 80 to 140 0 C, preferably 100 to 130 0 C.
  • Tackifiers are typically present at about 1 to about 50 wt% (preferably 2 to 40 wt%, preferably 5 to 20 wt%), based upon the weight of the composition. Preferably however, tackifier is not present, or is present at less than 10 wt% (preferably less than 5 wt%, preferably at less than 1 wt%).
  • plasticizers such as are commonly used for poly(vinyl chloride) are substantially absent, preferably present at 0 wt%.
  • plasticizers such as phthalates, adipates, trimellitate esters, polyesters, and other functionalized plasticizers as disclosed in, for example, US 3,318,835; US 4,409,345; WO 02/31044 Al; and PLAS ⁇ CS ADDITIVES 499-504 (Geoffrey Pritchard, ed., Chapman & Hall 1998) are substantially absent.
  • Preferred waxes suitable for use in the compositions of this invention include: polar waxes, non-polar waxes, Fischer-Tropsch waxes, oxidized Fischer-Tropsch waxes, hydroxystearamide waxes, functionalized waxes, polypropylene waxes, polyethylene waxes, wax modifiers, amorphous waxes, carnauba waxes, castor oil waxes, microcrystalline waxes, beeswax, carnauba wax, castor wax, spermaceti wax, vegetable wax, candelilla wax, japan wax, ouricury wax, douglas-fir bark wax, rice-bran wax, jojoba wax, bayberry wax, montan wax, peat wax, ozokerite wax, ear wax, ceresin wax, petroleum wax, paraffin wax, polyethylene wax, chemically modified hydrocarbon wax, substituted amide wax, and combinations and derivatives thereof.
  • the polar and non-polar waxes may
  • the polyolefin composition of this invention may be blended with up to 25 wt% (preferably up to 20 wt%, preferably up to 15 wt%, preferably up to 10 wt%, preferably up to 5 wt%), based upon the weight of the composition, of one or more additional polymeric additives.
  • Suitable polymers include: PMl) Polyethylenes, including (but not limited to):
  • Copolymers of ethylene and one or more polar monomers preferably selected from vinyl acetate, methyl acrylate, n-butyl acrylate, acrylic acid, and vinyl alcohol (i.e., EVA, EMA, EnBA, EAA, and EVOH); ethylene homopolymers and copolymers synthesized using a high- pressure free radical process, including LDPE; copolymers of ethylene and C 3 to C 4 o olefins
  • Non-EP Rubber Elastomers including (but not limited to): Polyisobutylene, butyl rubber, halobutyl rubber, copolymers of isobutylene and para- alkylstyrene, halogenated copolymers of isobutylene and para-alkylstyrene, natural rubber, polyisoprene, copolymers of butadiene with acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber, acrylonitrile chlorinated isoprene rubber, and polybutadiene rubber (both cis and trans).
  • Low-crystallinity propylene/olefin copolymers preferably random copolymers, comprising i) at least 70 wt% propylene, and ii) 5 to 30 wt% (preferably 5 to 20 wt%) of comonomer selected from ethylene and C 4 to C 12 olefins (preferably selected from ethylene, butene, and hexene; preferably ethylene); preferably made using a metallocene-type catalyst; and having one or more of the following properties: a) M w of 20 to 5,000 kg/mol (preferably 30 to 2,000 kg/mol, preferably 40 to 1,000 kg/mol, preferably 50 to 500 kg/mol, preferably 60 to 400 kg/mol); and/or b) molecular weight distribution index (M w /M n ) of 1.5 to 10 (preferably 1.7 to 5, preferably 1.8 to 3); and/or c) branching index (g*) of 0.9 or greater (preferably 0.95 or greater, preferably 0.
  • Useful low-crystallinity propylene/olefin copolymers are available from ExxonMobil Chemical; suitable examples include VistamaxxTM 6100, VistamaxxTM 6200 and
  • Olefin block copolymers including those described in WO 2005/090425, WO 2005/090426, and WO 2005/090427.
  • maleated polyolefins Polyolefins that have been post-reactor functionalized with maleic anhydride (so-called maleated polyolefins), including maleated ethylene polymers, maleated EP Rubbers, and maleated propylene polymers.
  • the amount of free acid groups present in the maleated polyolefin is less than about 1000 ppm (preferably less than about 500 ppm, preferably less than about 100 ppm), and the amount of phosphite present in the maleated polyolefin is less than 100 ppm.
  • SBCs Styrenic Block Copolymers
  • compositions of this invention comprise no added polymeric additives, or if they are present the polymeric additives are present at 0.5 wt% or less.
  • compositions of this invention comprise less than 10 wt% LLDPE having a density of 0.912 to 0.935 (preferably less than 5 wt%, preferably less than 1 wt%, preferably 0 wt%), based upon the weight of the composition.
  • polyolefm(s), NFP(s), filler(s), and optional additives components of the polyolefin composition of the present invention can be combined using any suitable means known in the polymer processing art. Those skilled in the art will be able to determine the appropriate procedure to balance the need for intimate mixing with the desire for process economy.
  • one or more polyolefin component can be in the form of pellets or reactor granules, which are combined with the NFP(s), filler(s), and optional additives by simple physical blending of constituent pellets and/or granules, since the forming of articles includes a (re)melting and mixing of the raw material(s).
  • a pelletized melt blend would be preferred over simple physical blends of the constituent pellets and/or granules.
  • the constituents are melt blended first, to provide a compounded product.
  • the polyolefin components may be in any physical form when blended with the NFP(s), filler(s), and optional additives.
  • they may be in the form of reactor granules (i.e., granules of polymer that are isolated from the polymerization reactor prior to any processing procedures), which typically have an average diameter of 50 ⁇ m to 5 mm, or in the form of pellets that are formed from melt extrusion of the reactor granules, which typically have an average diameter of from 1 to 10 mm.
  • the polyoiefin(s), NFP(s), filler(s), and optional additives can be blended by any suitable means.
  • they may be blended in a tumbler, static mixer, batch mixer, extruder, or a combination thereof that is sufficient to achieve an adequate dispersion of the components.
  • the components may be blended by any suitable means to form the polyolefin composition of the present invention, which is then suitable for further processing into useful articles.
  • the composition is prepared by combining the components in a melt- blending (compounding) step and subsequently pelletizing the blend, using either an underwater pelletizer or a strand-cut approach (i.e., a water batch and dry pelletizer); these pellets are then used in a process to fabricate articles.
  • This approach may involve an on-line “finishing" extruder associated with a polymerization unit, or it may involve an off-line “compounding" extruder dedicated to melt blending.
  • the composition may be prepared by combining the components during a process used to fabricate articles, without first making a pelletized version of the composition; here, NFP is added to other components in a production extruder, such as the extruder on an injection molding machine or on a continuous extrusion line, and thereafter directly processed into a film, sheet, fiber, profile, etc. In either case, production rates may be between 5 and 3000 kg/hr.
  • the blending may involve "dry blending" wherein the polyolefin(s) are combined with the NFP(s) without melting. For example, one method is to contact the components in a tumbler or bowl mixer, such as a high-speed Henschel mixer.
  • the polyolefin(s) are preferably in the form of reactor granules (this works particularly well with ICPs and propylene polymers), but dry blending can also involve pellets. The dry blending step can then be followed, if desired, by melt blending in an extruder.
  • Another method of blending the components is to melt blend the polyolefin(s), either in pellet or granule form, with the NFP(s) and optionally with the filler(s) and/or additives in a batch mixer, such as a Banbury mixer.
  • Another method of blending the components is to melt blend the polyolefin(s), either in pellet or granule form, with the NFP(s) and optionally the filler(s) and/or additives in an extruder, such as a single-screw extruder or a twin-screw extruder.
  • Extrusion technology for polyolefins and polyolefin blends is well known in the art, and is described in more detail in, for example, PLASTICS EXTRUSION TECHNOLOGY, F. Hensen, Ed. (Hanser, 1988), p. 26-37 and in POLYPROPYLENE HANDBOOK, E. P. Moore, Jr. Ed., (Hanser, 1996), p. 304-348.
  • Extruder melt mixing is a preferred method of blending when a high NFP loading is desired, or when large quantities of the polyolefin composition are desired.
  • Typical extruder characteristics associated with blending NFP into polyolefin(s) include: an operating temperature profile within the range of 120 to 280 0 C (usually 160 to 240 0 C); a melt temperature at least 10-50 0 C above T m of the polyolefin having the highest T n , (usually 140 to 220 0 C); an operating speed of 50 to 1200 rpm; and a specific energy input of 0.01 to 100 kWh/kg.
  • the extruder may be set up with or without screen pack(s) for filtration, and with or without a melt gear pump.
  • NFP may be directly injected into the polymer melt using a liquid injection device at some point along the barrel, as in the case of a twin-screw extruder, or through an opening in a hollow screw shaft, as in the case of a single-screw extruder.
  • NFP is preferably added downstream from the polymer melt zone, but alternatively the NFP can be added at a point where the polymer(s) have not fully melted yet.
  • NFP can be injected after the first barrel section (preferably after the first third of the barrel, more preferably in the last third of the barrel).
  • NFP is added downstream of filler addition.
  • An NFP addition point may be on top of conveying elements of screw, or on top of liquid mixing elements of screw, or prior to kneading elements of screw, or prior to liquid mixing elements of the screw.
  • the extruder may have more than one (preferably two or three) NFP addition points along the barrel or screw shaft.
  • the NFP can be added via the extruder fed throat.
  • Addition of NFP is preferably by controlled metering; e.g., using a loss-in-weight feeder or a calibrated flow-rate meter.
  • the extruder is a twin-screw extruder with a length to diameter ratio, L/D, of 20-80 (preferably 30-60, preferably 25-50, preferably 35-45) and/or a screw diameter of 20 to 200 mm.
  • the screw design contains liquid mixing elements (gear-type elements) that create high surface renewal of the polymer, which promotes homogenization at high fluid concentrations.
  • extruders are know in the art and are manufactured by Coperion Werner- Pfleiderer, Berstorff, Leistriz, and others.
  • the components may also be blended by a combination of methods, such as dry blending followed by melt blending in an extruder, or batch mixing of some components followed by melt blending with other components in an extruder.
  • One or more components may also be blended using a double-cone blender, ribbon blender, or other suitable blender, or in a Farrel Continuous Mixer (FCM).
  • FCM Farrel Continuous Mixer
  • Blending may also involve a "masterbatch" approach, where the target NFP concentration is achieved by combining neat polyolefin(s) and optionally filler and/or additives with an appropriate amount of ⁇ re-blended masterbatch (i.e. a blend of polymer, NFP, and optionally filler and additives that has been previously prepared at a higher concentration of NFP than desired in the final blend).
  • ⁇ re-blended masterbatch i.e. a blend of polymer, NFP, and optionally filler and additives that has been previously prepared at a higher concentration of NFP than desired in the final blend.
  • Dispersion (or "letdown") of the masterbatch may take place as part of a processing step used to fabricate articles, such as in the extruder on an injection molding machine or on a continuous extrusion line, or during a separate compounding step.
  • the components may be blended in solution by any suitable means to form the polyolefin composition, by using one or more solvents that dissolve the polyolef ⁇ n and NFP components to a significant extent.
  • the blending may occur at any temperature or pressure where the NFP and the polyolefin remain in solution. Preferred conditions include blending at high temperatures, such as 20 0 C or more above the melting point of the polymer. For example, iPP would typically be solution blended with the NFP at a temperature of 200°C or more.
  • Such solution blending would be particularly useful in processes where the polymer is made by a solution process and the NFP is added directly to the finishing train, rather than added to the dry polymer in another blending step altogether. It would also be particularly useful in processes where the polymer is made in a bulk or high pressure process where the polymer and the NFP were soluble in the monomer, where the NFP may be added directly to the finishing train. Similarly, a filler could be added to the finishing train.
  • compositions of this invention may be used in any known application involving molding or extrusion, including consumer goods, industrial goods, construction materials, packaging materials, and automotive parts.
  • Articles may be made or formed by any useful discrete molding or continuous extrusion means for forming and shaping polyolefins known in the art, including: compression molding, injection molding, co-injection molding, gas-assisted injection molding, blow molding, multi-layer blow molding, injection blow molding, stretch blow molding, extrusion blow molding, transfer molding; cast molding, rotational molding, foam molding, slush molding, transfer molding, wet lay-up or contact molding, cast molding, cold forming matched-die molding, thermoforming, vacuum forming, film blowing, film or sheet casting, sheet extrusion, profile extrusion or co-extrusion, fiber spinning, fiber spunbonding, fiber melt blowing, lamination, calendering, coating, pultrusion, protrusion, draw reduction, foaming, or other forms of processing such as described in, for example, PLASTICS PROCESSING
  • Non-limiting examples of desirable articles of manufacture made from compositions of the invention include films, tapes, sheets, fibers, tubing, pipes, coatings, fabrics (woven and nonwoven), tarps, agricultural barriers, packaging (durable and disposable), household appliances (washing machines, refrigerators, blenders, air conditioners, etc.), furniture (indoor and outdoor, such as tables, chairs, benches, shelving, etc.), sporting equipment (skis, surfboards, skateboards, skates, boots, sleds, scooters, kayaks, paddles, etc.), solid wheels, stadium seating, amusement park rides, personal protective equipment (safety helmets, shin guards, etc.), emergency response equipment, cookware, utensils, trays, pallets, carts, tanks, tubs, pond liners, storage containers (crates, pails, jars, bottles, etc.), toys, child car seats and booster chairs, medical devices, sportswear, luggage, tool housings (for drills, saws, etc.), electronics housings (for televisions
  • Such articles of manufacture made from compositions of the invention useful in vehicles include: bumpers and bumper fascias; exterior body panels, door panels, and grills; exterior trim, including body side moldings, side cladding and molding, end caps, hoods, deck lids, mirror housings, roof racks, wheel covers, wheel liners, wheel flares, fender liners, hub caps, running boards, step pads, sill plates, air dams, splash shields, mud guards, bed liners, and rocker panels; fuel tanks; interior trim, including steering column covers, consoles, door panels, pillars, supports, knobs, buttons, handles, and safety screens; instrument panels and dash boards; knee bolsters; passenger side airbag covers; headliners; glove
  • the article made from compositions of the invention has at least one overall dimension, such as length, greater than 30 cm (preferably greater than 60 cm, preferably greater than 90 cm, preferably greater than 120 cm). More preferably, said article is an automotive part. Most preferably, said article is fabricated by an injection molding process. [0209] In alternate embodiments, this invention relates to:
  • a hetero-phase polyolefin composition comprising: a) 30 to 99.7 wt% of a polypropylene-based TPO comprising at least 50 wt% propylene and at least 10 wt% ethylene, and b) 0.1 to 20 wt% of one or more non-functionalized plasticizer(s), and c) 0.2 to 50 wt% of one or more f ⁇ ller(s); based upon the weight of the composition, and having: i) an MFR of 5 dg/min or more, and ii) a flexural modulus of 500 MPa or more, and iii) a notched Charpy impact strength at -30 0 C of 1 kJ/m 2 or more or a notched Izod impact strength at -18°C of 50 J/m or more.
  • composition of paragraph 1 wherein the composition has an MFR of 10 dg/min or more.
  • composition of paragraph 1 or 2 wherein the composition has an MFR of 15 to 400 dg/min.
  • composition of any of paragraphs 1 to 3 wherein the composition has a flexural modulus of 800 MPa or more.
  • composition of any of paragraphs 1 to 4 wherein the composition has a flexural modulus of 900 to 3500 MPa.
  • composition of any of paragraphs 1 to 5 wherein the composition has a notched Charpy impact strength at -30 0 C of 2 kJ/m 2 or more and a notched Izod impact strength at -18°C of 50 J/m or more.
  • composition of any of paragraphs 1 to 6 wherein the composition has a notched Charpy impact strength at -30 0 C of 2.5 to 15 kJ/m 2 or more and a notched Izod impact strength at -18°C of 50 J/m or more.
  • composition of any of paragraphs 1 to 9 wherein the composition comprises 35 to 95 wt% of the polypropylene-based TPO.
  • composition comprises 40 to 90 wt% of the polypropylene-based TPO.
  • composition of any of paragraphs 1 to 11 wherein the polypropylene-based TPO comprises at least 55 wt% propylene. 13. The composition of any of paragraphs 1 to 12 wherein the polypropylene-based TPO comprises at least 60 wt% propylene.
  • composition of any of paragraphs 1 to 13 wherein the polypropylene-based TPO comprises at least 15 wt% ethylene.
  • composition of any of paragraphs 1 to 14 wherein the polypropylene-based TPO comprises at least 20 wt% ethylene.
  • composition of any of paragraphs 1 to 18 wherein the composition comprises 1 to 30 wt% of one or more filler(s).
  • composition of any of paragraphs 1 to 23 wherein the polypropylene-based TPO comprises a matrix having a T m of 110 0 C or more.
  • composition of any of paragraphs 1 to 24 wherein the polypropylene-based TPO comprises a matrix having a T n , of 120 0 C or more.
  • composition of any of paragraphs 1 to 25 wherein the polypropylene-based TPO comprises a matrix having a T m of 140 0 C or more.
  • composition of any of paragraphs 1 to 26 wherein the polypropylene-based TPO comprises a matrix having a T m of 160 0 C or more.
  • composition of any of paragraphs 1 to 27 wherein the polypropylene-based TPO comprises a dispersed phase having a T 8 of -20 0 C or less.
  • composition of any of paragraphs 1 to 28 wherein the polypropylene-based TPO comprises a dispersed phase having a T g of -30 0 C or less.
  • composition of any of paragraphs 1 to 29 wherein the polypropylene-based TPO comprises a dispersed phase having a T g of -40 0 C or less.
  • composition of any of paragraphs 1 to 30 wherein the polypropylene-based TPO comprises a dispersed phase having a T g of -50 0 C or less.
  • composition of any of paragraphs 1 to 35 wherein the polypropylene-based TPO comprises two or more in-situ impact copolymers.
  • ML 1+4, 125°C Mooney viscosity
  • composition of any of paragraphs 1 to 45 wherein the polypropylene-based TPO comprises at least one propylene polymer having a melting point of 110 0 C and at least one ethylene copolymer having a density of less than 0.90 g/cm .
  • composition of any of paragraphs 1 to 46 wherein the polypropylene-based TPO comprises at least one propylene polymer having a melting point of 110 0 C and at least one EP Rubber having a density of less than 0.87 g/cm 3 .
  • the polypropylene-based TPO comprises at least one propylene polymer and at least one ethylene copolymer having a density of less than 0.90 g/cm 3 and at least one EP Rubber having a density of less than 0.87 g/cm 3 .
  • MFR melt flow rate
  • composition of any of paragraphs 1 to 49 wherein the composition has: a) a melt flow rate (MFR) of lO to 500 dg/min, and b) a fiexural modulus of 900 to 3500 MPa, and c) a notched Charpy impact strength at -30°C of 1.5 to 15 kJ/m 2 , and d) a notched Izod impact strength at -18°C of 60 to 500 J/m, and e) a notched Charpy impact strength at 23 0 C of 20 kJ/m 2 or more. 52.
  • MFR melt flow rate
  • composition of any of paragraphs 1 to 49 wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a fiexural modulus of 900 to 3500 MPa, and c) a notched Charpy impact strength at -30°C of 1.5 to 15 kJ/m 2 , and d) a notched Izod impact strength at -18°C of 60 to 500 J/m, and e) a notched Izod impact strength at 23°C of 100 J/m or more.
  • MFR melt flow rate
  • composition of any of paragraphs 1 to 49 wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a fiexural modulus of 900 to 3500 MPa, and c) a notched Charpy impact strength at -30°C of 1.5 to 15 kJ/m 2 , and d) a notched Izod impact strength at -18°C of 60 to 500 J/m, and e) a ductile failure in a multi-axial impact strength test at 23°C.
  • MFR melt flow rate
  • composition of any of paragraphs 1 to 49 wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a fiexural modulus of 900 to 3500 MPa, and c) a notched Charpy impact strength at -30 0 C of 1.5 to 15 kJ/m 2 , and d) a notched Izod impact strength at - 18°C of 60 to 500 J/m, and e) a heat distortion temperature (HDT) of 60 0 C or more.
  • MFR melt flow rate
  • HDT heat distortion temperature
  • composition of any of paragraphs 1 to 49 wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a flexural modulus of 900 to 3500 MPa, and c) a notched Charpy impact strength at -3O 0 C of 1.5 to 15 kJ/m 2 , and d) a notched Izod impact strength at -18°C of 60 to 500 J/m, and e) a tensile strength of 10 MPa or more.
  • MFR melt flow rate
  • composition of any of paragraphs 1 to 49 wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a flexural modulus of 900 to 3500 MPa, and c) a notched Charpy impact strength at -30°C of 1.5 to 15 kJ/m 2 , and d) a notched Izod impact strength at -18°C of 60 to 500 J/m, and e) shrinkage upon injection molding of 0.1 to 5%.
  • MFR melt flow rate
  • composition of any of paragraphs 1 to 49 wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a flexural modulus of 900 to 3500 MPa, and c) a notched Charpy impact strength at -3O 0 C of 1.5 to 15 kJ/m 2 , and d) a notched Izod impact strength at -18°C of 60 to 500 J/m, and e) a fogging number of 70 or more.
  • MFR melt flow rate
  • Tg glass transition temperature
  • melt flow rate (MFR) of the composition increases by at least 2% for every 1 wt% of NFP present in the composition as compared to the same composition absent the NFP.
  • composition of any of paragraphs 1 to 83 wherein the NFP has a) a flash point of 200 0 C or more; b) a specific gravity of 0.86 or less; and cl) a pour point of -10 0 C or less and a viscosity index of 120 or more, or c2) a pour point of -20 0 C or less, or c3) a kinematic viscosity at 100 0 C of 35 cSt or more.
  • M n number- average molecular weight
  • composition of any of paragraphs 1 to 88 wherein the non-functionalized plasticizer has a kinematic viscosity at 100 0 C of 5 cSt or more, a viscosity index of 100 or more, a pour point of -20 0 C or less, a specific gravity less than 0.86, and a flash point greater than 200 0 C.
  • composition of any of paragraphs 1 to 89 wherein the non-functionalized plasticizer comprises at least 50 weight% of Ce to C 1S o isoparaffins.
  • composition of any of paragraphs 1 to 90 wherein the non-functionalized plasticizer has a pour point of -40 0 C or less and a specific gravity of less than 0.85.
  • the non-functionalized plasticizer comprises oligomers of C 5 to Cn alpha-olefins.
  • composition of any of paragraphs 1 to 92 wherein the non-functionalized plasticizer comprises oligomers of Ce to Ci 4 alpha-olefins.
  • composition of any of paragraphs 1 to 93 wherein the rion-functionalized plasticizer comprises oligomers of Cs to C12 alpha-olefins.
  • composition of any of paragraphs 1 to 94 wherein the non-functionalized plasticizer comprises oligomers of decene.
  • non-functionalized plasticizer comprises oligomers of C3 to C24 linear alpha-olefins wherein C 3 and C 4 linear alpha-olefins are present at 10 wt% or less.
  • non-functionalized plasticizer comprises oligomers of two or more C3 to Ci 8 linear alpha-olefins wherein C3 and C 4 linear alpha-olefins are present at 10 wt% or less.
  • non-functionalized plasticizer comprises oligomers of C 5 to Ci g linear alpha-olefins and has a branching ratio of 0.20 or less.
  • composition of any of paragraphs 1 to 95 wherein the non-functionalized plasticizer comprises C 15 to C 1500 oligomers of alpha-olefins and has a kinematic viscosity at 100 0 C of 3 cSt or more.
  • the non-functionalized plasticizer comprises C 20 to C 1000 oligomers of alpha-olefins and has a kinematic viscosity at 100 0 C of 5 cSt or more.
  • non-functionalized plasticizer comprises Ci 5 to Ci 500 oligomers of alpha-olefins and has a kinematic viscosity at 100 0 C of 8 cSt or more, a viscosity index of 120 or more, and a specific gravity of 0.86 or less.
  • non-functionalized plasticizer comprises C 1S to Cisoo oligomers of alpha-olefins and has a kinematic viscosity of 10 cSt or more at 100 0 C and a viscosity index of 120 or more, and a specific gravity of 0.86 or less.
  • non-functionalized plasticizer comprises oligomers of C 5 to Ci 8 linear alpha-olefins and has a kinematic viscosity of 8 cSt or more at 100 0 C 5 a viscosity index of 120 or more, and a pour point of -25°C or less.
  • non-functionalized plasticizer comprises: 1) a copolymer of a C 4 olefins derived from a C 4 raffmate stream or 2) a poly(n- butene) or 3) a copolymer of at least isobutylene derived units, 1-butene derived units, and 2- butene derived units; and has a pour point of -20 0 C or less and a kinematic viscosity at 100 0 C of 6 to 15O cSt.
  • non-functionalized plasticizer comprises a mineral oil having a saturates levels of 90% or more, a sulfur content of less than 0.03%, and a VI of 120 or more.
  • non-functionalized plasticizer comprises a paraffinic process oil with
  • non-functionalized plasticizer is a hydrocarbon fluid derived from a Gas-To-Liquids process comprising hydroisomerized Fischer- Tropsch waxes and having a pour point of about -20 to -60 0 C and a kinematic viscosity of about 6 to 20 cSt.
  • composition of any of paragraphs 1 to 89 wherein the non-functionalized plasticizer comprises a mixture of paraffins has two or more of the following properties:
  • VT viscosity index
  • composition of any of paragraphs 1 to 108 wherein the filler is selected from the group consisting of mineral aggregates (natural or synthetic), fibers, carbon black, graphite, wollastonite, natural and synthetic clays including nanoclays and organoclays, sand, and glass beads.
  • the filler has a median particle diameter of 0.1-100 microns.
  • composition of any of paragraphs 1 to 112 wherein the filler is selected from the group consisting of talc, mica, wollastonite, titanium dioxide, silicon carbide, silica, silicon dioxide and other oxides of silica (precipitated or not), calcium silicate, calcium and barium sulfates, calcium carbonate (calcite), lead carbonate, magnesium silicate, magnesium oxysulfates, antimony oxide, zinc white, lithopone, zircon, corundum, spinel, apatite, Barytes powder, magnesiter, dolomite, zinc borate, hydrotalcite compounds of the ions Mg, Ca, or Zn with Al, Cr or Fe and CO3 and/or HPO 4 (hydrated or not), quartz powder, hydrochloric magnesium carbonate, alumina, chrome, phosphorous and brominated flame retardants, antimony trioxide, silicone, and blends thereof.
  • the filler is selected from the group consisting of any of paragraphs 1 to 112 wherein the filler is selected from
  • composition of any of paragraphs 1 to 112 wherein the filler is selected from the group consisting of polyethylene terephthalate (PET) fibers and rayon fibers.
  • PET polyethylene terephthalate
  • composition of any of paragraphs 1 to 112 wherein the filler is selected from the group consisting of montmorillonite, sodium montrnorillonite, calcium montmorillonite, magnesium montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, sobockite, svindordite, stevensite, vermiculite, halloysite, aluminate oxides, hydrotalcite, illite, rectorite, tarosovite, ledikite, and florine mica.
  • the filler is selected from the group consisting of montmorillonite, sodium montrnorillonite, calcium montmorillonite, magnesium montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, sobockite
  • a nucleating agent selected from the group consisting of l,3:2,4-bis(3,4- dimethylbenzylidene)sorbitol, 2.2.1-heptane-bicyclodicarboxylic acid, l,3:2,4-bis-(p- methylbenzylidene)sorbitol, 2,2'-methylenebis(4,6-di-tertbutylphenol) phosphate salt, and sodium benzoate.
  • composition of any of paragraphs 1 to 128 wherein the composition has a scratch resistance rating of 3 N or more.
  • composition of any of paragraphs 1 to 128 wherein the non-functionalized plasticizer comprises a mixture of paraffins has two or more of the following properties: 1) a naphthenic content of less than 40 wt%, based on the total weight of the paraffin mixture; and/or
  • composition of any of paragraphs 1 to 130 wherein the non-functionalized plasticizer comprises a mixture of paraffins has two or more of the following properties: 1) a number-average molecular weight of 300 to 1800 g/mol; and/or
  • VI viscosity index
  • a molded automotive part comprising the composition of any of paragraphs 1 to
  • the article paragraph 132 where the article is selected from the group consisting of bumpers, bumper fascias; exterior body panels, door panels, grills, exterior trim, body side moldings, side cladding, side molding, end caps, hoods, deck lids, mirror housings, roof racks, wheel covers, wheel liners, wheel flares, fender liners, hub caps, running boards, step pads, sill plates, air dams, splash shields, mud guards, bed liners, and rocker panels; fuel tanks; interior trim, including steering column covers, consoles, door panels, pillars, supports, knobs, buttons, handles, safety screens, instrument panels, dash boards, knee bolsters; passenger side airbag covers, headliners, glove boxes, trays, cup holders, compartments, lids, seat components, backs, supports, safety belt securing devices, under-hood parts, battery trays, fan shrouds, electrical housings; cable bearings, structural components, door carriers, truck bed separators, load floors, and trunk dividers.
  • a vehicle comprising the composition of any of paragraphs 1 to 131 wherein the vehicle is selected from the group consisting of cars, trucks, buses, boats, all terrain vehicles, personal water craft, golf carts, snowmobiles, motorcycles, mopeds, tractors, mowers, wagons, bicycles, airplanes, helicopters, trains, military machines, and gondolas.
  • An article comprising the composition of any of paragraphs 1 to 131 wherein the article has at least one overall dimension greater than 30 cm.
  • An article comprising the composition of any of paragraphs 1 to 131 wherein the article has as a length greater than 30 cm.
  • An automotive part comprising the composition of any of paragraphs 1 to 131 wherein the article has as a length greater than 30 cm.
  • a process to prepare a molded part comprising heating the composition of any of paragraphs 1 to 131, then introducing the heated composition into a mold and thereafter cooling the composition and removing it from the mold.
  • a vehicle replacement part comprising the composition of any of paragraphs 1 to 131.
  • MI Melt Index
  • CDBI Composition Distribution Breadth Index
  • Carbon Type Composition (C A , C N , and Cp) ASTM D 2140 (see below)
  • the glass transition temperature (T g ) is measured using dynamic mechanical analysis. This test provides information about the small-strain mechanical response of a sample as a function of temperature over a temperature range that includes the glass transition region and the visco-elastic region prior to melting. Specimens are tested using a commercially available DMA instrument (e.g., TA Instruments DMA 2980 or Rheometrics RSA) equipped with a dual cantilever test fixture. The specimen is cooled to -130 0 C then heated to 6O 0 C at a heating rate of 2°C/min while subjecting to an oscillatory deformation at 0.1% strain and a frequency of 1 rad/sec.
  • DMA instrument e.g., TA Instruments DMA 2980 or Rheometrics RSA
  • the output of these DMA experiments is the storage modulus (E') and loss modulus (E").
  • the storage modulus measures the elastic response or the ability of the material to store energy
  • the loss modulus measures the viscous response or the ability of the material to dissipate energy.
  • the ratio of E"/E' gives a measure of the damping ability of the material; peaks in Tan-delta are associated with relaxation modes for the material.
  • T g is defined to be the peak temperature associated with the ⁇ -relaxation mode, which typically occurs in a temperature range of -80 to +20 0 C for polyolefms.
  • separate ⁇ - relaxation modes for each blend component may cause more than one T g to be detected for the blend; assignment of the T g for each component are preferably based on the T g observed when the individual components are similarly analyzed by DMA (although slight temperature shifts are possible).
  • DSC Differential Scanning Calorimetry
  • Crystallization temperature (T c ) and melting temperature (or melting point, T m ) are measured using Differential Scanning Calorimetry (DSC) on a commercially available instrument (e.g., TA Instruments 2920 DSC). Typically, 6 to 10 mg of molded polymer or plasticized polymer are sealed in an aluminum pan and loaded into the instrument at room temperature. Melting data (first heat) is acquired by heating the sample to at least 30 0 C above its melting temperature, typically 220 0 C for polypropylene, at a heating rate of 10°C/min. The sample is held for at least 5 minutes at this temperature to destroy its thermal history.
  • DSC Differential Scanning Calorimetry
  • Crystallization data are acquired by cooling the sample from the melt to at least 50 0 C below the crystallization temperature, typically -50 0 C for polypropylene, at a cooling rate of 20°C/min. The sample is held at this temperature for at least 5 minutes, and finally heated at 10°C/min to acquire additional melting data (second heat).
  • the endothermic melting transition (first and second heat) and exothermic crystallization transition are analyzed according to standard procedures.
  • the melting temperatures reported are the peak melting temperatures from the second heat unless otherwise specified.
  • the melting temperature is defined to be the peak melting temperature from the melting trace associated with the largest endothermic calorimetric response (as opposed to the peak occurring at the highest temperature).
  • the crystallization temperature is defined to be the peak crystallization temperature from the crystallization trace associated with the largest exothermic calorimetric response (as opposed to the peak occurring at the highest temperature).
  • H f upon melting or heat of crystallization
  • H 0 upon crystallization
  • the percent crystallinity (X%) is calculated using the formula: [area under the curve (in J/g) / H° (in J/g)] *
  • H° is the ideal heat of fusion for a perfect crystal of the homopolymer of the major monomer component.
  • H°(polyethylene) a value of 140 J/g is used for H° (polybutene), and a value of 207 J/g is used for H°(polypropylene).
  • Molecular weight (weight-average molecular weight, M w , number-average molecular weight, M n , and molecular weight distribution, M w /M n or MWD) are determined using a commercial High Temperature Size Exclusion Chromatograph (e.g., from Waters Corporation or Polymer Laboratories) equipped with three in-line detectors: a differential refractive index detector (DRI), a light scattering (LS) detector, and a viscometer.
  • DRI differential refractive index detector
  • LS light scattering
  • the TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/mL at room temperature and 1.324 g/mL at 135°C. Injection concentration range from 1.0 to 2.0 n ⁇ g/mL, with lower concentrations being used for higher molecular weight samples.
  • the DRI detector and injector Prior to running a set of samples, the DRI detector and injector are purged, the flow rate increased to 0.5 ml/min, and the DRI allowed to stabilize for 8-9 hours; the LS laser is turned on 1 hr before running samples.
  • the LS detector is a Wyatt Technology High Temperature mini-DAWN.
  • the molecular weight, M, at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M.B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971):
  • ⁇ R( ⁇ ) MP( ⁇ ) 2 [0220]
  • ⁇ R( ⁇ ) is the measured excess Rayleigh scattering intensity at scattering angle ⁇
  • c is the polymer concentration determined from the DRI analysis
  • P( ⁇ ) is the form factor for a monodisperse random coil
  • K 0 is the optical constant for the system: consult _ 4 ⁇ V(dn/dc) 2 ⁇ 4 N A where N A is Avogadro's number, and (dn/dc) is the refractive index increment for the system.
  • dn/dc 0.104 for propylene polymers and 0.1 otherwise.
  • a high temperature Viscotek Corporation viscometer which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure.
  • the specific viscosity, ⁇ s for the solution flowing through the viscometer is calculated from their outputs.
  • the branching index (g 1 ) is calculated using the output of the SEC-DRI-LS-VIS method as follows.
  • the average intrinsic viscosity, [ ⁇ javg, of the sample is calculated by: where the summations are over the chromotographic slices, i, between the integration limits.
  • M v is the viscosity-average molecular weight based on molecular weights determined by LS analysis.
  • Composition Distribution Breadth Index (CDBD) Composition Distribution Breadth Index
  • CDBI is a measure of the composition distribution of monomer within the polymer chains. It is measured as described in WO 93/03093, with the modification that any fractions having a weight-average molecular weight (M w ) below 20 kg/mol are ignored in the calculation.
  • Polypropylene microstructure is determined by 13 C-NMR spectroscopy, including the concentration of isotactic and syndiotactic diads ([m] and [r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]).
  • concentration of isotactic and syndiotactic diads [m] and [r]
  • triads [mm] and [rr]
  • pentads [mmmm] and [rrrr]
  • the "mm triad tacticity index" of a polymer is a measure of the relative isotacticity of a sequence of three adjacent propylene units connected in a head-to-tail configuration. More specifically, in the present invention, the mm triad tacticity index (also referred to as the "mm Fraction") of a polypropylene homopolymer or copolymer is expressed as the ratio of the number of units of meso tacticity to all of the propylene triads in the copolymer: _ . PPP(mm) mm Fraction- 5 —
  • PPP(mm)+ PPP(mr)+ PPP(rr) where PPP(mm), PPP(mr) and PPP(rr) denote peak areas derived from the methyl groups of the second units in the possible triad configurations for three head-to-tail propylene units, shown below in Fischer projection diagrams:
  • Ethylene content in ethylene copolymers is determined by ASTM D 5017-96, except that the minimum signal-to-noise should be 10,000:1.
  • Propylene content in propylene copolymers is determined by following the approach of Method 1 in Di Martino and Kelchermans, J. Appl. Polym. ScL 56, 1781 (1995), and using peak assignments from Zhang, Polymer 45, 2651 (2004) for higher olefin comonomers. Fluid Molecular Weight
  • M n The number-average molecular weight (M n ) is determined by one of two methods:
  • Carbon type composition is determined by ASTM D 2140, and gives the percentage of aromatic carbons (C A ), naphthenic carbons (C N ), and paraffinic carbons (Cp) in the fluid.
  • C A is the wt% of total carbon atoms in the fluid that are in aromatic ring-type structures
  • C N is the wt% of total carbon atoms in the fluid that are in saturated ring-type structures
  • Cp is the wt% of total carbon atoms in the fluid that are in paraffinic chain-type structures.
  • ASTM D 2140 involves calculating a "Viscosity Gravity Constant” (VGC) and "Refractivity Intercept” (RI) for the fluid, and determining the carbon type composition from a correlation based on these two values.
  • VGC Viscosity Gravity Constant
  • RI Refractivity Intercept
  • ASTM D 2140 the following protocol is used: If the calculated VGC (ASTM D 2140) for a fluid is 0.800 or greater, the carbon type composition including Cp is determined by ASTM D 2140. If the calculated VGC (ASTM D 2140) is less than 0.800, the fluid is considered to have C P of at least 80%.
  • VGC VGC
  • ASTM D 3238 is used to determine the carbon type composition including Cp. If application of ASTM D 3238 yields unphysical quantities (e.g., a negative C A value), then Cp is defined to be 100%. If the calculated VGC (ASTM D 2140) for a fluid is 0.765 or less, then C P is defined to be 100%.
  • Color is determined on the APHA scale by ASTM D 1209. Note that an APHA color of 100 corresponds to a Saybolt color (ASTM D 156) of about +10; an APHA color of 20 corresponds to a Saybolt color of about +25; and an APHA color of 0 corresponds to a Saybolt color of about +30.
  • composition and branching characteristics of paraffinic hydrocarbon fluids is determined by 13 C-NMR spectroscopy, following the general procedures and peak assignments outlined in Breitmaier and Voelter, CARBON-13 NMR SPECTROSCOPY, 3 RD ED. (VCH, 1986). NFP Content
  • the preferred method to determine the NFP content (weight percent basis) in a polyolefin composition is the Extraction Method.
  • the NMR Method can be used. In event of conflict, the Extraction Method shall control.
  • the Extraction Method involves Soxhlet extraction, wherein at least a majority of the NFP is extracted with refluxing n-heptane. Analysis of the base polymer is also required because it may contain low molecular weight and/or amorphous material that is soluble in refluxing n- heptane.
  • the level of NFP in the blend is determined by correcting its extractables level, in weight percent, by the extractables level for the base polymer, as described below.
  • the Soxhlet extraction apparatus consists of a 400 mL Soxhlet extractor, with a widened overflow tube (to prevent siphoning and to provide constant flow extraction); a metal screen cage fitted inside the main Soxhlet chamber; a Soxhlet extraction thimble (Whatman, single thickness, cellulose) placed inside the screen cage; a condenser with cooling water and drain; and a one-neck 1000 mL round bottom flask with appropriately sized stir bar and heating mantle.
  • the procedure is as follows. Dry the soxhlet thimbles in a 95°C oven for 60 min. Weigh the dry thimble directly after removal from oven; record this weight as A in g. Weigh out 15-20 g of sample (either in pellet or ground pellet form.) into the thimble; record as B in g. Place the thimble containing the polymer in the Soxhlet apparatus. Pour 300 mL of HPLC-grade n- heptane into the round bottom flask with stir bar and secure the flask on the heating mantle. Connect the round bottom flask, the soxhlet, and the condenser in series.
  • the NMR Method requires constructing a model based on a calibration curve (or set of calibration curves) of measured parameter(s) as a function of NFP concentration.
  • the calibration blends are prepared using the same polymer and NFP as the blend(s) under investigation but at known NFP concentrations.
  • This set of calibrants must number at least five, and include the neat polymer as well as at least one NFP concentration above the maximum for the blend(s) under investigation but not greater than 50 wt% NFP.
  • the blend(s) under investigation are analyzed under the same conditions as the calibrants, and the NFP content determined by applying the model.
  • the NMR Method involves high-temperature solution-phase 13 C-nuclear magnetic resonance (HTS-CNMR).
  • the composition is determined using the reference spectra of the neat polymer and neat NFP, as well as spectra for a set of calibration blends (i.e., prepared from the neat polymer and NFP at known wt% NFP).
  • the spectra are analyzed to determine a set of one or more diagnostic resonances or clusters of resonances that increase or decrease in strength monotonically with increasing NFP content.
  • the corresponding peaks are integrated and their fractional contribution to the total integral calculated as a function of NFP content (weight %) to generate a set of calibration curves.
  • a chemometrics model is developed using these calibration curves to provide a method to calculate the NFP content.
  • the number of diagnostic resonances is chosen to allow the model to predict NFP content with a precision of 1 wt% or better over the calibration range.
  • chemometrics and how to develop a chemometrics model see CHEMOMETRIC TECHNIQUES FOR QUANTITATIVE ANALYSIS, Richard Kramer (Marcel Dekker, 1998).
  • the blend(s) of unknown concentration are then run following the same HTS-CNMR procedure as used for the calibrants, and the results analyzed according to the model to determine the wt% NFP.
  • a typical HTS-CNMR procedure is as follows.
  • Samples are prepared in 1,1,2,2- tetrachloroethane- ⁇ , with chromium acetylacetonate [Cr(acac) 3 ] added as a relaxation agent to accelerate data acquisition.
  • the Cr(acac) 3 concentration in the stock solvent is approximately 15 mg/ml.
  • Sample concentrations are between 10 and 15 wt%.
  • Free induction decays of 15,000 transients are accumulated at a temperature of 120 0 C on a Varian UnityPlus 500 instrument using a 10 mm broadband probe. Spectra are acquired with a 90° carbon excitation pulse, and inverse- gated WALTZ-16 proton decoupling. An acquisition time of approximately 1 second and recycle delay of 3.5 seconds are used to allow quantitative integration.
  • Solvent choice and sample concentration may be adjusted to accommodate different solubility and to minimize spectral interference based on the specific composition of the blend. See CARBON-13 NMR SPECTROSCOPY: HIGH-RESOLUTION METHODS AND APPLICA ⁇ ONS IN ORGANIC CHEMISTRY AND BIOCHEMISTRY, 3rd Ed., Eberhard Breitmaier and Wolfgang Voelter (VCH, 1990) for a general description of CNMR techniques.
  • the unplasticized composition is the same composition as the plasticized composition but without NFP added.
  • AFM is used to determine if a polyolefm blend is a hetero-phase blend.
  • AFM "phase images" acquired using the "tapping-mode” method provide a morphological map of the sample based primarily on modulus, which is a strong function of crystallinity for polyolefins. Therefore, if the sample is a hetero-phase blend, distinct domains will be observed if they have different crystallinity, as is the case for domains of EP Rubber and/or ethylene copolymer in a polypropylene matrix. Other factors that influence the tapping-mode AFM signal, such as adhesion and electrostatic charge, will generally not affect the ability to determine if a polyolefm blend is a hetero-phase blend.
  • a smooth surface for analysis is prepared by cryofacing a representative sample of the blend using a cryo-ultramicrotome equipped with a diamond knife and operated at a temperature of -130 to -150°C.
  • the typical scan size is 20 microns by 20 microns, but smaller or larger scan sizes can be used depending on the size scale of the morphological features.
  • the minimum size scale for a domain detectable by AFM is about 0.1 micron.
  • a cantilever equipped with a tip and housed in a scanner head
  • Typical frequencies used are 50-100 kHz, but will vary depending on the actual stiffness of the assembly.
  • the tip intermittently strikes the sample as the scanner head moves over the surface.
  • a feedback loop maintains a constant oscillation amplitude of the cantilever based on the signal acquired by a photodiode detector that measures the intensity of light reflected from a laser aimed at the cantilever, which varies as the cantilever deflects.
  • This constant oscillation amplitude insures a constant tip-sample interaction so features seen in the image are due to tip response to the sample and not factors driving the cantilever.
  • the height image is determined by the vertical (z position) of the scanner at any (x, y) position on the surface.
  • the phase image is determined by the phase shift between the driving oscillation for the cantilever and the response oscillation at any point on the surface. Higher modulus (harder) regions absorb more energy and therefore yield a larger phase shift compared to lower modulus (softer) regions.
  • Specific parameters used to set the response of the feedback loop integrated and proportional gains
  • the oscillation amplitude set-point which is a fraction of the free oscillation amplitude
  • Blend components used to prepare the Example Blends are reported in Table 1; compositions of Example (E) and Comparative (C) blends are reported in Tables 2a and 2b; evaluation results for Example (E) and Comparative (C) blends are reported in Tables 3a and 3b.
  • Blends were prepared by melt-mixing all components on a ZSK-30 twin-screw extruder (30 mm diameter) with underwater pelletizer, using loss-in-weight feeders for adding components through the extruder feed-throat.
  • Example blends were prepared by melt-mixing a masterbatch composition with other components to yield the final composition, again using the ZSK-30 twin- screw extruder and feed-throat addition of all components except wollastonite, which was added using a side feeder.
  • Two masterbatch (MB) compositions were prepared on a ZSK-25 twin-screw extruder (25 mm diameter, 44 UD, 400 RPM) with underwater pelletizer, loss-in-weight feeders for addition of the solid components through the extruder feed-throat and for liquid injection of the NFP (injection point at barrel section 8 of 11):
  • MB-A 72 wt% Plastomer-1 / 20 wt%
  • PAO-2 / 8 wt% ICP-I MB-B 72 wt% Plastomer-1 / 20 wt%
  • PAO-I / 8 wt% ICP-I MB-C 72 wt% Plastomer-2 / 20 wt% PAO-2 / 8 wt% ICP-l
  • Test specimens were injection molded, conditioned, and tested as described in the Experimental Methods section. Table 1
  • ICP-I propylene/ethylene in-situ ICP Ziegler-Natta catalyst
  • ethylene content ⁇ 9 wt%
  • EP Rubber content - 18 wt%
  • MFR 35 dg/min
  • flexural modulus ⁇ 1270 MPa
  • ICP-2 propylene/ethylene in-situ ICP Ziegler-Natta catalyst
  • ethylene content ⁇ 4 wt%
  • EP Rubber content ⁇ 8 wt%
  • MFR 80 dg/min
  • flexural modulus ⁇ 1660 MPa
  • ICP-3 propylene/ethylene in-situ ICP Ziegler-Natta catalyst
  • ethylene content ⁇ 16 wt%
  • EP Rubber content ⁇ 30 wt%
  • MFR 15 dg/min
  • flexural modulus ⁇ 940 MPa
  • PAO-I octene/decene/dodecene
  • PAO-2 octene/decene/dodecene
  • ICP-2 (wt%) 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0
  • Plastomer-1 (wt%) 25.0 14.4 14.4 14.4 17.2 17.2 — 19.4 —
  • PAO-I (wt%) — — 4.0 — — — — — 4.0 4.0
  • PAO-2 (wt%) — 4.0 — 4.0 2.0 2.0 2.0 — ⁇
  • ICP-I (wt%) 15.0 21.6 21.6 21.6 20.8 20.8 20.8 16.6 16.6
  • ICP-2 (wt%) 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0
  • Plastomer-1 (wt%) 25.0 14.4 14.4 14.4 17.2 17.2 — 19.4 —
  • PAO-2 (wt%) — 4.0 — 4.0 2.0 2.0 2.0 — —
  • ICP-2 (wt%) — — 15.0 35.0 15.0 — ⁇ —
  • ICP-3 (wt%) 75.0 75.0 — — -- 72.0 63.4 89.8
  • Plastomer-2 (wt%) — 7.2 17.0 15.0 24.8 5.0 15.0 5.0
  • PAO-I (wt%) 2.0 2.0 3.0 3.0 0.2 3.0 1.6 2.0
  • Multi-Axial Impact -30 0 C 26. 22. 19. 21. 22. 21. 21.
  • Multi-Axial Impact -30 0 C 25. 12. 16. 17. 21. 21.5 21.

Abstract

This invention relates to hetero-phase polyolefin compositions comprising: a) 30 to 99.7 wt% of a polypropylene-based TPO comprising at least 50 wt% propylene and at least 10 wt% ethylene, and b) 0.1 to 20 wt% of one or more non-functionalized plasticizer, and c) 0.2 to 50 wt% of one or more filler; based upon the weight of the composition, and having: i) an MFR of 5 dg/min or more, and ii) a flexural modulus of 500 MPa or more, and iii) a notched Charpy impact strength at -30°C of 1 kJ/m2 or more or a notched Izod impact strength at -18°C of 50 J/m or more. These compositions are especially useful in applications such as automotive parts that demand both high stiffness and high impact toughness, as well as good processibility during fabrication.

Description

PLASTICIZED HETERO-PHASE POLYOLEFIN BLENDS
FIELD OF THE INVENTION
[0001] This invention relates to hetero-phase polyolefin compositions, such as 5 polypropylene-based thermoplastic polyolefin compositions, for use in the manufacture of automotive components, among other uses, and for articles made from such compositions.
BACKGROUND OF THE INVENTION
[0002] Multi-phase polyolefin compositions — often consisting of a "plastic" matrix phase and a "rubber" dispersed phase - are used in many applications that require a material that is
10 lightweight, tough, stiff, and easily processed.
[0003] It would be particularly desirable to use a simple compound such as a conventional mineral oil as the low molecular weight additive for this purpose. After all, such compounds are routinely used as process oils or extender oils in polyolefin elastomers. However, it has been taught that conventional mineral oils, even paraffinic mineral oils, impair the properties of
15. polyolefins, in particular semi-crystalline polyolefins (see WO 01/18109 Al and Chemical Additives for the Plastics Industry, Radian Corp., 1987, p. 107-116). Indeed, such compounds are often detrimental to semicrystalline polypropylene, in that they migrate to the surface causing, parts to become oily (except at very low concentrations), or they degrade mechanical properties because they fail to depress the glass transition temperature effectively. The plasticizers 0 described herein overcome these limitations.
[0004] WO 04/014998 discloses blends of polyolefins with non-functionalized plasticizers. In particular, Tables 8, 11, and 21a to 22f describe blends of certain impact copolymers with certain liquids and/or plasticizers, and Tables 23a to 23f describe blends of a certain thermoplastic polyolefin composition with certain liquids and/or plasticizers. These blends 5 however are unsuitable for automotive TPO applications because they do not have the appropriate balance of stiffness, toughness, and flow properties.
[0005] Plasticized polyolefin compositions and their applications are also described in WO 04/014997 and US 2004/260001. Additional references of interest include: US 4132698, US 4536537, US 4774277, JP 09-208761, WO 98/44041, WO 03/48252, and US 2004/034148. 0 [0006] TPOs, including compositions that comprise polypropylene and or filler, are described in POLYPROPYLENE HANDBOOK, 2ND ED., N. Pasquini, Ed. (Hanser, 2005), p. 314-330; POLYMER BLENDS, D.R. Paul and CB. Bucknall, Eds. (Wiley-Interscience. 2000), Vol. 2; US 5681897; US 6245856; and US 6399707. However, the addition of both a filler and a non-functionalized plasticizer to a polypropylene-based TPO to give an improved balance of properties, as described herein, has not been previously disclosed.
SUMMARY OF THE INVENTION
[0007] This invention relates to the use of certain of hydrocarbon liquids as plasticizers for hetero-phase polyolefin compositions based on polypropylene. Such compositions are especially useful in automotive components and other applications that demand high stiffness, excellent impact toughness at low temperatures, and good processibility during fabrication. [0008] More specifically, this invention relates to a hetero-phase polyolefin composition comprising: a) 30 to 99.7 wt% of a polypropylene-based TPO comprising at least 50 wt% propylene and at least 10 wt% ethylene, and b) 0.1 to 20 wt% of one or more non-functionalized plasticizer(s), and c) 0.2 to 50 wt% of one or more filler(s); based upon the weight of the composition, and having: i) a melt flow rate, 230 0C, 2.16kg, (MFR) of 5 dg/min or more, and ii) a flexural modulus of 500 MPa or more, and iii) a notched Charpy impact strength at -300C of 1 kJ/m2 or more, or a notched Izod impact strength at -18°C of 50 J/m or more.
DEFINITIONS
[0009] The following definitions are made for purposes of this invention and the claims thereto.
[0010] When a polymer or oligomer is referred to as comprising an olefin, the olefin present in the polymer or oligomer is the polymerized or oligomerized form of the olefin, respectively.
The term polymer is meant to encompass homopolymers and copolymers. The term copolymer includes any polymer having two or more different monomers in the same chain, and encompasses random copolymers, statistical copolymers, interpolymers, and (true) block copolymers.
[0011] When a polymer blend is said to comprise a certain percentage of a monomer, that percentage of monomer is based on the total amount of monomer units in all the polymer components of the blend. For example if a blend comprises 50 wt% of polymer A, which has 20 wt % monomer X, and 50 wt% of a polymer B, which has 10 wt% monomer X, the blend comprises 15 wt% of monomer X.
[0012] A "polymer" has a number-average molecular weight (Mn) of 20 kg/mol or more, while an "oligomer" has a Mn of less than 20 kg/mol.
[0013] The term "hetero-phase" refers to the presence of two or more morphological phases in a blend of two or more polymers, where each phase comprises a different ratio of the polymers as a result of partial or complete immiscibiliry (i.e., thermodynamic incompatibility). A common example is a morphology consisting of a "matrix" (continuous) phase and at least one "dispersed" (discontinuous) phase. The dispersed phase takes the form of discrete domains (particles) distributed within the matrix (or within other phase domains, if there are more than two phases). Another example is a co-continuous morphology, where two phases are observed but it is unclear which is the continuous phase and which is the discontinuous phase. The presence of multiple phases is determined using microscopy techniques, e.g., optical microscopy, scanning electron microscopy (SEM)5 or atomic force microscopy (AFM); or by the presence of two glass transition peaks in a dynamic mechanical analysis (DMA) experiment; in the event of disagreement among these methods, the AFM determination shall be used.
[0014] A "liquid" is defined to be a material that flows at room temperature, having a pour point of less than +200C and a kinematic viscosity at 25°C of 30,000 cSt or less. [0015] The term "paraffin" refers to saturated hydrocarbons, including normal paraffins, branched paraffins, isoparaffms, cycloparaffins, and blends thereof, and may be derived synthetically or from refined crude oil by means known in the art. More specifically, the following terms have the indicated meanings: "isoparaffins" are branched chain-type saturated hydrocarbons (i.e., branched alkanes, having at least one tertiary or quaternary carbon atom), which possess at least one Ci to Cis (more commonly Ci to C10) alkyl branch along at least a portion of each chain; "normal paraffins" are un-branched chain-type saturated hydrocarbons (i.e., normal alkanes); and "cycloparaffins" (also known as "naphthenes") are cyclic (mono-ring and/or multi-ring) saturated hydrocarbons and branched cyclic saturated hydrocarbons. For each class of paraffin, various structural isomers will typically be present for each carbon number. Unsaturated hydrocarbons include alkenes (olefins, diolefins, etc.), alkynes, and "aromatics" (unsaturated mono-ring and/or multi-ring cyclic moieties, including branched cyclic unsaturated hydrocarbons).
[0016] The term "mineral oil" includes any hydrocarbon liquid of lubricating viscosity (i.e., a kinematic viscosity at 1000C of 1 cSt or more) derived from petroleum crude oil and subjected to one or more refining and/or hydroprocessing steps (such as fractionation, hydrocracking, dewaxing, isomerization, and hydrofinishing) to purify and chemically modify the components to achieve a final set of properties. Such "refined" oils are in contrast to "synthetic" oils, which are manufactured by combining monomer units using catalysts and/or heat. In the lubricant industry, refined "basestocks" (which are mineral oils) are commonly divided into three categories based on their properties, as follows: Category Saturates Sulfur Viscosity Index
Group I < 90 wt% and/or > 0.03 wt% and 80 - 119 Group π > 90 wt% and ≤ 0.03 wt% and 80 - 119 Group m > 90 wt% and < 0.03 wt% and > 120
[0017] However, even if a mineral oil is not specifically identified by one of these basestocks classification, it is still possible to categorize it using this scheme. Accordingly, herein, a "Group HI Mineral Oil" is defined to be a mineral oil having a viscosity index of 120 or more, whereas a "Group m basestock" is defined according to the above table; therefore, any Group HI basestock will also be a Group HI Mineral Oil, but the opposite is not necessarily true. [0018] In the polymer industry, mineral oils are often called '^process oils" (or "extender oils"). A common classification system for process oils is to identify them as either "paraffmic", "naphthenic", or "aromatic" mineral (or process or extender) oils based on the relative content of paraffinic, naphthenic, and aromatic moieties (see Typical in the table below). Herein, the three common classes are defined based on the compositions described under Definitions in the table below:
Figure imgf000005_0001
where Cp, CN, and CΛ indicate the percentage of carbons in paraffinic chain-like (i.e., isoparaffinic and normal paraffinic) structures, naphthenic (i.e., saturated ring) structures, and aromatic (i.e., unsaturated ring) structures, respectively.
[0019] The term "substantially absent" means that the compounds in question are not added deliberately to the compositions and, if present, are present at less than 1 wt%, based upon the total weight of the composition. Preferably, the compounds in question are present at less than
0.5 wt% (preferably less than 0.1 wt%, preferably less than 0.05 wt%, preferably less than 0.01 wt%, preferably less than 0.001 wt%), based upon the total weight of the composition.
[0020] For purpose of this invention and the claims thereto, unless otherwise noted, physical and chemical properties described herein are measured using the test methods described under the
Experimental Methods section.
DETAILED DESCRIPTION OF THE INVENTION
[0021] This invention relates to plasticized hetero-phase polyolefin compositions comprising a polypropylene-based TPO, one or more non-functionalized plasticizers, and one or more filler. [0022] The non-functionalized plasticizer (NFP) compounds of the present invention are hydrocarbon liquids with certain characteristics as described herein. We discovered that addition of one or more NFP improves the overall performance of polypropylene-based TPO compositions that meet the stringent array of mechanical property requirements for automotive (and other) applications. In particular, these compositions exhibit better processibility than can be achieved using previous formulation approaches. Generally, the compositions comprise a polypropylene- based TPO5 an NFP, and a filler, and optionally additives.
[0023] More specifically, this invention relates to a hetero-phase polyolefin composition comprising: a) 30 to 99.7 wt% of a polypropylene-based TPO comprising at least 50 wt% propylene and at least 10 wt% ethylene, and b) 0.1 to 20 wt% of one or more non-functionalized plasticizer, and c) 0.2 to 50 wt% of one or more filler; based upon the weight of the composition, and having: i) an MFR of 5 dg/min or more, and ii) a flexural modulus of 500 MPa or more, and iii) a notched Charpy impact strength at -300C of 1 kJ/m2 or more, and/or a notched Izod impact strength at -18°C of 50 J/m or more.
[0024] The polypropylene-based TPO may be an impact copolymer (especially an in-situ ICP), or it may be a physical blend of an ICP with a plastomer and/or ethylene-propylene rubber (EP Rubber), or it may be a physical blend of a propylene polymer (especially a homopolymer polypropylene (hPP) or a random copolymer polypropylene (RCP)) with a plastomer and/or EP Rubber. Preferred polymeric components are described more fully below, hi a preferred embodiment, the polypropylene-based TPO comprises a matrix having a melting point (Tm) of 110°C or more (preferably 1200C or more, preferably 125°C or more, preferably 1300C or more, preferably 1400C or more, preferably 1500C or more, preferably 1600C or more), hi another preferred embodiment, the polypropylene-based TPO comprises a dispersed phase having a glass transition temperature (Tg) of -200C or less (preferably -25°C or less, preferably -300C or less, preferably -35°C or less, preferably -400C or less, preferably -45°C or less, preferably -500C or less, preferably -55°C or less).
[0025] The non-functional plasticizer (NFP) may be a PAO oligomer, or it may be a Group IH Mineral Oil, or it may be a GTL basestock, or it may be an Exceptional Paraffinic Process Oil. Preferably, the NFP has a kinematic viscosity at 1000C of 5 cSt or more, a viscosity index of 100 or more, a pour point of -200C or less, a specific gravity less than 0.86, and a flash point greater than 2000C. Preferred NFPs are described more fully below.
[0026] The filler may be inorganic mineral particulates, inorganic fibers, or engineering thermoplastic fibers. Preferred fillers are described more fully below.
Hetero-phase PoWolefin Composition
[0027] In one embodiment, this invention relates to a hetero-phase polyolefm composition comprising: a) 30 to 99.7 wt% (preferably 35 to 95 wt%, preferably 40 to 90 wt%, preferably 45 to 85 wt%) of a polypropylene-based TPO, b) 0.1 to 20 wt% (preferably 0.5 to 15 wt%, preferably 1 to 10 wt%, preferably 1.5 to 5 wt%) of one or more NFP(s), and c) 0.2 to 50 wt% (preferably 0.5 to 40 Wt0Zo, preferably 1 to 30 wt%, preferably 5 to 20 wt%) of one or more filler(s), based upon the weight of the composition; and having i) a melt flow rate of 5 dg/min or more (preferably 10 dg/min or more, preferably 15 to 400 dg/min, preferably 20 to 300 dg/min, preferably 30 to 200 dg/min or more, preferably 35 to 100 dg/min), ii) a flexural modulus of 500 MPa or more (preferably 800 MPa or more, preferably 900 to
3500 MPa, preferably 1000 to 3000 MPa, preferably 1100 to 2500 MPa), and iii) a notched Charpy impact strength at -300C of 1 kJ/m2 or more (preferably 2 kJ/m2 or more, preferably 2.5 to 15 kJ/m2, preferably 3 to 12 kJ/m2), and/or a notched Izod impact strength at -18°C of 50 J/m or more (preferably 60 J/m or more, preferably 70 to 500 J/m, preferably 80 to 400 J/m, preferably 90 to 300 J/m, preferably 100 to 200 J/m); where the polypropylene-based TPO comprises at least 50 wt% (preferably at least 55 wt%, preferably at least 60 wt%, preferably at least 65 wt%) propylene and at least 10 wt% (preferably at least 15 wt%, preferably at least 20 wt%, preferably at least 25 wt%) ethylene, based on the total weight of the propylene based-TPO. The polypropylene-based TPO may comprise one or more ICP(s); or one or more propylene polymer and one or more ethylene copolymer and/or EP Rubber; or one or more ICP and one or more propylene polymer and one or more ethylene copolymer and/or EP Rubber.
[0028] In any of the above embodiments that comprise one or more ICP(s), preferably at least one of the ICP(s) is an in-situ ICP; more preferably all the ICP(s) are in-sini ICP(s). Alternately, the combination of ICP(s) comprises two in-situ ICPs; alternately, the composition comprises only one in-situ ICP.
[0029] In any of the above embodiments that comprise one or more propylene polymers(s): Preferably the propylene polymer of the combination of propylene polymer(s) has a melting point of at least 1100C (preferably at least 1200C, preferably at least 1300C, preferably at least 1400C. preferably at least 1500C5 preferably at least 1600C, preferably at least 165°C).
[0030] In any of the above embodiments that comprise one or more ethylene copolymers):
Preferably the ethylene copolymer or the combination of ethylene copolymers) has a density of less than 0.90 g/cm3 (preferably less than 0.89 g/cm3, preferably less than 0.88 g/cm3, preferably less than 0.87 g/cm3).
[0031] In any of the above embodiments that comprise one or more EP Rubber(s): Preferably the EP Rubber or the combination of EP Rubber(s) has density of less than 0.87 g/cm3 (preferably less than 0.86 g/cm3). [0032] In any of the above embodiments, preferably the NFP has a kinematic viscosity at
1000C of 4 cSt or more (preferably 6 cSt or more, preferably 8 cSt or more, preferably 10 cSt or more), a viscosity index of 100 or more (preferably 110 or more, preferably 120 or more, preferably 130 or more), a pour point of -15°C or less (preferably -200C or less, preferably -25°C or less, preferably -300C or less), a flash point of 2000C or more (preferably 2200C or more, preferably 2400C or more, preferably 2600C or more), and a specific gravity of 0.88 or less
(preferably 0.87 or less, preferably 0.86 or less).
[0033] In any of the above embodiments, preferably the filler is an inorganic mineral filler with a median particle diameter of less than 50 microns.
[0034] In a preferred embodiment, any hetero-phase polyolefin composition of the present invention has: a) melt flow rate (MFR) of 10 to 500 dg/min (preferably 15 to 200 dg/min, preferably 20 to 100 dg/min, preferably 25-80 dg/min), and b) flexural modulus of 900 to 3500 MPa (preferably 1000 to 3000 MPa, preferably 1100 to 2800 MPa); and one or both of the following properties : c) notched Charpy impact strength at -300C of 1.5 to 15 kJ/m2 (preferably 2 to 12 kJ/m2, preferably 2.5 tolO kJ/m2), and/or d) notched Izod impact strength at -18°C of 60 to 500 J/m (preferably 70 to 400 J/m, preferably 80 to 350 J/m, preferably 90 to 300 J/m, preferably 100 to 250 J/m); and optionally one or more of the following properties: e) notched Charpy impact strength at 23°C of 20 kJ/m2 or more (preferably 30 kJ/m2 or more, preferably 40 kJ/m2 or more), and/or f) notched Izod impact strength at 23°C of 100 J/m or more (preferably 150 J/m or more, preferably 200 J/m or more, preferably a "no break"), and/or g) ductile failure in a multi-axial impact strength test at 23°C (preferably ductile failure at 00C, preferably ductile failure at -300C), and/or h) heat distortion temperature (HDT) of 600C or more (preferably 700C or more, preferably 800C or more, preferably 900C or more), and/or i) a tensile strength of 10 MPa or more (preferably 12 MPa or more, preferably 14 MPa or more, preferably, 16 MPa or more, preferably 18 MPa or more), and/or j) shrinkage upon injection molding of 0.1 to 5% (preferably 0.15 to 3.5%, preferably 0.2 to 2.5%), and/or k) a fogging number (as measured by SAE J 1756) of 70 or more (preferably 80 or more, preferably 90 or more, preferably 95 or more).
[0035] In another embodiment, the hetero-phase polyolefin composition in the absence of any optional additives has a fogging number (SAE Jl 756) of 80 or more (preferably 90 or more, preferably 95 or more, preferably 98 or more).
Changes in properties of the blend with addition of NFP [0036] Preferred compositions of the present invention can be characterized in that the glass transition temperature (Tg) of at least one polymer component in the composition is depressed by at least 20C (preferably at least 4°C, preferably at least 6°C, preferably at least 8°C, preferably at least 8°C, preferably at least 100C) for every 1 wt% of NFP present in the composition, while the peak melting temperature of the highest melting component remains within 50C (preferably within 4°C, preferably within 3°C, preferably within 2°C) of its value for the same composition absent the NFP.
[0037] Preferred compositions of the present invention can be characterized in that the glass transition temperature (Tg) of at least one component in the composition is depressed at least 2°C (preferably at least 4°C, preferably at least 6°C, preferably at least 8°C, preferably at least 10°C, preferably at least 12°C, preferably at least 15°C, preferably at least 200C) relative to its value for the same composition absent the NFP, while the peak melting temperature of the highest melting component remains within 5°C (preferably within 4°C, preferably within 3°C, preferably within 2°C) of its value for the same composition absent the NFP. [0038] Preferred compositions of the present invention can be characterized in that the weight loss of the composition containing the NFP is less than 3% (preferably less than 2%, preferably less than 1%) when permanence of the NFP is determined as described in the Experimental Methods section. Weight loss here refers to the reduction in weight in excess of that measured for the same composition without the NFP under the same test conditions. [0039] Preferred compositions of the present invention can be characterized in that the melt flow rate (MFR) of the composition increases by at least 2% (preferably at least 4%, preferably at least 6%, preferably at least 8%, preferably at least 10%, preferably at least 12%, preferably at least 15%, preferably at least 20%) for every 1 wt% of NFP present in the composition as compared to the same composition absent the NFP.
[0040] In another embodiment, the hetero-phase polyolefin composition exhibits reduced flow marks, either in severity (visibility rating) or tendency (onset distance from gate) as compared to the same hetero-phase polyolefin composition without NFP (i.e., where the ratio of the remaining component weight fractions is the unchanged). Preferably, the compositions of this invention have a flow mark visibility rating of 3 or less (preferably 2 or less, preferably 1 or less, preferably 0). Preferably, the distance from the gate to the first visible flow mark is 5 in or more (preferably 7 in or more, preferably 9 in or more, preferably 11 in or more,' preferably 13 in or more). Preferably, no flow marks are detected. Flow marks are evaluated following the protocol outlined in the Experimental Methods section. [0041] In another embodiment, the hetero-phase polyolefin composition exhibits an equal or better scratch resistance rating as compared the same hetero-phase polyolefin composition without NFP (i.e., where the ratio of the remaining component weight fractions is the unchanged). Preferably, the compositions of this invention have a scratch resistance rating of 3 N or more (preferably 5 N or more, preferably 7 N or more, preferably 10 N or more, preferably 12 N or more). The scratch resistance rating is determined following the protocol outlined in the Experimental Methods section.
Polyolefins
[0042] The hetero-phase polyolefin compositions of the present invention include one or more matrix phase component(s), comprised of polypropylene impact copolymer (ICP) and/or propylene homopolymer or copolymer, as well as one or more dispersed phase component(s), comprised of ethylene copolymer and/or EP Rubber. The classes of materials described herein that are useful for the matrix phase can be utilized alone or admixed to obtain desired properties. The classes of materials described herein that are useful for the dispersed phase can be utilized alone or admixed to obtain desired properties. Any polymeric component useful in the present invention may be described by any number of, or any combination of, parameters described herein.
Polypropylene Impact Copolymer (ICP)
[0043] The ICP comprises a polypropylene component (A) of hPP or RCP, and a rubber component (B) of propylene copolymer. The morphology is such that the matrix phase is comprised primarily of (A) while the dispersed phase is comprised primarily of (B). Preferred ICPs useful in this invention include those having one or more of the following properties:
1) total propylene content of at least 75 wt% (preferably at least 80 wt%, preferably at least 85 wt%, preferably at least 90 wt%, preferably at least 95 wt%) based on the weight of the ICP; and/or
2) total comonomer content of 1 to 35 wt% (preferably 2 to 30 wt%, preferably 3 to 25 wt%, preferably 5 to 20 wt%) based on the weight of the ICP; and/or
3) rubber content of 5 to 40 wt% (preferably 6 to 35 wt%, preferably 7 to 30 wt%, preferably 8 to 30 wt%) based upon the weight of the ICP; and/or 4) propylene content of the rubber component of 25 to 80 wt% (preferably 30 to 75 wt%, preferably 35 to 70 wt%, preferably at least 40 wt%) based on the weight of the rubber component; and/or
5) ratio of the intrinsic viscosity (IV) of the rubber component to the IV of the polypropylene component of 0.5 to 15 (preferably 0.75 to 12, preferably 1 to 8); and/or 6) propylene meso diads in the polypropylene component of 90% or more (preferably 92% or more, preferably 94% or more, preferably 96% or more); and/or
7) Mw of 20 to 2,000 kg/mol (preferably 50 to 1,000 kg/mol, preferably 90 to 500 kg/mol); and /or
8) melt flow rate (MFR) of 1 to 300 dg/min (preferably 5 to 150 dg/min, preferably 10 to 100 dg/min. preferably 15 to 80 dg/min, preferably 20 to 60 dg/min); and/or
9) melting point (Tm, second heat, peak) of 1000C or more (preferably 1100C or more, preferably 1200C or more, preferably 1300C or more, preferably 1400C or more, preferably 1500C or more, preferably 155°C or more, preferably 160°C or more); and/or
10) heat of fusion (Hf, second heat) of 60 J/g or more (preferably 70 J/g or more, preferably 80 J/g or more, preferably 90 J/g or more, preferably 95 J/g or more, preferably 100 J/g or more); and/or
11) glass transition temperature (Tg) of the rubber component of -300C or less (preferably -400C or less, preferably -500C or less); and/or
12) glass transition temperature (Tg) of the polypropylene component of-10°C or more (preferably -5°C or more, preferably 00C or more); and/or
13) flexural modulus of 300 to 3000 MPa (preferably 500 to 2500 MPa, preferably 700 to 2000 MPa, preferably 900 to 1500 MPa); and/or
14) notched Izod impact strength at 23°C of 2.5 J/m or more (preferably 5 J/m or more, preferably 7.5 J/m or more, preferably 10 J/m or more, preferably 15 J/m or more, preferably 20 J/m or more, preferably 25 J/m or more, preferably 50 J/m or more); and/or
15) Gardner impact strength at -300C of 2 to 100 J (preferably 3 to 80 J, preferably 4 to 60 J); and/or
16) heat deflection temperature (HDT) of 800C or more (preferably 850C or more, preferably 900C or more, preferably 95°C or more).
[0044] Comonomers used in conjunction with propylene to make an ICP are chosen from ethylene and C4 to Cs 1 -olefins, preferably from ethylene and 1-butene. In a preferred embodiment, the comonomer is ethylene and is present in the ICP at 1 to 50 wt% (preferably 2 to 40 wt%, preferably 3 to 30 wt%, preferably 5 to 20 wt%) based on the weight of the ICP. In another preferred embodiment, the rubber component of the ICP comprises 20 to 75 wt% (preferably 25 to 70 wt%, preferably 30 to 65 wt%, preferably less than 60 wt%) ethylene, and the balance propylene, based on the weight of the rubber component. More than one comonomer may also be employed, preferable selected from ethylene and C4 to Cs 1 -olefins, such as ethylene and butene-1 or ethylene and hexene-1, such that the rubber component comprises a propylene terpolymer.
[0045] In-situ ICPs are particularly preferred. For in-situ ICPs, the polypropylene (A) and rubber (B) components may be made using any appropriate polymerization process, including gas-phase, solution, slurry, and high-pressure polymerization processes. Preferably, (A) is made in a solution or slurry process, and (B) is made in a gas-phase process. More preferably, the in- situ ICP is made using a slurry reactor to produce an hPP (A) component, and a gas-phase reactor to produce an EP Rubber (B) component. The in-situ ICP polymerization processes may employ any appropriate polymerization catalyst or combination of catalysts, including Ziegler-Natta and/or single-site (e.g., metallocene) polymerization catalysts, which may be supported (for use in heterogeneous catalysis processes) or not (for use in homogeneous catalysis processes). Preferably, (A) and (B) are made using a common supported Ziegler-Natta or single-site catalyst. [0046] In another embodiment, the rubber component comprises a propylene copolymer with a weight-average molecular weight (Mw) of at least 50 kg/mol (preferably 100 kg/mol, preferably 150 kg/mol, preferably 200 kg/mol); a molecular weight distribution (Mw/Mn) of less than 3.5 (preferably less than 3.0, preferably 1.8 to 2.5); and a CDBI of greater than 60% (preferably greater than 65%, preferably greater than 70%, preferably greater than 75%, preferably greater than 80%, preferably greater than 85%). CDBI is a measure of the composition distribution of monomer within the polymer chains. It is measured as described in WO 93/03093, with the modification that any fractions having a weight-average molecular weight (Mw) below 20 kg/mol are ignored in the calculation. [0047] In-situ ICPs useful in the present invention are commercially available from many manufacturers, including ExxonMobil Chemical, Borealis, Dow Chemical (including INSPIRE™ grades), Sunoco Chemical, and Total Petrochemicals. Suitable examples include: ExxonMobil Chemical in-situ ICPs
MFR Flexural Modulus
Grade (dg/min) (MPa)
AXO3B 35 1270
PP7032 4-5 1100-1345
PP7033 5-8 1000-1250
PP7035 35 1100
PP7414 20 1034
PP7575 54 1100
PP7684 20 1290
PP8013 8 900
PP8244 15 940 [0048] Suitable ICPs are also commercially available from Basell Polyolefins, including "Advanced Polyolefins" grades made using their CATALLOY™ polymerization process, some of which are commercially available under the ADFLEX™ tradename. Basell also sells ICPs under the HIFAX™ and PROF AX™ tradenames.
[0049] Useful in-situ-impact copolymers may be prepared by the process described in US 4,379,759; US 6,342,566; and US 6,384,142. A general description of in-situ ICPs can be found in POLYPROPYLENE HANDBOOK, E.P. Moore, Ed. (Hanser-Verlag, 1996).
Propylene Polymers (Homopolymers and Copolymers')
[0050] Preferred propylene polymers (homopolymers and copolymers) useful in this invention include those having one or more of the following properties: 1) propylene content of at least 85 wt% (preferably at least 90 wt%, preferably at least 95 wt%, preferably at least 97 wt%, preferably 100 wt%); and/or
2) Mw of 30 to 2,000 kg/mol (preferably 50 to 1 ,000 kg/mol, preferably 90 to 500 kg/mol); and/or
3) Mw/Mn of 1 to 40 (preferably 1.4 to 20, preferably 1.6 to 10, preferably 1.8 to 3.5 , preferably 1.8 to 2.5); and/or
4) branching index (g?) of 0.2 to 2.0 (preferably 0.5 to 1.5, preferably 0.7 to 1.3, preferably 0.9 to 1.1); and/or
5) melt flow rate (MFR) of 1 to 300 dg/min (preferably 5 to 150 dg/min, preferably 10 to 100 dg/min, preferably 20 to 60 dg/min); and/or 6) melting point (Tm, peak second melt) of at least 1000C (preferably at least 1100C, preferably at least 1200C, preferably at least 1300C, preferably at least 1400C, preferably at least 1500C, preferably at least 1600C, preferably at least 165°C); and/or
7) crystallization temperature (T0, peak) of at least 700C (preferably at least 900C, preferably at least 1100C, preferably at least 1300C); and/or
8) heat of fusion (Hf) of 40 to 160 J/g (preferably 50 to 140 J/g, preferably 60 to 120 J/g, preferably 80 to 100 J/g); and/or
9) crystallinity of 5 to 80% (preferably 10 to 75%, preferably 20 to 70%, preferably 30 to 65%, preferably 40 to 60%); and/or
10) propylene meso diads of 90% or more (preferably 92% or more, preferably 94% or more, preferably 96% or more); and/or 11) heat deflection temperature (HDT) of 45 to 14O0C (preferably 60 to 135°C, preferably 75 to 125°C); and/or
12) Gardner impact strength at 23°C of 30 to 1300 J (preferably 40 to 800 J, preferably 50 to 600 J); and/or
13) flexural modulus of 300 to 3000 MPa (preferably 600 to 2500 MPa, preferably 800 to 2000 MPa, preferably 1000 to 1500 MPa).
[0051] In a preferred embodiment, the propylene polymer is selected from polypropylene homopolymer, polypropylene copolymers, and blends thereof. The homopolymer may be atactic polypropylene, isotactic polypropylene, highly isotactic polypropylene, syndiotactic polypropylene, and blends thereof. The copolymer can be a random copolymer, a statistical copolymer, a block copolymer, and blends thereof.
[0052] The method of making the polypropylene is not critical, as it can be made by slurry, solution, gas-phase, high-pressure, or other suitable processes, through the use of catalyst systems appropriate for the polymerization of polyolefms, such as Ziegler-Natta-type catalysts, metallocene-type catalysts, other appropriate catalyst systems or combinations thereof. In a preferred embodiment the propylene polymers are made by the catalysts, activators and processes described in US 6,342,566, US 6,384,142, WO 03/040201, WO 97/19991 and US 5741563. Such catalysts are well known in the art, and are described in, for example, ZIEGLER CATALYSTS (Gerhard Fink, Rolf Mϋlhaupt and Hans H. Brintzinger, eds., Springer- Verlag 1995); Resconi et al., Selectivity in Propene Polymerization with Metallocene Catalysts, 100 CHEM. REV. 1253- 1345 (2000); and I, H METALLOCENE-BASED POLYOLEFINS (Wiley & Sons 2000).
[0053] Polypropylene homopolymers or copolymers useful in the present invention may have some level of isotacticity or syndiotacticity. In one embodiment, the polypropylene is isotactic polypropylene, and in another embodiment, the polypropylene is highly isotactic polypropylene. In a desirable embodiment, the polypropylene is a polypropylene homopolymer having at least 85% (preferably at least 90%) isotactic pentads. In another desirable embodiment, the polypropylene is a polypropylene homopolymer having at least 85% (preferably at least 90%) syndiotactic pentads.
[0054] In a particularly preferred embodiment, the propylene polymers useful herein are produced by a metallocene catalyst system, and have a Mw/Mn of 1.5 to 3 (preferably 1.8 to 2.5) and a CDBI of 80 wt% or more (preferably 90 wt% or more).
[0055] In another embodiment the propylene polymer is a random copolymer, also known as an "RCP," comprising propylene and up to 20 mole % of ethylene or a C4 to C20 olefin, preferably up to 20 mole % ethylene, preferably from 1 to 10 mole % ethylene. [0056] Propylene polymers that are useful in this invention include hPP and RCP grades commercially available from many manufacturers, including ExxonMobil Chemical (including hPP grades sold under the ACHIEVE™ tradename), Basell Polyolefins, Borealis, Dow Chemical, Sunoco Chemical, and Total Petrochemicals.
Ethylene Copolymers [0057] Preferred ethylene copolymers useful in this invention include those having one or more of the following properties:
1) ethylene content of 60 to 90 wt% (preferably 65 to 85 wt%, preferably 65 to 80 wt%, preferably 65 to 75 wt%); and/or
2) ethylene content of 80 to 96 mol% (preferably 82 to 92 mol%, preferably 82 to 88 mol%, preferably 84 to 86 mol%); and/or
3) propylene content of 10 to 20 wt%; and/or
4) butene-1 content of 15 wt% or more (preferably 20 wt% or more, preferably 25 wt% or more); and/or
5) hexene-1 content of 20 wt% or more (preferably 25 wt% or more, preferably 30 wt% or more); and/or
6) octene-1 content of 25 wt% or more (preferably 30 wt% or more, preferably 35 wt% or more); and/or
7) density of 0.91 g/cm3 or less (preferably 0.90 g/cm3 or less, preferably 0.89 g/cm3 or less, preferably 0.88 g/cm3 or less, preferably 0.87 g/cm3 or less, preferably 0.85 g/cm3 or more, preferably 0.855 g/cm3 or more, preferably 0.86 g/cm3 or more, preferably 0.85 to 0.91 g/cm3, preferably 0.85 to 0.90 g/cm3, preferably 0.85 to 0.89 g/cm3, preferably 0.85 to 0.88 g/cm3, preferably 0.855 to 0.88 g/cm3, preferably 0.855 to 0.87 g/cm3, preferably 0.86 to 0.87 g/cm3); and/or
8) heat of fusion (Hf) of 90 J/g or less (preferably 70 J/g or less, preferably 50 J/g or less, preferably 30 J/g or less, preferably 10 to 70 J/g, preferably 10 to 50 J/g, preferably 10 to 30 J/g); and/or
9) crystallinity of 40% or less (preferably 30% or less, preferably 20% or less, preferably at least 5%, preferably 5 to 30%, preferably 5 to 20%); and/or 10) melting point (Tm, peak first melt) of 1000C or less (preferably 900C or less, preferably 800C or less, preferably 700C or less, preferably 600C or less, preferably 500C or less); and/or
11) crystallization temperature (Tc, peak) of 900C or less (preferably 800C or less, preferably 700C or less, preferably 600C or less, preferably 5O0C or less, preferably 400C or less); and/or
12) glass transition temperature (Tg) of -200C or less (preferably -300C or less, preferably -400C or less); and/or
13) Mw of 30 to 2,000 kg/mol (preferably 50 to 1 ,000 kg/mol, preferably 90 to 500 kg/mol); and/or
14) Mw/Mn of 1 to 40 (preferably 1.4 to 20, preferably 1.6 to 10, preferably 1.8 to 3.5, preferably 1.8 to 2.5); and/or 15) branching index (g1) of 0.9 or greater (preferably 0.95 or greater, preferably 0.99 or greater); and/or
16) melt index (MT) of 0.1 to 100 dg/min (preferably 0.3 to 60 dg/min, preferably 0.5 to 40 dg/min, preferably 0.7 to 20 dg/min); and/or
17) CDBI of at least 60 wt% (preferably at least 70 wt%, preferably at least 80 wt%, preferably at least 90 wt%, preferably at least 95 wt%).
[0058] In preferred embodiment, the ethylene copolymer is an ethylene-based plastomer with a density of 0.86 to 0.91 g/cm3 (preferably 0.86 to 0.90 g/cm3, preferably 0.86 to 0.89 g/cm3, preferably 0.86 to 0.88 g/cm3, preferably 0.86 to 0.87 g/cm3). Preferred plastomers comprise less than 85 wt% (preferably less than 75 wt%) ethylene and up to 50 wt% (preferably 20 to 40 wt%) of one or more olefin comonomers selected from propylene and C4-C2O olefins (preferably 1- butene, 1-hexene, and/or 1-octene).
[0059] In another preferred embodiment, the ethylene copolymer is an ethylene elastomer with a density of less than 0.86 g/cm3, comprised of ethylene and at least 30 wt% of one or more C4-C20 olefin comonomers (preferably 1-butene, 1-hexane, and/or 1-octene). [0060] In any embodiment, the ethylene copolymer can be a random copolymer, a statistical copolymer, a block copolymer, and blends thereof.
[0061] The method of making the ethylene copolymer is not critical, as it can be made by slurry, solution, gas-phase, high-pressure, or other suitable processes, through the use of catalyst systems appropriate for the polymerization of polyolefins, such as Ziegler-Natta catalysts, metallocene catalysts, other appropriate catalyst systems or combinations thereof. [0062] In a particularly preferred embodiment, the ethylene copolymers useful herein are produced using a metallocene catalyst system, i.e., a mono- or bis-cyclopentadienyl transition metal catalysts in combination with an activator of alumoxane and/or a non-coordinating anion in solution, slurry, high-pressure, or gas-phase. The catalyst and activator may be supported or unsupported and the cyclopentadienyl rings by may substituted or unsubstituted. For more information on the methods and catalysts/activators to produce such mPE homopolymers and copolymers see WO 94/26816; WO 94/03506; EPA 277,003; EPA 277,004; U.S. Pat. No. 5,153,157; U.S. Pat. No. 5,198,401; U.S. Pat. No. 5,240,894; U.S. Pat. No. 5,017,714; CA 1,268,753; U.S. Pat. No. 5,324,800; EPA 129,368; U.S. Pat. No. 5,264,405; EPA 520,732; WO 92 00333; U.S. Pat. No. 5,096,867; U.S. Pat. No. 5,507,475; EPA 426 637; EPA 573 403; EPA 520 732; EPA 495 375; EPA 500 944; EPA 570 982; WO91/09882; WO94/03506; and U.S. Pat. No. 5,055,438. More generally, preferred plastomers are produced using a single-site catalyst, whether a metallocene catalyst or not, and have a Mw/Mn of 1.5 to 3 (preferably 1.8 to 2.5) and a CDBI of 70% or more (preferably 80% or more, preferably 90% or more).
[0063] Plastomers that are useful in this invention include those available from ExxonMobil Chemical (sold under the EXACT™ tradename), Dow Chemical (sold under the AFFINITY™, ENGAGE™, and FLEXOMER™ tradenames), and Mitsui Chemicals (sold under the TAFMER™ tradename). Examples include: ExxonMobil Chemical EXACT™ Plastomers
Grade Comonomer Density Melt-Index DSC Melting Peak
(g/cm3) (dg/min) (0C, 10°C/min)
3024 butene 0.905 4.5 98
3035 butene 0.900 3.5 88
3128 butene 0.900 1.2 92
4006 butene 0.880 10 60
4011 butene 0.888 2.2 70
4033 butene 0.880 0.8 60
4049 butene 0.873 4.5 55
3040 hexene 0.900 16.5 96
3131 hexene 0.900 3.5 95
3132 hexene 0.900 1.2 96
3139 hexene 0.900 7.5 95
4056 hexene 0.883 2.2 72
4151 hexene 0.895 2.2 89
0201 octene 0.902 1.1 95
0203 octene 0.902 3.0 95
0210 octene 0.902 10 96
0230 octene 0.902 30 95
5061 octene 0.868 0.5 53 5062 octene 0.860 0.5 43
5101 octene 0.902 1.1 98
5171 octene 0.870 1.0 55
5181 octene 0.882 1.1 73
5361 octene 0.860 3.0 36
5371 octene 0.870 5.0 64
8201 octene 0.882 1.1 67
8203 octene 0.882 3.0 73
8210 octene 0.882 10 67
8230 octene 0.882 30 77
EP Rubbers
[0064] Preferred EP Rubbers useful in this invention include those having one or more of the following properties:
1) ethylene content of 25 to 80 wt% (preferably 30 to 75 wt%, preferably 35 to 70 wt%, preferably 40 to 65 wt%); and/or
2) diene content of 15 wt% or less (preferably 12 wt% or less, preferably 9 wt% or less, preferably 6 wt% or less, preferably 3 wt% or less, preferably 0 wt%); and/or
3) density of 0.87 g/cm3 or less (preferably 0.865 g/cm3 or less, preferably 0.86 g/cm3 or less, preferably 0.855 g/cm3 or less); and/or 4) heat of fusion (Hf), if detected, of less than 20 J/g (preferably less than 15 J/g, preferably less than 10 J/g, preferably less than 5 J/g, preferably a heat of fusion is indiscernible); and/or 5) ethylene or propylene crystallinity, if measurable, of less than 10 wt% (preferably less than 7.5 wt%, preferably less than 5 wt%, preferably less than 2.5 wt%, preferably crystallinity is undetected); and/or 6) melting point (Tm, peak first melt), if detected, of 600C or less (preferably 500C or less, preferably 400C or less, preferably 35°C or less); and/or
7) glass transition temperature (Tg) of -30°C or less (preferably -400C or less, preferably -500C or less, preferably -600C or less); and/or
8) Mw of 50 to 3,000 kg/mol (preferably 100 to 2,000 kg/mol, preferably 200 to 1,000 kg/mol); and/or
9) Mw/Mn of 1.5 to 40 (preferably 1.6 to 30, preferably 1.7 to 20, preferably 1.8 to 10, preferably 1.8 to 5, preferably 1.8 to 3, preferably 1.8 to 2.5); and/or
10) Mooney viscosity, ML(l+4) @ 125°C, of 10 to 100 (preferably 15 to 90, preferably 20 to 85). [0065] Particularly preferred EP Rubbers for use herein contain no diene (i.e., an ethylene- propylene copolymers). If diene is present (i.e., an ethylene-propylene-diene terpolymer), preferably the diene is a norbornene-derived diene such as ethylidene norbornene (ENB) or vinylidene norbornene (VNB). Diene content is measured by ASTM D-6047. [0066] The method of making the EP Rubber is not critical, as it can be made by slurry, solution, gas-phase, high-pressure, or other suitable processes, through the use of catalyst systems appropriate for the polymerization of polyolefins, such as Ziegler-Natta catalysts, metallocene catalysts, other appropriate catalyst systems or combinations thereof.
[0067] In a particularly preferred embodiment, the EP Rubbers useful herein are produced using a vanadium-based catalyst system in a solution or slurry process. In another embodiment, the EP Rubbers useful herein are produced using a metallocene-based catalyst system in a solution or slurry process. In yet another embodiment, the EP Rubbers useful herein are produced using any single-sited catalyst system in a solution or slurry process. Preferably, the EP Rubbers made by a vanadium, metallocene, or other single-sited catalyst system has a molecular weight distribution (Mw/Mn) of 1.8 to 2.5.
[0068] EP Rubbers that are useful in this invention include those available from ExxonMobil Chemical (sold under the Vistalon™ tradename), including: ExxonMobil Chemical Vistalon™ EP Rubbers
Grade Mooney Viscosity Ethylene Diene Molecular Weight
(ML1+4, 125°C) (wt%) (wt%) Distribution
404 28 45 — very broad
504 25 60 — broad
606 65 54 — broad
703 21 73 — narrow
706 42 65 — bimodal
707 23 72 — very broad
722 16 72 — narrow
785 30 49 — narrow
805 33 78 — narrow
878 51 60 — narrow
MDV 91-9 18 59 — narrow
1703P 25 77 0.9 VNB very broad
Till 44 57 2.0 ENB broad
3708 52 70 3.4 ENB broad
2504 25 58 4.7 ENB broad
2727 44 56 2.0 ENB broad
4600 90 60 4.5 ENB bimodal
4709 78 75 4.4 ENB narrow
5504 25 45 4.7 ENB medium
5601 72 68 5.0 ENB tailored
6505 53 57 9.2 ENB broad
7000 59 73 5.0 ENB narrow
7001 60 73 5.0 ENB tailored
7500 82 56 5.7 ENB bimodal
7800(P) 20 79 6.0 ENB bimodal
8600 81 58 8.9 ENB bimodal
8609 83 68 8.0 ENB bimodal 8800 15 73 10.0 ENB bimodal
9500 72 60 11.0 ENB bimodal
Non-Functionalized Plasticizer (NFP)
[0069] The hetero-phase polyolefin compositions of the present invention include at least one non-fimctionalized plasticizer ("NFP"). The classes of materials described herein that are useful as non-functionalized plasticizers can be utilized alone or admixed other NFPs described herein to obtain desired properties. Any NFP useful in the present invention may also be described by any number of, or any combination of, parameters described herein.
[0070] An NFP is defined to be a hydrocarbon liquid compound comprising carbon and hydrogen, having functional groups selected from hydroxide, aryls, substituted aryls, halogens, alkoxys, carboxylates, esters, carbon unsaturation, acrylates, oxygen, nitrogen, and carboxyl present to an unappreciable extent. By "unappreciable extent", it is meant that these groups and compounds comprising these groups are not deliberately added to the NFP, and if present at all for any reason, are present at less than 5 wt%. Preferably the these groups and compounds are present at less than 4 wt%, preferably less than 3 wt%, preferably less than 2 wt%, preferably less than 1 wt%, preferably less than 0.7 wt%, preferably less than 0.5 wt%, preferably less than 0.3 wt%, preferably less than 0.1 wt%, preferably less than 0.05 wt%, preferably less than 0.01 wt%, preferably less than 0.001 wt%), based upon the weight of the NFP.
[0071] In one embodiment, aromatic moieties (including compounds whose molecules have the ring structure characteristic of benzene, naphthalene, phenanthrene, anthracene, etc.) are substantially absent from the NFP. In another embodiment, naphthenic moieties (including compounds whose molecules have a saturated ring structure such as would be produced by hydrogenating benzene, naphthalene, phenanthrene, anthracene, etc.) are substantially absent from the NFP.
[0072] In another embodiment, the NFP is a hydrocarbon that contains olefinic unsaturation to an unappreciable extent. By "unappreciable extent of olefinic unsaturation" it is meant that the carbons involved in olefinic bonds account for less than 10% (preferably less than 8%, preferably less than 6%, preferably less than 4%, preferably less than 2%, preferably less than 1%, preferably less than 0.7%, preferably less than 0.5%, preferably less than 0.3%, preferably less than 0.1%, preferably less than 0.05%, preferably less than 0.01%, preferably less than 0.001%) of the total number of carbons. In some embodiments, the percent of carbons of the NFP involved in olefinic bonds is between 0.001 and 10% of the total number of carbon atoms in the NFP (preferably between 0.01 and 5%, preferably between 0.1 and 2%, preferably less than 1%). [0073] In another embodiment, the NFP comprises Ce to C2oo paraffins, and Cg to Cioo paraffins in another embodiment. In another embodiment, the NFP consists essentially of Ce to C200 paraffins, or essentially of C8 to Cioo paraffins in another embodiment. In yet another embodiment, the NFP comprises C2o to C1S0O paraffins, preferably C25 to C500 paraffins, preferably C25 to C500 paraffins, preferably C3o to C500 paraffins, preferably C40 to C500 paraffins, preferably C40 to C250 paraffins, preferably C30 to C150 paraffins, preferably C20 to Cioo paraffins. In a preferred embodiment, the NFP comprises oligomers of C5 to C24 olefins. [0074] Particularly preferred NFPs include a) isoparaffins, b) PAOs, c) Group IQ Mineral Oils, d) high purity hydrocarbon fluids derived from a so-called Gas-To-Liquids processes, and e) mineral oils; with a viscosity index greater than 100 (preferably greater than 120), pour point less than -15°C (preferably less than -200C), specific gravity less than 0.86 (preferably less than 0.855), and flash point greater than 2000C (preferably greater than 2300C).
Isoparafflns
[0075] In one embodiment of the present invention, the NFP is an isoparaffin-rich hydrocarbon liquid with a pour point of -500C or less (preferably -6O0C or less) and a specific gravity of 0.84 or less (preferably 0.83 or less). By "isoparaffin-rich" is meant that the NFP comprises at least 50 wt% (preferably at least 60 wt%, preferably at least 70 wt%, preferably at least 80 wt%, preferably at least 90 wt%, preferably 100 wt%) of C6 to Q5O (preferably C6 to Cioo, preferably C6 to C25, preferably Cs to C20) isoparaffms. Preferably the paraffin chains possess C1 to C1O alkyl branching along at least a portion of each paraffin chain, where any combination of regio and stereo placement of the alkyl branches may be involved. Isoparaffin liquids may also include a minor amount of (less than 50 wt%, preferably less than 30 wt%, preferably less than 10 wt%) of cycloparafflns with isoparaffϊnic branched side chains. Isoparaffms may include any combination of regio and stereo placement of the alkyl branches. [0076] In one embodiment, the number-average molecular weight of the isoparaffin-rich fluid is in the range of 100 to 1000 (preferably 120 to 500, preferably 150 to 300) g/mol. Li another embodiment, the isoparaffin-rich NFP has a kinematic viscosity at 400C of l to 15 cSt (preferably 2 to 10 cSt). In another embodiment, the isoparaffin-rich NFP has a kinematic viscosity at 25°C of 1 to 30 cSt (preferably 2 to 25 cSt, preferably 3 to 20 cSt, preferably 5 to 15 cSt) and a glass transition temperature (Tg) that cannot be determined by ASTM E 1356 or if it can be determined then it is less than 00C (preferably less than -100C, preferably less than -200C, preferably less than -3O0C).
[0077] In another embodiment the isoparaffin-rich NFP has one or more of the following properties:
1. a pour point of -400C or less (preferably -500C or less, preferably -6O0C or less); and/or 2. a glass transition temperature (Tg) determined by ASTM E 1356 of less than -200C (preferably less than -300C, preferably less than -500C), or a Tg that can not be determined by ASTM E 1356; and/or
3. a kinematic viscosity at 250C of from 1 to 30 cSt; and/or 4. a number average molecular weight (Mn) between 2,000 and 100 g/mol (preferably between 1500 and 150 g/mol, preferably between 1000 and 200 g/mol); and/or
5. a flash point (ASTM D 56 or D 93) of 50 to 2000C; and/or
6. a specific gravity (15.6/15.6°C) of less than 0.85 (preferably less than 0.84, preferably less than 0.83, preferably from 0.65 to 0.85, preferably from 0.70 to 0.84, preferably from 0.75 to 0.83, preferably from 0.800 to 0.840); and/or
7. a density of from 0.70 to 0.85 g/cm3; and/or
8. a distillation range having a difference between the upper and lower temperatures of 400C or less (preferably 300C or less, preferably 200C or less, preferably 100C or less, preferably between 6 and 4O0C); and/or 9. a final boiling point of from 115 to 5000C (preferably from 200 to 4500C, preferably from 250 to 4000C).
[0078] Suitable isoparaffin-rich hydrocarbon liquids are described in, for example US 3818105, US 3439088 and US 6197285, and are commercially available under the tradename ISOP AR™ (ExxonMobil Chemical), some of which are summarized in the table below. Other suitable isoparaffin-rich hydrocarbon liquids are commercial available under the trade names SHELLSOL™ (Royal Dutch/Shell), SOLTROL™ (Chevron Phillips) and SASOL™ (Sasol Limited). The percentage of carbons in chain-type paraffinic structures (Cp) in such liquids is close to 100% (95% or more). ISOPAR™ Series Isoparaffms
_, . KV @ 25°C pour point specific flash point ° β (cSt) (°C) gravity (0C)
H 1.8 -63 0.76 53
K 1.9 -60 0.76 55
L 2.0 -57 0.77 62
M 3.8 -57 0.79 92
V 14.8 -63 0.82 130 [0079] In another embodiment, the isoparaffin-rich NFP is a mixture of branched and normal paraffins having 6 to 50 (preferably 8 to 40, preferably 10 to 30) carbon atoms in the molecule. The isoparaffin composition has a ratio of branch paraffin to n-paraffin of 1:1 to 100:1 (preferably 1 :1 to 10:1). The distribution of branches in the isoparaffms of the mixture is such that at least 50% (preferably at least 70%) are methyl branches, with less than 50% (preferably less than 30%) of branches with carbon number greater than 1 (for example, ethyl, propyl, butyl or the like). The isoparaffinic mixture boils within a range of from 100 to 3500C (preferably from 110 to 3200C) and with a narrow boiling range (preferably 350C or less). These branch paraffin/n-paraffm blends are described in, for example, US 5906727. Polyalphaolefins
[0080] In another embodiment of the present invention, the NFP comprises a polyalphaolefin (PAO) liquid with a pour point of -100C or less and a kinematic viscosity at 1000C of 3 cSt or more. In general, a PAO liquid comprises hydrocarbon oligomers manufactured by catalytic oligomerization of alpha-olefins, preferably linear alpha-olefins. A PAO may be characterized by any type of tacticity, including isotactic or syndiotactic and/or atactic, and by any degree of tacticity, including isotactic-rich or syndiotactic-rich or fully atactic. PAO liquids are described in, for example, US 3149178; US 4827064; US 4S27073; US 5171908; and US 5783531 and in SYNTHETIC LUBRICANTS AND HIGH-PERPORMANCE FUNCTIONAL FLUIDS, Leslie R. Rudnick & Ronald L. Shubkin, eds. (Marcel Dekker, 1999), p. 3-52. A PAO is not a polymer. [0081] PAO liquids may be conveniently prepared by the oligomerization of an α-olefin in the presence of a polymerization catalyst, such as a Friedel-Crafts catalyst (including, for example, AlCl3, BF3, and complexes of BF3 with water, alcohols, carboxylic acids, or esters), a coordination complex catalyst (including, for example, the ethylaluminum sesquichloride + TiCl4 system), or a homogeneous or heterogeneous (supported) catalyst more commonly used to make polyethylene and/or polypropylene (including, for example, Ziegler-Natta catalysts, metallocene or other single-site catalysts, and chromium catalysts).
[0082] hi one embodiment, the PAO comprises C15 to C1SOo (preferably C2o to C1OOO* preferably C30 to CSOOJ preferably C35 to C4oo5 most preferably C40 to C250) oligomers of alpha- olefins. These oligomers are dimers, trimers, tetramers, pentamers, etc. In another embodiment, the PAO comprises C3 to C24 (preferably C5 to C18, preferably C6 to C14, even preferably Cs to C12, most preferably C10) branched or linear alpha-olefins, provided that C3 and C4 alpha-olefins are present at 10 wt% or less. In another embodiment, the PAO comprises C3 to C24 (preferably C5 to C1S, preferably C6 to Ci4, most preferably C8 to C12) linear alpha-olefins (LAOs), provided that C3 and C4 LAOs are present at 10 wt% or less. Suitable olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1- tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, and blends thereof. Oligomers of LAOs with only even carbon numbers between 6 and 18 (inclusive) are particularly preferred. [0083] hi one embodiment, a single LAO is used to prepare the oligomers. In this case, a preferred embodiment involves the oligomerization of 1-decene, and the PAO is a mixture of oligomers (including, for example, dimers, trimers, tetramers, pentamers, and higher) of 1- decene. In another embodiment, the PAO comprises oligomers of two or more C3 to Ci 8 LAOs (preferably C5 to C1S LAOs), to make 'bipolymer' or 'terpolymer' or higher-order copolymer combinations, provided that C3 and C4 LAOs are present at 10 wt% or less. In this case, a preferred embodiment involves the oligomerization of a mixture of 1-octene, 1-decene, and 1- dodecene, and the PAO is a mixture of oligomers (for example, dimers, trimers, tetramers, pentamers, and higher) of 1-octene/l-decene/l-dodecene 'terpolymer'.
[0084] In another embodiment, the PAO comprises oligomers of a single alpha-olefin species having a carbon number of 5 to 24 (preferably 6 to 18, preferably 8 to 12, most preferably 10). In another embodiment, the NFP comprises oligomers of mixed alpha-olefins (i.e., involving two or more alpha-olefin species), each alpha-olefin having a carbon number of 3 to 24 (preferably 5 to 24, preferably 6 to 18, most preferably 8 to 12), provided that alpha-olefins having a carbon number of 3 or 4 are present at 10 wt% or less. In a particularly preferred embodiment, the PAO comprises oligomers of mixed alpha-olefins (i.e., involving two or more alpha-olefin species) where the weighted average carbon number for the alpha-olefin mixture is 6 to 14 (preferably 8 to 12, preferably 9 to 11).
[0085] In another embodiment, the PAO comprises oligomers of one or more α-olefin with repeat unit formulas of: -[CHR-CH2]- where R is a C3 to Ci 8 saturated hydrocarbon branch. Preferably, R is constant for all oligomers. In another embodiment, there is a range of R substituents covering carbon numbers from 3 to 18. Preferably, R is linear, i.e., R is (CH2)zCH3, where z is 2 to 17 (preferably 3 to 11, preferably 4 to 9). Optionally, R may contain one methyl or ethyl branch, i.e.,
R is (CH2)m[CH(CH3)](CH2)nCH3 or (CH2)χ[CH(CH2CH3)](CH2)yCH3, where (m + n) is 1 to 15 (preferably 1 to 9, preferably 3 to 7) and (x ■+■ y) is 1 to 14 (preferably 1 to 8, preferably 2 to 6). Preferably m > n. Preferably m is 0 to 15 (preferably 2 to 15, preferably 3 to 12, preferably 4 to 9) and n is 0 to 10 (preferably 1 to 8, preferably 1 to 6, preferably 1 to 4). Preferably x > y. Preferably x is 0 to 14 (preferably 1 to 14, preferably 2 to 11, preferably 3 to 8) and y is 0 to 10 (preferably 1 to 8, preferably 1 to 6, preferably 1 to 4.) Preferably, the repeat units are arranged in a head-to-tail fashion with minimal heat-to-head connections. [0086] The PAO may be atactic, isotactic, or syndiotactic. In one embodiment, the PAO has essentially the same population of meso [m] and racemϊc [r] dyads (preferably neither [m] nor [r] greater than 60%, preferably neither greater than 55%) as measured by 13C-NMR, making it atactic. In another embodiment, the PAO has more than 60% (preferably more than 70%, preferably more than 80%, preferably more than 90%) meso dyads [m]. In another embodiment, the PAO has more than 60% (preferably more than 70%, preferably more than 80%, preferably more than 90%) racemic dyads [r]. In one embodiment, [m]/[r] determined by 13C-NMR is between 0.9 and 1.1 in one embodiment, [m]/[r] is greater than 1 in another embodiment, and [m]/[r] is less than 1 in yet another embodiment.
[0087] Preferred PAOs have a "branching ratio" as defined in US 4827064 and measured according to the method described therein, of 0.20 or less (preferably 0.19 or less, preferably 0.18 or less, preferably 0.17 or less, preferably 0.15 or less, preferably 0.12 or less, preferably 0.10 or less).
[0088] hi one embodiment of the present invention, the PAO has a number average molecular weight of from 100 to 20,000 g/mol (preferably 300 to 15,000 g/mol, preferably 400 to 10,000 g/mol, preferably 500 to 5,000 g/mol, preferably 600 to 3,000 g/mol, preferably 600 to 1,500 g/mol).
[0089] In a preferred embodiment, the PAO has a kinematic viscosity at 1000C of 3 cSt or more (preferably 5 cSt or more, preferably 6 cSt or more, preferably 8 cSt or more, preferably 10 cSt or more, preferably 20 cSt or more, preferably 30 cSt or more, preferably 40 cSt or more, preferably 100 or more, preferably 150 cSt or more). In another embodiment, the PAO has a kinematic viscosity at 1000C of 300 cSt or less (preferably 100 cSt or less). In another embodiment, the PAO has a kinematic viscosity at 1000C of 3 to 3,000 cSt (preferably 4 to 1,000 cSt, preferably 6 to 300 cSt, preferably 8 to 150 cSt, preferably 8 to 100 cSt, preferably 8 to 40 cSt). In another embodiment, the PAO has a kinematic viscosity at 1000C of 10 to 1000 cSt (preferably 10 to 300 cSt, preferably 10 to 100 cSt). In yet another embodiment, the PAO has a kinematic viscosity at 1000C of about 4 to 8 cSt. In yet another embodiment, the PAO has a kinematic viscosity at 1000C of 1 to 3 cSt.
[0090] In another preferred embodiment, the PAO has a Viscosity Index of 120 or more (preferably 130 or more, preferably 140 or more, preferably 150 or more, preferably 170 or more, preferably 190 or more, preferably 200 or more, preferably 250 or more, preferably 300 or more). In another embodiment, the PAO or blend of PAOs has a viscosity Index of 120 to 350 (preferably 130 to 250).
[0091] In yet another preferred embodiment, the PAO has a pour point of -1O0C or less (preferably -200C or less, preferably -25°C or less, preferably -300C or less, preferably -35°C or less, preferably -400C or less, preferably -500C or less). In another embodiment, the PAO or blend of PAOs has a pour point of -15 to -700C (preferably -25 to -600C).
[0092] In yet another preferred embodiment, the PAO has a glass transition temperature (Tg) of -400C or less (preferably -500C or less, preferably -6O0C or less, preferably -700C or less, preferably -800C or less). In another embodiment, the PAO or blend of PAOs has a Tg of -50 to -1200C (preferably -60 to -1000C, preferably -70 to -900C).
[0093] In yet another preferred embodiment, the PAO has a flash point of 2000C or more (preferably 2100C or more, preferably 2200C or more, preferably 2300C or more), preferably between 240°C and 2900C. [0094] In yet another preferred embodiment, the PAO has a specific gravity (15.6/15.6°C) of 0.86 or less (preferably 0.855 or less, preferably 0.85 or less, preferably 0.84 or less).
[0095] Particularly preferred PAOs are those having A) a flash point of 2000C or more (preferably 2100C or more, preferably 2200C or more, preferably 230°C or more); and B) a pour point less than -200C (preferably less than -250C, preferably less than -300C, preferably less than -35°, preferably less than -400C) and/or a kinematic viscosity at 1000C of 10 cSt or more (preferably 35 cSt or more, preferably 40 cSt or more, preferably 50 cSt or more).
[0096] Further preferred PAOs have a kinematic viscosity at 1000C of at least 3 cSt (preferably at least 6 cSt, preferably at least 8 cSt, most preferably at least 10 cSt); a viscosity index of at least 120 (preferably at least 130, preferably at least 140, most preferably at least 150); a pour point of -100C or less (preferably -200C or less, preferably -300C or less, most preferably -400C or less); and a specific gravity (15.6/15.6°C) of 0.86 or less (preferably 0.855 or less, preferably 0.85 or less, most preferably 0.84 or less).
[0097] The PAO may be comprised of one or more distinct PAO components. In one embodiment, the NFP is a blend of one or more PAOs with different compositions (e.g., different α-olefin(s) were used to make the oligomers) and/or different physical properties (e.g., kinematic viscosity, pour point, viscosity index, and/or glass transition temperature).
[0098] Desirable PAOs are available as SpectraSyn™ and SpectraSyn Ultra™ from ExxonMobil Chemical in Houston, Texas (previously sold under the SHF and SuperSyn™ tradenames by ExxonMobil Chemical Company), some of which are summarized in the table below. Other useful PAOs include Synfluid™ available from ChevronPhillips Chemical Company (Pasedena, Texas), Durasyn™ available from Innovene (Chicago, Illinois), Nexbase™ available from Neste Oil (Keilaniemi, Finland), and Synton™ available from Chemtura Corporation (Middlebury, Connecticut). The percentage of carbons in chain-type paraffϊnic structures (CP) is close to 100% (typically greater than 98% or even 99%) for PAOs. SpectraSyn™ Series Polyalphaolefins
Grade KV @ κv @ VI Pour Point, 0C Specific Flash
ID 1000C, cSt 400C, cSt gravity Point, 0C
4 4 19 126 -66 0.820 220
Plus 4 4 17 122 -60 0.820 228
6 6 31 138 -57 0.827 246
Plus 6 6 30 140 -54 0.827 246
8 8 48 139 -48 0.833 260
10 10 66 137 -48 ' 0.835 266
40 39 396 147 -36 0.850 281
100 100 1240 170 -30 0.853 283
Ultra 150 1,500 218 -33 0.850 > 265
150
Ultra 300 3,100 241 -27 0.852 > 265
300
Ultra 1,000 10,000 307 -18 0.855 > 265
1000
[0099] This invention also relates to hetero-phase polyolefm compositions comprising one or more polyolefins, preferably polypropylene, and one or more non-functionalized plasticizers where the non-functionalized plasticizer comprises a polyalphaolefin comprising oligomers of C5 to C18 olefins (preferably Ce to C14, preferably C8 to C12, preferably Qo); having a kinematic viscosity at 1000C of 5 cSt or more (preferably 8 cSt or more, preferably 10 cSt or more); a viscosity index of 120 or more (preferably 130 or more); and a pour point of -100C or less (preferably -200C or less, preferably -300C or less). [0100] This invention also relates to polyolefm compositions comprising a polypropylene- based TPO and one or more non-functionalized plasticizers where the non-functionalized plasticizer comprises oligomers of linear olefins having 5 to 18 carbon atoms (preferably 6 to 14 carbon atoms, preferably 8 to 12 carbon atoms, preferably 10 carbon atoms); a kinematic viscosity at 1000C of 5 to 300 cSt (preferably 8 to 150 cSt, preferably 10 to 100 cSt); a viscosity index of 120 or more (preferably 130 or more, preferably 140 or more); and a pour point of -200C or less (preferably -300C or less, preferably -400C or less). Polvbutenes
[0101] In some embodiments of the present invention, the NFP comprises oligomers of C4 olefins (including 1-butene, 2-butene, isobutylene, and butadiene, and mixtures thereof) and up to 10 wt% other olefins, often referred to as a "polybutenes" liquid when the oligomers comprise primarily isobutylene and 1-butene. As used herein, the term "polybutenes" also includes homopolymer oligomers of isobutylene or 1-butene, copolymer oligomers of a C4 raffϊnate stream, and copolymer oligomers of C4 olefins with ethylene and/or propylene and/or Cs olefins.
Such liquids are commonly used as additives for polyolefins; e.g. to introduce tack or as a processing aid. The ratio of C4 olefin isomers can vary by manufacturer and by grade, and the material may or may not be hydrogenated after synthesis. Polybutenes are described in, for example, SYNTHETIC LUBRICANTS AND HIGH-PERFORMANCE FUNCTIONAL FLUIDS (Leslie R. Rudnick & Ronald L. Shubkin, ed., Marcel Dekker 1999), p. 357-392. [0102] Preferred polybutenes include those in which isobutylene derived units comprise 40 to 100 wt% (preferably 40 to 99 wt%, preferably 40 to 96 wt%) of the polymer; and/or the 1-butene derived units comprise 0 to 40 wt% (preferably 2 to 40 wt%) of the copolymer; and/or the 2- butene derived units comprise 0 to 40 wt% (preferably 0 to 30 wt%, preferably 2 to 20 wt%) of the polymer. [0103] Suitable polybutenes may have a kinematic viscosity at 1000C of 3 to 50,000 cSt (more commonly 5 to 3000 cSt), a pour point of -60 to 100C (more commonly -40 to 00C), and a number-average molecular weight of 300 to 10,000 g/mol (more commonly 500 to 2,000 g/mol). Note that, at the same kinematic viscosity or molecular weight, a polybutenes liquid has a higher specific gravity and lower flash point than a PAO liquid. [0104] Desirable polybutenes liquids are commercially available from a variety of sources including Innovene (Indopol™ grades) and Infineum (C-Series grades). When the C4 olefin is exclusively isobutylene, the material is referred to as "polyisobutylene" or PIB. Commercial sources of PIB include Texas Petrochemical (TPC Enhanced PIB grades). When the C4 olefin is exclusively 1-butene, the material is referred to as "poly-n-butene" or PNB. [0105] Properties of some polybutenes liquids made from C4 olefin(s) are summarized in the table below. In general, grades with a flash point of 2000C or more also have a pour point greater than -100C and/or a VI less than 120. The percentage of carbons in chain-type parafQnic structures (CP) is close to 100% (typically greater than 98% or even 99%) for polybutenes. Commercial Examples of Oligomers of C4 olefin(s)
Grade KV @ VI Pour Specific Flash Point,
1000C, cSt Point, 0C gravity 0C
TPC 137 (PIB) 6 132 -51 0.843 120
TPC 1105 (PIB) 220 145 -6 0.893 200
TPC 1160 (PIB) 660 190 +3 0.903 230
Innovene Indopol 52 87 -23 0.869 -150
H-25
Innovene Indopol 108 90 -13 0.884 -190
H-50
Innovene Indopol 218 121 -7 0.893 -210
H-100
Infineum C9945 11 74* -34 0.854 170
Infineum C9907 78 103* -15 0.878 204
Infineum C9995 230 131* -7 0.888 212 ftifineum C9913 630 174 +10 0.888 240
Estimated based on the kinematic viscosity at 1000C and 38°C [0106] In a preferred embodiment of the present invention, the NFP is not an oligomer of C4 olefins (i.e., 1-buteπe, 2-butene, isobutylene, butadiene, and mixtures thereof), including polybutenes and/or PIB and/or PNB. In another embodiment, the NFP contains less than 90 wt% (preferably less than 80 wt%, preferably less than 70 wt%, preferably less than 60 wt%, preferably less than 50 wt%, preferably less than 40 wt %, preferably less than 30 wt%, preferably less than 20 wt%, preferably less than 10 wt %, preferably less than 5 wt%, preferably less than 2 wt%, preferably less than 1 wt%, preferably 0 wt %) of C4 olefins, in particular 1- butene and isobutylene. [0107] In yet another embodiment, when an NFP is present, oligomers of C4 olefins (i.e., 1- butene, 2-butene, isobutylene, butadiene, and mixtures thereof) may also be present in the composition. Ih a preferred embodiment, the composition comprises less than 50 wt% (preferably less than 40%, preferably less than 30 wt%, preferably less than 20 wt%, preferably less than 10 wt%, preferably less than 5 wt%, preferably less than 1 wt%, preferably 0 wt%) of oligomers of C4 olefins, including polybutenes and/or PIB and/or PNB.
High Purity Hydrocarbon Fluids
[0108] In another embodiment, the NFP is a high purity hydrocarbon fluid of lubricating viscosity comprising a mixture of C20 to C12O paraffins, 50 wt% or more being isoparaffϊnic hydrocarbons and less than 50 wt% being hydrocarbons that contain naphthenic and/or aromatic structures. Preferably, the mixture of paraffins comprises a wax isomerate lubricant basestock or oil, which includes:
1. hydroisomerized natural and refined waxes, such as slack waxes, deoiled waxes, normal alpha-olefin waxes, microcrystalline waxes, and waxy stocks derived from gas oils, fuels hydrocracker bottoms, hydrocarbon raffinates, hydrocracked hydrocarbons, lubricating oils, mineral oils, polyalphaolefms, or other linear or branched hydrocarbon compounds with carbon number of about 20 or more; and
2. hydroisomerized synthetic waxes, such as Fischer-Tropsch waxes (i.e., the high boiling point residues of Fischer-Tropsch synthesis, including waxy hydrocarbons); or mixtures thereof. Most preferred are lubricant basestocks or oils derived from hydrocarbons synthesized in a Fischer-Tropsch process as part of an overall Gas-to-Liquids (GTL) process.
[0109] In one embodiment, the mixture of paraffins has two or more of the following properties:
1. a naphthenic content of less than 40 wt% (preferably less than 30 wt%, preferably less than 20 wt%, preferably less than 15 wt%, preferably less than 10 wt%, preferably less than 5 wt%, preferably less than 2 wt%, preferably less than 1 wt%) based on the total weight of the hydrocarbon mixture; and/or
2. a normal paraffins content of less than 5 wt% (preferably less than 4 wt%, preferably less than 3 wt%, preferably less than 1 wt%) based on the total weight of the hydrocarbon mixture; and/or
3. an aromatic content of 1 wt% or less (preferably 0.5 wt% or less); and/or
4. a saturates level of 90 wt% or higher (preferably 95 wt% or higher, preferably 98 wt% or higher, preferably 99 wt% or higher); and/or 5. the percentage of carbons in chain-type paraffinic structures (Cp) of 80% or more (preferably 90% or more, preferably 95% or more, preferably 98% or more); and/or 6. a branched paraffin:normal paraffin ratio greater than about 10:1 (preferably greater than 20:1, preferably greater than 50:1, preferably greater than 100:1, preferably greater than 500:1, preferably greater than 1000:1); and/or 7. sidechains with 4 or more carbons making up less than 10% of all sidechains (preferably less than 5%, preferably less than 1%); and/or
8. sidechains with 1 or 2 carbons making up at least 50% of all sidechains (preferably at least 60%, preferably at least 70%, preferably at least 80%, preferably at least 90%, preferably at least 95%, preferably at least 98%); and/or 9. a sulfur content of 300 ppm or less (preferably 100 ppm or less, preferably 50 ppm or less, preferably 10 ppm or less) where ppm is on a weight basis; and/or
10. a nitrogen content of 300 ppm or less (preferably 100 ppm or less, preferably 50 ppm or less, preferably 10 ppm or less) where ppm is on a weight basis; and/or
11. a number-average molecular weight of 300 to 1800 g/mol (preferably 400 to 1500 g/mol, preferably 500 to 1200 g/mol, preferably 600 to 900 g/mol); and/or
12. a kinematic viscosity at 4O0C of 10 cSt or more (preferably 25 cSt or more, preferably between about 50 and 400 cSt); and/or
13. a kinematic viscosity at 100°C ranging from 2 to 50 cSt (preferably 3 to 30 cSt, preferably 5 to 25 cSt, preferably 6 to 20 cSt, preferably 8 to 16 cSt); and/or 14. a viscosity index (VI) of 80 or greater (preferably 100 or greater, preferably 120 or greater, preferably 130 or greater, preferably 140 or greater, preferably 150 or greater, preferably 160 or greater, preferably 180 or greater); and/or
15. a pour point of -5°C or lower (preferably -100C or lower, preferably -15°C or lower, preferably -200C or lower, preferably -25°C or lower, preferably -300C or lower); and/or 16. a flash point of 2000C or more (preferably 2200C or more, preferably 2400C or more, preferably 2600C or more); and/or
17. a specific gravity (15.6°C/15.6°C) of 0.86 or less (preferably 0.85 or less, preferably 0.84 or less); and/or 18. an aniline point of 1200C or more; and/or 19. a bromine number of 1 or less.
[0110] In a preferred embodiment, the mixture of paraffins comprises a GTL basestock or oil. GTL basestocks and oils are fluids of lubricating viscosity that are generally derived from waxy synthesized hydrocarbons, that are themselves derived via one or more synthesis, combination, transformation, and/or rearrangement processes from gaseous carbon-containing compounds and hydrogen-containing compounds as feedstocks, such as: hydrogen, carbon dioxide, carbon monoxide, water, methane, ethane, ethylene, acetylene, propane, propylene, propyne, butane, butylenes, and butynes. Preferably, the feedstock is "syngas" (synthesis gas, essentially CO and H2) derived from a suitable source, such as natural gas and/or coal. GTL basestocks and oils include wax isomerates, comprising, for example, hydroisomerized synthesized waxes, hydroisomerized Fischer-Tropsch (F-T) waxes (including waxy hydrocarbons and possible analogous oxygenates), or mixtures thereof. GTL basestocks and oils may further comprise other hydroisomerized basestocks and base oils. Particularly preferred GTL basestocks or oils are those comprising mostly hydroisomerized F-T waxes and/or other liquid hydrocarbons obtained by a F-T synthesis process.
[0111] The synthesis of hydrocarbons, including waxy hydrocarbons, by F-T may involve any suitable process known in the art, including those involving a slurry, a fixed-bed, or a fluidized- bed of catalyst particles in a hydrocarbon liquid. The catalyst may be an amorphous catalyst, for example based on a Group VHI metal such as Fe, Ni, Co, Ru, and Re on a suitable inorganic support material, or a crystalline catalyst, for example a zeolitic catalyst. The process of making a lubricant basestock or oil from a waxy stock is characterized as a hydrodewaxing process. A hydrotreating step, while typically not required for F-T waxes, can be performed prior to hydrodewaxing if desired. Some F-T waxes may benefit from removal of oxygenates while others may benefit from oxygenates treatment prior to hydrodewaxing. The hydrodewaxing process is typically conducted over a catalyst or combination of catalysts at high temperatures and pressures in the presence of hydrogen. The catalyst may be an amorphous catalyst, for example based on Co, Mo, W, etc. on a suitable oxide support material, or a crystalline catalyst, for example a zeolitic catalyst such as ZSM-23 and ZSM-48 and others disclosed in US patents 4906350, often used in conjunction with a Group VDI metal such as Pd or Pt. This process may be followed by a solvent and/or catalytic dewaxing step to lower the pour point of the hydroisomerate. Solvent dewaxing involves the physical fractionation of waxy components from the hydroisomerate. Catalytic dewaxing converts a portion of the hydroisomerate to lower boiling hydrocarbons; it often involves a shape-selective molecular sieve, such as a zeolite or silicoaluminophosphate material, in combination with a catalytic metal component, such as Pt, in a fixed-bed, fluidized-bed, or slurry type process at high temperatures and pressures in the presence of hydrogen.
[0112] Useful catalysts, processes, and compositions for GTL basestocks and oils, Fischer- Tropsch hydrocarbon derived basestocks and oils, and wax isomerate hydroisomerized basestocks and oils are described in, for example, U.S. Patents 2,817,693; 4,542,122; 5,5456,74; 4,568,663; 4,621,072; 4,663,305; 4,897,178; 4,900,407; 4,921,594; 4,923,588; 4,937,399; 4,975,177; 5,059,299; 5,158,671; 5,182,248; 5,200,382; 5,290,426; 5,516,740; 5,580,442; 5,885,438; 5,935,416; 5,935,417; 5,965,475; 5,976,351; 5,977,425; 6,025,305; 6,080,301; 6,090,989; 6,096,940; 6,103,099; 6,165,949; 6,190,532; 6,332,974; 6,375,830; 6,383,366; 6,475,960; 6,620,312; and 6,676,827; European Patents 324528, 532116, 532118, 537815, 583836, 666894, 668342, 776959; WO patent applications 97/31693, 99/20720, 99/45085, 02/64710, 02/64711, 02/70627, 02/70629, 03/33320; and British Patents 1350257; 1390359; 1429494; and 1440230. Particularly favorable processes are described in European Patent Applications 464546 and 464547. Processes using Fischer-Tropsch wax feeds are described in U,S, Patent Nos. 4,594,172; 4,943,672; 6,046,940; 6,103,099; 6,332,974; 6,375,830; and 6,475,960.
[0113] Desirable GTL-derived fluids are expected to become broadly available from several sources, including Chevron, ConocoPhillips, ExxonMobil, Sasol, SasolChevron, Shell, Statoil, and Syntroleum. [0114] This invention also relates to plasticized polyolefm compositions comprising one or more polyolefins and one or more non-functionalized plasticizers, where one or more NFP is a high purity hydrocarbon fluid derived from a GTL process comprising a mixture of paraffins of carbon number ranging from about C20 to Ci 00, a molar ratio of isoparaffinsrn-paraffms greater than about 50:1, the percentage of carbons in paraffinic structures (Cp) of 98% or more, a pour point ranging from about -20 to -6O0C, and a kinematic viscosity at 1000C ranging from about 6 to 20 cSt.
[0115] As used herein, the following terms have the indicated meanings: "hydroisomerized" describes a catalytic process in which normal paraffins and/or slightly branched isoparaffms are converted by rearrangement into more branched isoparaffins (also known as "isodewaxing"); "wax" is a hydrocarbonaceous material existing as a solid at or near room temperature, with a melting point of 00C or above, and consisting predominantly of paraffinic molecules, most of which are normal paraffins; "slack wax" is the wax recovered from petroleum oils such as by solvent dewaxing, and may be further hydrotreated to remove heteroatoms. Group III Mineral Oils
[0116] In another embodiment, the NFP comprises a Group IH Mineral Oil. Preferably the NFP has a saturates levels of 90% or more (preferably 92% or more, preferably 94% or more,' preferably 95% or more, preferably 98% or more); a sulfur content of less than 0.03% (preferably between 0.001 and 0.01%); and a VI of 120 or more (preferably 130 or more, preferably 140 or more). Preferably the Group HI Mineral Oil has a kinematic viscosity at 1000C of 3 to 50, preferably 4 to 40 cSt, preferably 6 to 30 cSt, preferably 8 to 20; and/or a number average molecular weight of 300 to 5,000 g/mol, preferably 400 to 2,000 g/mol, preferably 500 to 1,000 g/mol. Preferably the Group HI Mineral Oil has a pour point of -100C or less, a flash point of 2000C or more, and a specific gravity (15.6°C/15.6°C) of 0.86 or less. [0117] Preferably, the Group m Mineral Oil is a Group m basestock. Desirable Group IH basestocks are commercially available from a number of sources and include those described in the table below. The percentage of carbons in chain-type paraffinic structures (Cp) in such liquids is greater than 80%.
Commercially available Group III Basestocks
KV @ 1000C, VI Pour Point, Specific Flash cSt 0C gravity Point, 0C
UCBO 4R1 4.1 127 -18 0.826 . 216
UCBO 7Rl 7.0 135 -18 0.839 250
Nexbase 3043 2 4.3 124 -18 0.831 224
Nexbase 30502 5.1 126 -15 0.835 240
Nexbase 30602 6.0 128 -15 0.838 240
Nexbase 30802 8.0 128 -15 0.843 260
Yubase YU-43 4.2 122 -15 0.843 230
Yubase YU-63 6.5 131 -15 0.842 240
Yubase YU-83 7.6 128 -12 0.850 260
Ultra-S 44 4.3 123 -20 0.836 220
Ultra-S 64 5.6 128 -20 0.839 234
Ultra-S 84 7.2 127 -15 0.847 256
VHVI 45 4.6 128 -21 0.826
VHVI 85 8.0 127 -12 0.850 248
Visom 46 4.0 210
Visom 66 6.6 148 -18 0.836 250 1 Available from ChevronTexaco (USA).
2 Available from Neste Oil (Finland).
3 Available from SK Corp (South Korea). 4 Available from ConocoPhillips (USA) / S-OiI (South Korea).
5 Available from PetroCanada (Canada).
6 Available from ExxonMobil (USA).
Exceptional Paraffinic Process Oils [0118] In another embodiment, the NFP is an Exceptional Paraffinic Process Oil, which is a paraffinic process oil with
A) a viscosity index less than 120 (preferably 90 to 119), and
B) a Cp of 65% or more (preferably 68% or more, preferably 70% or more, preferably 75% or more, preferably 80% or more), and C) a CA of 1 % or less (preferably 0.5% or less, preferably 0%), and
D) a kinematic viscosity at 400C of 80 cSt or more (preferably 90 cSt or more, preferably 100 cSt or more, preferably 120 cSt or more, preferably 150 cSt or more, preferably 200 cSt or more, preferably 250 cSt or more, preferably 300 cSt or more), and
E) a pour point of -15°C or less (preferably -18°C or less, preferably -200C or less, preferably -25°C or less, preferably -300C or less, preferably -35°C or less).
[0119] Examples of commercially available paraffinic process oils are described in the tables below; each has a viscosity index less than 120, so none are Group El Mineral Oils. Furthermore, all have less than 80% carbons in paraffinic chain-like structures (Cp < 80%), meaning they also all have more than 20% carbons in aromatic and/or naphthenic ring-like structures (CA + CN)- Conventional Paraffinic Process Oils, as shown in the first table, are low viscosity and/or have relatively high pour points. The Exceptional Paraffinic Process Oils in the second table are examples from a very select subcategory of paraffinic process oils that have a kinematic viscosity at 400C of 80 cSt or more (indicating the potential for high permanence) and a pour point of -15°C or less (indicating the potential for high plasticization efficiency). Commercial Examples of Conventional Paraffinic Process Oils κv @ KV @ VI Pour Specific Flash Cp %
4O0C cSt 1000CcSt Point gravity Point 0C
0C
Drakeol 34 * 76 9 99 -12 0.872 254 68
Paralux 1001R 20 4 99 -17 0.849 212 68
2
Paralux 2401R 43 6 101 -12 0.866 234 66
2
Sunpar 1203 41 6 106 -15 0.872 228 68
Sunpar 1503 94 11 97 -12 0.881 245 65
Sunpar 22803 475 31 95 -9 0.899 305 67
Plastol 1354 24 5 104 -9 0.865 210 67
Plastol 5374 103 11 97 -3 0.880 240 66
Plastol 21054 380 30 110 -15 0.885 270 Flexon 8434 30 5 91 -12 0.869 218 65
Flexon 8654 106 11 93 _3 0.879 252 69
Flexon 8154 457 32 101 -9 0.895 310 67
Shellflex 2105 19 4 95 -18 0.860 216 66
Shellflex 3305 70 9 95 -10 0.875 256 68
Shellflex 8105 501 33 95 -9 0.896 324 69
Diana PW326 31 5 104 -18 0.862 226 67
1 Available from Penreco (USA).
2 Available from Chevron (USA).
3 Available from Sunoco (USA).
4 Available from ExxonMobil (USA).
5 Available from Royal Dutch Shell (UK/Netherlands).
6 Available from Idemitsu (Japan).
Commercial Examples of Exceptional Paraffinic Process Oils
KV @ KV @ VI Pour Specific Flash CP
40°C cSt 1000CcSt Point 0C gravity Point 0C %
Paralux όOOIR 1 118 12 102 -21 0.875 274 70
Diana PW902 90 11 105 -22 0.872 262 71
Diana PW3802 376 26 106 -19 0.877 293 73
1 Available from Chevron (USA).
2 Available from Idemitsu (Japan). [0120] Preferably, the NFP is not a naphthenic mineral oil (also called a naphthenic process oil or a naphthenic extender oil), nor is it an aromatic mineral oil (also called an aromatic process
011 or an aromatic extender oil). More preferably, naphthenic and aromatic mineral oils are substantially absent from the compositions of the present invention. In certain embodiments, paraffinic mineral oils with a kinematic viscosity at 40°C of less than 80 cSt and a pour point of greater than -15°C are substantially absent from the compositions of the present invention.
General Characteristics of Useful NFPs
[0121] Ih preferred embodiments, the NFP has a kinematic viscosity at 1000C (KV1Oo) of 3 cSt or more, preferably 4 cSt or more, preferably 5 cSt or more, preferably 6 cSt or more, preferably 8 cSt or more, preferably 10 cSt or more, preferably 20 cSt or more, preferably 40 cSt or more, preferably 6 to 5000 cSt, preferably 8 to 3000 cSt, preferably 10 to 1000 cSt, preferably
12 to 500 cSt, preferably 15 to 400 cSt, preferably 20 to 350 cSt, preferably 35 to 300 cSt, preferably 40 to 200 cSt, preferably 8 to 300 cSt, preferably 6 to 150 cSt, preferably 10 to 100 cSt, preferably less than 50 cSt, wherein a desirable range may be any combination of any lower KVioo limit with any upper KV1Oo limit described herein. [0122] In preferred embodiments, the NFP has a pour point of -10°C or less, preferably -200C or less, preferably -300C or less, preferably -400C or less, preferably -45°C or less, preferably -500C or less, preferably -10 to -1000C, preferably -15 to -800C, preferably -15 to -75°C, preferably -20 to -700C, preferably -25 to -65°C, preferably greater than -1200C, wherein a desirable range may be any combination of any lower pour point limit with any upper pour point limit described herein. In another embodiment, the NFP has a pour point of less than -300C when the kinematic viscosity at 400C is from 20 to 600 cSt (preferably 30 to 400 cSt, preferably 40 to 300 cSt). Most mineral oils, which typically include aromatic moieties and other functional groups, have a pour point of from 10 to -200C in the same kinematic viscosity range. [0123] In a preferred embodiment, the NFP has a glass transition temperature (Tg) of -400C or less, preferably -500C or less, preferably -600C or less, preferably -700C or less, preferably -800C or less, preferably -45 to -1200C, preferably -65 to -900C, wherein a desirable range may be any combination of any lower Tg limit with any upper Tg limit described herein.
[0124] In preferred embodiments, the NFP has a Viscosity Index (VI) of 100 or more, preferably 110 or more, preferably 120 or more, preferably 130 or more, preferably 115 to 350, preferably 135 to 300, preferably 140 to 250, preferably 150 to 200, preferably 125 to 180, wherein a desirable range may be any combination of any lower VI limit with any upper VI limit described herein.
[0125] In preferred embodiments, the NFP has a flash point of 2000C or greater, preferably 210° or greater, preferably 2300C or greater, preferably 200 to 3500C, preferably 210 to 3000C, preferably 215 to 290°C, preferably 220 to 2800C, preferably 240 to 2800C, wherein a desirable range may be any combination of any lower flash point limit with any upper flash point limit described herein.
[0126] In preferred embodiments, the NFP has a specific gravity of 0.86 or less, preferably 0.855 or less, preferably 0.84 or less, preferably 0.78 to 0.86, preferably 0.79 to 0.855, preferably 0.80 to 0.85, preferably 0.81 to 0.845, preferably 0.82 to 0.84, wherein a desirable range may be any combination of any lower specific gravity limit with any upper specific gravity limit described herein.
[0127] In preferred embodiments, the NFP has a number-average molecular weight (Mn) of 250 g/mol or more, preferably 300 g/mol or more, preferably 500 g/mol or more, preferably 300 to 21,000 g/mol, preferably 300 to 10,000 g/mol, preferably 400 to 5,000 g/mol, preferably 500 to 3,000 g/mol, preferably 10 kg/mol or less, preferably 5 kg/mol or less, preferably 3 kg/mol or less, preferably 2 kg/mol or less, preferably 1 kg/mol or less, wherein a desirable range may be any combination of any lower Mn limit with any upper Mn limit described herein. , [0128] In preferred embodiments, the NFP has a low degree of color, such as typically identified as "water white", "prime white", "standard white", or "bright and clear," preferably an APHA color of 100 or less (preferably 80 or less, preferably 60 or less, preferably 40 or less, preferably 20 or less).
[0129] In other embodiments, any NFP may have an initial boiling point of from 300 to 6000C (preferably 350 to 5000C, preferably greater than 4000C).
[0130] Any of the NFPs for use in the present invention may be described by any embodiment described herein, or any combination of the embodiments described herein. For example, in one embodiment, the NFP is a Cg to C200 paraffin having a pour point of less than -25°C. Alternately, the NFP comprises an aliphatic hydrocarbon having a kinematic viscosity of from 0.1 to 1000 cSt at 1000C. Alternately, the NFP is selected from isoparaffins and PAOs and blends thereof having from 8 to 25 carbon atoms. [0131] In another embodiment, the NFP of the present invention comprises C25 to C 1500 paraffins, and C30 to C500 paraffins in another embodiment, and has a flash point of 2000C or more and a pour point of -100C or less and a viscosity index of 120 or more. Alternately the NFP comprises C25 to
Figure imgf000037_0001
paraffins, preferably C30 to C500 paraffins, and has a flash point of 2000C or more and a pour point of -2O0C or less. Alternately the NFP comprises C25 to C1SOo paraffins, preferably C30 to C500 paraffins, and has a flash point of 2000C or more and a kinematic viscosity at 1000C of 35 cSt or more. In another embodiment, the NFP consists essentially of C35 to C300 paraffins, preferably the NFP consists essentially of C40 to C2so paraffins, and has a flash point of 2000C or more and a pour point of -1O0C or less and a viscosity index of 120 or more. Alternately the NFP consists essentially of C35 to C300 paraffins, preferably C4o to C250 paraffins, and has a flash point of 2000C or more and a pour point of -200C or less. Alternately the NFP consists essentially of C35 to C300 paraffins, preferably C40 to C250 paraffins, and has a flash point of 2000C or more and a kinematic viscosity at 1000C of 35 cSt or more. Alternately the NFP has a flash point of 2000C or more and a pour point of -200C or less. Alternately the NFP has a flash point of 2000C or more and a kinematic viscosity at 1000C of 35 cSt or more. [0132] In a preferred embodiment, any NFP described herein has a flash point of 2000C or more (preferably 2100C or more) and a pour point of -200C or less (preferably -25°C or less, preferably -300C or less, preferably -35°C or less, preferably -45°C or less, preferably -500C or less). [0133] In another preferred embodiment, the NFP has a flash point of 2200C or more (preferably 23O0C or more) and a pour point of -100C or less (preferably -25°C or less, preferably -3O0C or less, preferably -35°C or less, preferably -45°C or less, preferably -50°C or less). [0134] In another preferred embodiment, the NFP has a kinematic viscosity at 1000C of 35 cSt or more (preferably 40 cSt or more, preferably 50 cSt or more, preferably 60 cSt or more) and. a specific gravity (15.6/15.6°C) of 0.87 or less (preferably 0.865 or less, preferably 0.86 or less, preferably 0.855 or less) and a flash point of 200°C or more (preferably 2300C or more). [0135] In another preferred embodiment, the NFP has a) a flash point of 2000C or more; b) a specific gravity of 0.86 or less; and cl) a pour point of -1O0C or less and a viscosity index of 120 or more, or c2) a pour point of -200C or less, or c3) a kinematic viscosity at 1000C of 35 cSt or more.
[0136] In another preferred embodiment, the NFP has a) a specific gravity (15.6/15.6°C) of 0.85 or less (preferably between 0.80 and 0.85); and bl) a kinematic viscosity at 1000C of 3 cSt or more (preferably 4 or more, preferably 5 cSt or more, preferably 8 cSt or more, preferably 10 cSt or more, preferably 15 cSt or more, preferably 20 cSt or more) and/or b2) a number-average molecular weight (Mn) of at least 280 g/mol.
[0137] In another preferred embodiment, the NFP has a) a specific gravity (15.6/15.6°C) of 0.86 or less (preferably between 0.81 and 0.855, preferably between 0.82 and 0.85); and bl) a kinematic viscosity at 1000C of 5 cSt or more (preferably 6 or more, preferably 8 cSt or more, preferably 10 cSt or more, preferably 12 cSt or more, preferably 15 cSt or more, preferably 20 cSt or more) and/or b2) a number-average molecular weight (Mn) of at least 420 g/mol (preferably at least 450 g/mol, preferably at least 480 g/mol, preferably at least 500 g/mol). [0138] In another preferred embodiment, the NFP has a) a specific gravity (15.6/15.6°C) of 0.87 or less (preferably between 0.82 and 0.87); and bl) a kinematic viscosity at 1000C of 10 cSt or more (preferably 12 cSt or more, preferably 15 cSt or more, preferably 20 cSt or more, preferably 30 cSt or more, preferably 40 cSt or more) and/or b2) a number-average molecular weight (Mn) of at least 700 g/mol (preferably at least 800 g/mol, preferably at least 900 g/mol, preferably at least 1000 g/mol).
[0139] In another preferred embodiment, the NFP has a) a specific gravity (15.6/15.6°C) of 0.88 or less (preferably 0.87 or less, preferably between 0.82 and 0.87); and bl) a kinematic viscosity at 1000C of 15 cSt or more (preferably 20 cSt or more, preferably 25 cSt or more, preferably 30 cSt or more, preferably 40 cSt or more) and/or b2) a number-average molecular weight (Mn) of at least 840 g/mol (preferably at least 900 g/mol).
[0140] In another preferred embodiment the NFP has a kinematic viscosity at 1000C of 3 to 3000 cSt (preferably 6 to 300 cSt. preferably 8 to 100 cSt); and a number average molecular weight (Mn) of 300 to 21,000 g/mol (preferably 500 to 5,000 g/mol, preferably 600 to 3,000 g/mol).
[0141] In another preferred embodiment the NFP has a kinematic viscosity at 1000C of 3 to 500 cSt (preferably 6 to 200 cSt, preferably 8 to 100 cSt, preferably 8 to 25 cSt); and a number average molecular weight (Mn) of 300 to 10,000 g/mol (preferably 400 to 5,000 g/mol, preferably 500 to 2,500 g/mol, preferably 300 to 1,200 g/mol).
[0142] Li another preferred embodiment the NFP has a kinematic viscosity at 100°C of 3 to 100 cSt (preferably 4 to 50 cSt, preferably 6 to 25 cSt, preferably 6 to 15 cSt); and a number average molecular weight (Mn) of 300 to 3,000 g/mol (preferably 350 to 2,000 g/mol, preferably 400 to 1,000 g/mol, preferably 300 to 800 g/mol).
[0143] In another preferred embodiment, the NFP has a pour point of -25°C or less (preferably between -300C and -900C), and a kinematic viscosity in the range of from 20 to 5000 cSt at 400C. In another preferred embodiment, the NFP has a pour point of -25°C or less and a Mn of 400 g/mol or greater. Most mineral oils, which typically include functional groups, have a pour point of from 100C to -25°C at the same viscosity and molecular weight ranges.
[0144] In another preferred embodiment the NFP has kinematic viscosity at 1000C of 3 cSt or greater (preferably 6 cSt or greater, preferably 8 cSt or greater) and one or more of the following properties:
1. a pour point of -100C or less (preferably -20°C or less, preferably -300C or less, preferably -400C or less); and/or,
2. a Viscosity Index of 120 or greater; and/or,
3. a low degree of color, such as typically identified as "water white", "prime white", "standard white", or "bright and clear," preferably an APHA color of 100 or less, preferably 80 or less, preferably 60 or less, preferably 40 or less, preferably 20 or less (preferably 15 or less); and/or 4. a flash point of 2000C or more (preferably 2200C or more, preferably 2400C or more); and/or
5. a specific gravity (15.6°C) of less than 0.86.
[0145] Most mineral oils at the same viscosity range have a pour point greater than -200C or an APHA color of greater than 20 or a specific gravity (15.6°C) of 0.86 or more.
[0146] In another preferred embodiment, the NFP has a Viscosity Index of 120 or more and one or more of the following properties:
1. a pour point of -100C or less (preferably -200C or less, preferably -300C or less, preferably -400C or less); and/or,
2. a kinematic viscosity at 1000C of 3 cSt or greater (preferably 6 cSt or greater, preferably 8 cSt or greater, preferably 10 cSt or greater); and/or, 3. a low degree of color, such as typically identified as "water white", "prime white", "standard white", or "bright and clear," preferably an APHA color of 100 or less (preferably 80 or less, preferably 60 or less, preferably 40 or less, preferably 20 or less, preferably 15 or less); and/or
4. a flash point of 2000C or more (preferably 2200C or more, preferably 2400C or more); and/or
5. a specific gravity (15.6°C) of less than 0.86. [0147] Most mineral oils have a Viscosity Index of less than 120.
[0148] In another preferred embodiment, the NFP has a pour point of -200C or less, preferably -300C or less, and one or more of the following properties:
1. a kinematic viscosity at 1000C of 3 cSt or greater (preferably 6 cSt or greater, preferably 8 cSt or greater, preferably 10 cSt or more); and/or,
2. a Viscosity Index of 120 or greater (preferably 130 or greater); and/or,
3. a low degree of color, such as typically identified as "water white", "prime white", "standard white", or "bright and clear," preferably APHA color of 100 or less (preferably 80 or less, preferably 60 or less, preferably 40 or less, preferably 20 or less, preferably 15 or less); and/or 4. a flash point of 2000C or more (preferably 2200C or more, preferably 2400C or more); and/or
5. a specific gravity (15.6°C) of less than 0.86.
[0149] Most mineral oils have a kinematic viscosity at 1000C of less than 6 cSt, or an APHA color of greater than 20, or a flash point less than 2000C when their pour point is less than -200C.
[0150] In another preferred embodiment the NFP has a glass transition temperature (Tg) that cannot be determined by ASTM E 1356 or, if it can be determined, then the Tg according to
ASTM E 1356 is less than -200C (preferably less than -300C, preferably less than -400C), and has one or more of the following properties:
1. a pour point of -100C or less (preferably -15°C or less, preferably -25°C or less, preferably
-35°C or less, preferably -45°C or less); and/or 2. a weight average molecular weight (Mw) between 30,000 and 400 g/mol (preferably between
15,000 and 500 g/mol, preferably between 5,000 and 600 g/mol); and/or
3. a number average molecular weight (Mn) between 10,000 and 400 g/mol (preferably between 5,000 and 500 g/mol, preferably between 2,000 and 600 g/mol); and/or
4. a flash point of 2000C or greater; and/or 5. a specific gravity (15.6/15.6°C) of less than 0.88 (preferably less than 0.86, preferably less than 0.84, preferably from 0.80 to 0.88, preferably from 0.82 to 0.86); and/or
6. an initial boiling point greater than 3000C (preferably greater than 3500C, preferably greater than 4000C); and/or
7. a final boiling point of from 3000C to 8000C (preferably from 4000C to 7000C, preferably greater than 5000C).
[0151] In certain particularly preferred embodiments, the NFP has a specific gravity of 0.86 or less (preferably 0.855 or less, preferably 0.85 or less), and one or more of the following: a) a VI of 120 or more (preferably 135 or more, preferably 140 or more), and/or b) a flash point of 2000C or more (preferably 2200C or more, preferably 2400C or more). [0152] In certain particularly preferred embodiments, the NFP has a pour point of -100C or less (preferably -15°C or less, preferably -20°C or less, preferably -250C or less), a VI of 120 or more (preferably 135 or more, preferably 140 or more), and optionally a flash point of 2000C or more (preferably 2200C or more, preferably 2400C or more). [0153] In certain particularly preferred embodiments, the NFP has a pour point of -200C or less (preferably -25°C or less, preferably -300C or less, preferably -400C or less) and one or more of the following: a) a flash point of 2000C or more (preferably 2200C or more, preferably 2400C or more), and/or b) a VI of 120 or more (preferably 135 or more, preferably 140 or more), and/or c) a KVlOO of 4 cSt or more (preferably 6 cSt or more, preferably 8 cSt or more, preferably 10 cSt or more), and/or d) a specific gravity of 0.86 or less (preferably 0.855 or less, preferably 0.85 or less). [0154] In certain particularly preferred embodiments, the NFP has a KVlOO of 4 cSt or more (preferably 5 cSt or more, preferably 6 cSt or more, preferably 8 cSt or more, preferably 10 cSt or more), a specific gravity of 0.86 or less (preferably 0.855 or less, preferably 0.85 cSt or less), and a flash point of 2000C or more (preferably 2200C or more, preferably 2400C or more). [0155] In a preferred embodiment, the NFP has a flash point of 2000C or more (preferably 2200C or more, preferably 2400C or more), a pour point of -100C or less (preferably -15°C or less, preferably -200C or less, preferably -25°C or less), a specific gravity of 0.86 or less (preferably 0.855 or less, preferably 0.85 or less), a KVlOO of 4 cSt or more (preferably 5 cSt or more, preferably 6 cSt or more, preferably 8 cSt or more, preferably 10 cSt or more), and optionally a VI of 100 or more (preferably 120 or more, preferably 135 or more). [0156] In a preferred embodiment, the NFP has a KVlOO of 35 cSt or more (preferably 40 or more) and a specific gravity of 0.86 or less (preferably 0.855 or less), and optionally one or more of the following: a) a flash point of 2000C or more (preferably 2200C or more, preferably 2400C or more), and/or b) a pour point of -100C or less (preferably -15°C or less, preferably -200C or less, preferably -25°C or less).
[0157] In a preferred embodiment, the NFP has a flash point of 2000C or more (preferably 2100C or more, preferably 2200C or more), a pour point of -100C or less (preferably -200C or less, preferably -300C or less), and a KVlOO of 6 cSt or more (preferably 8 cSt or more, preferably 10 cSt or more, preferably 15 cSt or more).
[0158] Ih a preferred embodiment, the NFP has a pour point of -400C or less (preferably -500C or less) and a specific gravity of 0.84 or less (preferably 0.83 or less). [0159] In a preferred embodiment, the percentage of carbons in chain-type paraffins (Cp) for any NFP is at least 80% (preferably at least 85%, preferably at least 90%, even preferably at least 95%, even preferably at least 98%, most preferably at least 99%).
[0160] Preferred NFPs of this invention are characterized in that, when blended with the polyolefin(s) to form a plasticized composition, the NFP is miscible with the polyolefin(s) as indicated by no change in the number of tan-delta peaks in the Dynamic Mechanical Analysis trace (DMA Tan-Delta vs temperature) as compared to the same composition without the NFP added. Lack of miscibility is indicated by an increase in the number of tan-delta peaks in DMA trace over those in the composition absent the NFP. Fillers
[0161] The hetero-phase polyolefm compositions of the present invention include at least one filler. The classes of materials described herein that are useful as fillers can be utilized alone or admixed to obtain desired properties. In any of the embodiments, filler, may be present at 0.1 to 50 wt% (preferably 1 to 40 wt%, preferably 2 to 30 wt%, preferably 5 to 20 wt%) based on the weight of the total composition. Filler content is equated with the wt% ash content as determined by the ISO 3451-1 (A) test method.
[0162] Desirable fillers include but not limited to: mineral aggregates (natural or synthetic), fibers, carbon black, graphite, wollastonite, natural and synthetic clays including nanoclays and organoclays, sand, glass beads, and the like, and any other porous or nonporous fillers and supports known in the art.
[0163] In preferred embodiments the filler has a median particle diameter of 0.1-100 microns (preferably 0.5-50 microns, preferably 1 to 20 microns). In other preferred embodiments the filler has a filler shape that is needle-like or plate-like, with an aspect ratio greater than 1.2 (preferably greater than 2, preferably greater than 3, preferably greater than 5, preferably greater than 10, preferably from 2 to 20, preferably from 3-10), where the aspect ratio is the ratio of the longest dimension to the shortest dimension of the particles, on average, and is typically reported by filler manufacturers. In other embodiments the filler has an aspect ratio of essentially 1 (0.9 to 1.1); i.e., it is not needle-like or plate-like but is essentially spherical. In another embodiment, the filler is pulverized. Useful fillers have a specific surface area of 10 to 300 m2/cm3. [0164] In one embodiment of the present invention, the NFP or some portion of the NFP is blended with a filler, desirably a porous filler. The NFP and filler may be blended by, for example, a tumbler or other wet blending apparatus, for a time suitable to form a homogenous composition of NFP and filler, desirably from 1 minute to 5 hours. In another embodiment, a filler may be pre-contacted or pre-absorbed with the NFP or some portion of the NFP prior to contacting the filler with the pqlyolefin. In another embodiment, the filler, polyolefm, and NFP are contacted simultaneously (or in the same blending apparatus).
Mineral Aggregates
[0165] Preferred natural or synthetic mineral fillers include talc, mica, wollastonite, titanium dioxide, silicon carbide, silica, silicon dioxide and other oxides of silica (precipitated or not), calcium silicate, calcium and barium sulfates, calcium carbonate (calcite), lead carbonate, magnesium silicate, magnesium oxysulfates, antimony oxide, zinc white, lithopone, zircon, corundum, spinel, apatite, Barytes powder, magnesiter, dolomite, zinc borate, hydrotalcite compounds of the ions Mg, Ca, or Zn with Al, Cr or Fe and CO3 and/or HPO4 (hydrated or not), quartz powder, hydrochloric magnesium carbonate, alumina, chrome, phosphorous and brominated flame retardants, antimony trioxide, silicone, other metal oxides, other metal carbonates, other metal hydroxides, and blends thereof. Fibers [0166] Preferred fibers include glass fibers (long or short), carbon fibers, and natural and synthetic polymer fibers including polyethylene terephthalate (PET) fibers and rayon fibers.
Clays
[0167] Preferred clays include nanoclays or organoclays to produce a nanocomposite. These clays may comprise one or more of ammonium, primary alkylammonium, secondary alkylammonium, tertiary alkylammonium, quaternary alkylammonium, phosphonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines or sulfides or sulfonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines or sulfides. The organoclay may be selected from one or more of montmorillonite, sodium montmorillonite, calcium montmorillonite, magnesium montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, sobockite, svindordite, stevensite, vermiculite, halloysite, aluminate oxides, hydrotalcite, illite, rectorite, tarosovite, ledikite, and/or florine mica. In another embodiment the filler is a nano-clay with mean particle diameter of less than 1 micron.
Additives
[0168] Additives such as antioxidants and stabilizers (including UV stabilizers and other UV absorbers, such as chain-breaking antioxidants), nucleating agents, slip agents, block, antiblock, pigments, dyes, color masterbatches, waxes, processing aids (including pine or coal tars or resins and asphalts), neutralizers (such as hydro talcite), adjuvants, oils, lubricants, low molecular weight resins, surfactants, acid scavengers, anticorrosion agents, cavitating agents, blowing agents, quenchers, antistatic agents, cure or cross linking agents or systems (such as elemental sulfur, organo-sulfur compounds, and organic peroxides), fire retardants, coupling agents (such as silane). and combinations thereof may also be present in the polyolefin compositions described herein. Typical additives used in polypropylene and polypropylene blends are described in POLYPROPYLENE HANDBOOK 2ND ED., N. Pasquini, ed. (Hanser Publishers, 2005). The additives may be present in the typically effective amounts well known in the art, preferably at 0.001 to 50 wt% (preferably 0.01 to 20 wt%, preferably 0.1 to 10 wt%, preferably 0.1 to 1 wt%), based upon the weight of the composition. Pigments, dyes, and other colorants may be present from 0.01 to 10 wt% (preferably 0.1 to 6 wt%).
Antioxidants and stabilizers [0169] Particularly useful antioxidants and stabilizers such as organic phosphites, hindered amines (including high and low molecular weight hindered amine light stabilizers, or "HALS"), and phenolic antioxidants may be present in the thermoplastic polyolefin compositions of the invention from 0.001 to 2 wt% (preferably from 0.01 to 0.8 wt%, preferably from 0.02 to 0.5 wt%). Non-limiting examples of organic phosphites that are suitable are tris(2,4-di-tert- butylphenyl)phosphite (IRGAFOS 168) and di(2,4-di-tert-butylphenyl)pentaerithritol diphosphite (ULTRANOX 626). Non-limiting examples of hindered amines include poly[2-N,N'-di(2,2,6,6- teframethyl-4-piperidinyl)-hexanediamine-4-(l-amino-l,l,3,3-tetramethylbutane)sym-triazine] (CHJMASORB 944); bis(l,2,2,6,6-pentamethyl-4-piperidyl)sebacate (TINUVIN 770). Non- limiting examples of phenolic antioxidants include pentaerythrityl tetrakis(3,5-di-tert-butyl-4- hydroxyphenyl) propionate (IRGANOX 1010); and l,3,5-Tri(3,5-di-tert-butyl-4-hydroxybenzyl- isocyanurate (IRGANOX 3114). Preferred antioxidants include phenolic antioxidants, such as Lrganox 1010, Irganox, 1076 both available from Ciba-Geigy.
[0170] Li another embodiment, the polymer concentrate may comprise one or more phenolic antioxidants. Slip Agent
[0171] The polyolefin compositions of the present invention may include a slip agent. Preferably, the slip agent is preferably a fast bloom slip agent, and can be a hydrocarbon having one or more functional groups selected from hydroxide, aryls and substituted aryls, halogens, alkoxys, carboxylates, esters, carbon unsaturation, acrylates, oxygen, nitrogen, carboxyl, sulfate and phosphate. In one embodiment the slip agent is an ionic compound. Ionic slip agents include salt derivatives of aromatic or aliphatic hydrocarbon oils, notably metal salts of fatty acids, including metal salts of carboxylic, sulfuric, and phosphoric aliphatic saturated or unsaturated acid having a chain length of 7 to 26 carbon atoms, preferably 10 to 22 carbon atoms. Suitable fatty acids include the monocarboxylic acids lauric acid, stearic acid, succinic acid, stearyl lactic acid, lactic acid, phthalic acid, benzoic acid, hydroxystearic acid, ricinoleic acid, naphthenic acid, oleic acid, palmitic acid, erucic acid, and the like, and the corresponding sulfuric and phosphoric acids. Suitable metals include Li, Na, Mg, Ca, Sr, Ba, Zn, Cd, Al, Sn, Pb and so forth. Suitable salts include magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate, zinc oleate, magnesium oleate, and so on, as well as the corresponding metal higher alkyl sulfates and metal esters of higher alkyl phosphoric acids.
[0172] In another embodiment, fatty acid metal salts are substantially absent from the polyolefm compositions of the present invention. [0173] In one embodiment the slip agent is a non-ionic fiinctionalized compound. Suitable functionalized compounds include: (a) esters, amides, alcohols and acids of oils including aromatic or aliphatic hydrocarbon oils, for example, mineral oils, naphthenic oils, paraffinic oils; natural oils such as castor, corn, cottonseed, olive, rapeseed, soybean, sunflower, other vegetable and animal oils, and so on. Representative functionalized derivatives of these oils include, for example, polyol esters of monocarboxylic acids such as glycerol monostearate, pentaerythritol monooleate, and the like, saturated and unsaturated fatty acid amides or ethylenebis(amides), such as oleamide, erucamide, linoleamide, and mixtures thereof, glycols, polyether polyols like Carbowax, and adipic acid, sebacic acid, and the like; (b) waxes, such as carnauba wax, microcrystalline wax, polyolefin waxes, e.g. polyethylene waxes; (c) fluoro-containing polymers such as polytetrafluoroethylene, fluorine oils, fluorine waxes and so forth; and (d) silicon compounds such as silanes and silicone polymers, including silicone oils, polydimethylsiloxane, amino-modified polydimethylsiloxane, and so on.
[0174] The fatty amides useful in the present invention are represented by the formula: R1C(O)NHR2 where R1 is a saturated or unsaturated alkyl group having of from 7 to 26 carbon atoms, preferably 10 to 22 carbon atoms, and R2 is independently hydrogen or a saturated or unsaturated alkyl group having from 7 to 26 carbon atoms, preferably 10 to 22 carbon atoms. Compounds according to this structure include for example, palmitamide, stearamide, arachidamide, behenamide, oleamide, erucamide, linoleamide, stearyl stearamide, palmityl palmitamide, stearyl arachidamide and mixtures thereof. [0175] The ethylenebis(amides) useful in the present invention are represented by the formula: RC(O)NHCH2CH2NHC(O)R where each R is independently is a saturated or unsaturated alkyl group having of from 7 to 26 carbon atoms, preferably 10 to 22 carbon atoms. Compounds according to this structure include for example, stearamidoethylstearamide, stearamidoethylpalmitamide, pahnitamido-ethylstearamide, ethylenebisstearamide, ethylenebisoleamide, stearylerucamide, erucamidoethylerucamide, oleamidoethyloleamide, erucamidoethyloleamide, oleamidoethylerucamide, stearamidoethylerucamide, erucamidoethylpalmitamide, palmitamidoethyloleamide and mixtures thereof. [0176] Commercially available examples of fatty amides include Ampacet 10061 which comprises 5% of a 50:50 mixture of the primary amides of erucic and stearic acids in polyethylene; Elvax 3170 which comprises a similar blend of the amides of erucic and stearic acids in a blend of 18% vinyl acetate resin and 82% polyethylene. These slip agents are available from DuPont. Slip agents also are available from Croda Universal, including Crodamide OR (an oleamide), Crodamide SR (a stearamide), Crodamide ER (an erucamide), and Crodamide BR (a behenamide); and from Crompton, including Kemamide S (a stearamide), Kemamide B (a behenamide), Kemamide O (an oleamide), Kemamide E (an erucamide), and Kemamide (an N.N'-ethylenebisstearamide). Other commercially available slip agents include Erucamid ER erucamide.
[0177] Generally preferred concentrations of the slip agent are in the range of from about 0.001% to about 0.5% by weight of the composition, preferably of from about 0.01% to about 0.4% by weight and most preferably of from about 0.1 parts to about 0.3% by weight based on the weight of the composition.
Nucleating Agent
[0178] The polyolefin composition described herein may also include the addition of at least one nucleating agent. Typically, nucleating agents increase the rate of crystallization (isothermal and/or non-isothermal) of the polyolefin. A special class of nucleating agents known as clarifying agents typically reduces the size of crystallites, thereby improving the transparency and clarity of articles made from the polyolefin.
[0179] Suitable nucleating agents for use herein are disclosed in Plastics Additive Handbook, 5th Ed.; H. Zweifel, Ed.; Hanser-Gardner Publications, (2001); Chapter 18, p. 949-972. Suitable nucleating agents for use herein are also disclosed by H.N. Beck in Heterogeneous Nucleating Agents for Polypropylene Crystallization, J. APPLIED POLY. SCI. Vol. 11, p. 673-685 (1967) and in Heterogeneous Nucleation Studies on Polypropylene, J. POLY. SCI.: POLY. LETTERS, Vol. 21, p. 347-351 (1983). Useful nucleating agents can be either homogeneous nucleating agents (i.e., melt-soluble, meaning dissolved into the polyolefin) and heterogeneous nucleating agents (i.e., melt-insoluble, meaning suspended or dispersed in the polyolefin). Typical nucleating agents promote at least one crystal polymorph for the polyolefin. For example, when the polyolefin is isotactic polypropylene (iPP), known crystal forms include the so-called alpha, beta, and gamma polymorphs; useful nucleating agents therefore include those that promote alpha crystals in iPP, those that promote beta crystals in iPP, and those that promote gamma crystals in iPP. Suitable nucleating agents also include those that promote crystallization in syndiotactic polypropylene (sPP).
[0180] Suitable nucleating agents preferably improve one or more performance parameters of the polyolefin, such as increased clarity, reduced haze, increased stiffness, increased impact toughness, increased heat deflection temperature; and/or processing parameters, such as reduced cycle time or increased line speed. Suitable nucleating agents can be organic, inorganic, or polymeric, and may include combinations of one or more nucleating agent.
[0181] The appearance and mechanical properties of the compositions of the present invention can be controlled to some extent by the type of nucleating agent used. The nucleating agent(s) are typically present in the composition of this invention at 0.01 to 1 wt% (100 to 10,000 ppm), preferably 0.02 to 0.5 wt% (200 to 5,000 ppm), preferably 0.03 to 0.3 wt% (300 to 3,000 ppm), preferably 0.05 to 0.25 wt% (500 to 2,500 ppm), based upon the weight of the composition (where ppm is parts-per-million by weight).
Crosslinking Agents [0182] In another embodiment, the polyolefin composition may further comprise a crosslinking agent. Preferred crosslinking agents include those having functional groups that can react with functional groups present on the polyolefin, including alcohols, multiols, amines, diamines and/or triamines. Particular examples of crosslinking agents useful in this invention include polyamines such as ethylene-diamine, diethylene-triamine, hexamethylene-diamme, diethylaniinopropyl-amine, and menthane-diamine.
Oils
[0183] In some embodiments, conventional mineral oils may be present in the composition of this invention, such as paraffϊnic or naphthenic mineral oils, white oils, technical white oils, bright stocks, Group I or Group II basestocks, vegetable oils, or the like. In other embodiments, functionalized oils other than amide slip agents are substantially absent from the polyolefin composition.
[0184] In preferred embodiments, naphthenic and aromatic mineral oils are substantially absent from the compositions of the present invention, preferably present at 0 wt%. In another embodiment, aromatic moieties and carbon-carbon unsaturation are substantially absent from the non-functionalized plasticizers used in the present invention. Aromatic moieties include a compound whose molecules have the ring structure characteristic of benzene, naphthalene, phenanthrene, anthracene, etc.
Tackiflers
[0185] In another embodiment, tackifϊers may be blended with the polyolefin composition of this invention. Examples of useful tackifiers include, but are not limited to, aliphatic hydrocarbon resins, aromatic modified aliphatic hydrocarbon resins, hydrogenated polycyclopentadiene resins, polycyclopentadiene resins, gum rosins, gum rosin esters, wood rosins, wood rosin esters, tall oil rosins, tall oil rosin esters, polyterpenes, aromatic modified polyterpenes, terpens phenolics, aromatic modified hydrogenated polycyclopentadiene resins, hydrogenated aliphatic resin, hydrogenated aliphatic aromatic resins, hydrogenated terpenes and modified terpenes, and hydrogenated rosin esters. In some embodiments the tackifϊer is hydrogenated. In other embodiments the tackifϊer is non-polar. (Non-polar meaning that the polar groups are substantially absent from the tackifϊer, or preferably polar groups are not present.) In some embodiments the tackifier has a softening point (Ring and Ball, ASTM E 28) of 80 to 1400C, preferably 100 to 1300C.
[0186] Tackifiers, if present, are typically present at about 1 to about 50 wt% (preferably 2 to 40 wt%, preferably 5 to 20 wt%), based upon the weight of the composition. Preferably however, tackifier is not present, or is present at less than 10 wt% (preferably less than 5 wt%, preferably at less than 1 wt%).
Conventional plasticizers
[0187] In one embodiment of compositions of the present invention, conventional plasticizers such as are commonly used for poly(vinyl chloride) are substantially absent, preferably present at 0 wt%. Ih particular, plasticizers such as phthalates, adipates, trimellitate esters, polyesters, and other functionalized plasticizers as disclosed in, for example, US 3,318,835; US 4,409,345; WO 02/31044 Al; and PLASΉCS ADDITIVES 499-504 (Geoffrey Pritchard, ed., Chapman & Hall 1998) are substantially absent.
Waxes
[0188] Preferred waxes suitable for use in the compositions of this invention include: polar waxes, non-polar waxes, Fischer-Tropsch waxes, oxidized Fischer-Tropsch waxes, hydroxystearamide waxes, functionalized waxes, polypropylene waxes, polyethylene waxes, wax modifiers, amorphous waxes, carnauba waxes, castor oil waxes, microcrystalline waxes, beeswax, carnauba wax, castor wax, spermaceti wax, vegetable wax, candelilla wax, japan wax, ouricury wax, douglas-fir bark wax, rice-bran wax, jojoba wax, bayberry wax, montan wax, peat wax, ozokerite wax, ear wax, ceresin wax, petroleum wax, paraffin wax, polyethylene wax, chemically modified hydrocarbon wax, substituted amide wax, and combinations and derivatives thereof. In some embodiments, the polar and non-polar waxes may be used together in the same composition. In a preferred embodiment, compositions of this invention comprise no waxes. Polymers
[0189] In some embodiments the polyolefin composition of this invention may be blended with up to 25 wt% (preferably up to 20 wt%, preferably up to 15 wt%, preferably up to 10 wt%, preferably up to 5 wt%), based upon the weight of the composition, of one or more additional polymeric additives. Suitable polymers include: PMl) Polyethylenes, including (but not limited to):
Copolymers of ethylene and one or more polar monomers, preferably selected from vinyl acetate, methyl acrylate, n-butyl acrylate, acrylic acid, and vinyl alcohol (i.e., EVA, EMA, EnBA, EAA, and EVOH); ethylene homopolymers and copolymers synthesized using a high- pressure free radical process, including LDPE; copolymers of ethylene and C3 to C4o olefins
(preferably propylene and/or butene) with a density of greater than 0.91 g/cm3 to less than 0.94 g/cm3), including LLDPE; and high density PE (0.94 to 0.98 g/cm3). PM2) Polybutene-1 and copolymers of polybutene-1 with ethylene and/or propylene. PM3) Non-EP Rubber Elastomers, including (but not limited to): Polyisobutylene, butyl rubber, halobutyl rubber, copolymers of isobutylene and para- alkylstyrene, halogenated copolymers of isobutylene and para-alkylstyrene, natural rubber, polyisoprene, copolymers of butadiene with acrylonitrile, polychloroprene, alkyl acrylate rubber, chlorinated isoprene rubber, acrylonitrile chlorinated isoprene rubber, and polybutadiene rubber (both cis and trans). PM4) Low-crystallinity propylene/olefin copolymers, preferably random copolymers, comprising i) at least 70 wt% propylene, and ii) 5 to 30 wt% (preferably 5 to 20 wt%) of comonomer selected from ethylene and C4 to C12 olefins (preferably selected from ethylene, butene, and hexene; preferably ethylene); preferably made using a metallocene-type catalyst; and having one or more of the following properties: a) Mw of 20 to 5,000 kg/mol (preferably 30 to 2,000 kg/mol, preferably 40 to 1,000 kg/mol, preferably 50 to 500 kg/mol, preferably 60 to 400 kg/mol); and/or b) molecular weight distribution index (Mw/Mn) of 1.5 to 10 (preferably 1.7 to 5, preferably 1.8 to 3); and/or c) branching index (g*) of 0.9 or greater (preferably 0.95 or greater, preferably 0.99 or greater); and/or d) density of 0.85 to about 0.90 g/cm3 (preferably 0.855 to 0.89 g/cm3, preferably 0.86 to about 0.88 g/cm3); and/or e) melt flow rate (MFR) of at least 0.2 dg/min (preferably 1-500 dg/min, preferably 2-300 dg/min); and/or f) heat of fusion (Hf) of 0.5 J/g or more (preferably 1 J/g or more, preferably 2.5 J/g or more, preferably 5 J/g or more) but less than or equal to 75 J/g (preferably less than or equal to 50 J/g, preferably less than or equal to 35 J/g, preferably less than or equal to 25 J/g); and/or g) DSC-determined crystallinity of from 1 to 30 wt% (preferably 2 to 25 wt%, preferably 2 to 20 wt%, preferably 3 to 15 wt%); and/or h) a single broad melting transition with a peak melting point of 25 to about 1050C (preferably 25 to 85°C, preferably 30 to 70°C, preferably 30 to 600C), where the highest peak considered the melting point; and i) crystallization temperature (Tc) of 900C or less (preferably 6O0C or less); and/or j) greater than 80% of the propylene residues (exclusive of any other monomer such as ethylene) arranged as 1,2 insertions with the same stereochemical orientation of the pendant methyl groups, either meso or racemic, as determined by 13C-NMR; and/or k) C-NMR-determined propylene tacticity index of more than 1; and/or 1) 13C-NMR-determined mm triad tacticity index of 75% or greater (preferably 80% or greater, preferably 82% or greater, preferably 85% or greater, preferably 90% or greater).
Useful low-crystallinity propylene/olefin copolymers are available from ExxonMobil Chemical; suitable examples include Vistamaxx™ 6100, Vistamaxx™ 6200 and
Vistamaxx™ 3000. Other useful low-crystallinity propylene/olefin copolymers are described in WO 03/040095, WO 03/040201, WO 03/040233, and WO 03/040442, all to Dow
Chemical, which disclose propylene-ethylene copolymers made with non-metallocene catalyst compounds. Still other useful low-crystallinity propylene/olefin copolymers are described in US 5504172 to Mitsui Petrochemical. Preferred low-crystallinity propylene/olefin copolymers are described in US 2002/0004575 to ExxonMobil Chemical. PM5) Propylene oligomers suitable for adhesive applications, such as those described in WO
2004/046214, particular those at pages 8 to 23.
PM5) Olefin block copolymers, including those described in WO 2005/090425, WO 2005/090426, and WO 2005/090427.
PM6) Polyolefins that have been post-reactor functionalized with maleic anhydride (so-called maleated polyolefins), including maleated ethylene polymers, maleated EP Rubbers, and maleated propylene polymers. Preferably, the amount of free acid groups present in the maleated polyolefin is less than about 1000 ppm (preferably less than about 500 ppm, preferably less than about 100 ppm), and the amount of phosphite present in the maleated polyolefin is less than 100 ppm. PM6) Styrenic Block Copolymers (SBCs), including (but not limited to):
Unhydrogenated SBCs such as SI, SIS, SB, SBS, SIBS and the like, where S=styrene, I=isobutylene, and B=butadiene; and hydrogenated SBCs, such as SEBS, where EB = ethylene/butene. PM7) Engineering Thermoplastics, including (but are not limited to):
Polycarbonates, such as poly(bisphenol-a carbonate); polyamide resins, such as nylon 6 (N6). [0190] In a preferred embodiment, compositions of this invention comprise no added polymeric additives, or if they are present the polymeric additives are present at 0.5 wt% or less. [0191] In a particularly preferred embodiment, compositions of this invention comprise less than 10 wt% LLDPE having a density of 0.912 to 0.935 (preferably less than 5 wt%, preferably less than 1 wt%, preferably 0 wt%), based upon the weight of the composition.
Preparing the Polyolefin Composition [0192] The polyolefm(s), NFP(s), filler(s), and optional additives components of the polyolefin composition of the present invention can be combined using any suitable means known in the polymer processing art. Those skilled in the art will be able to determine the appropriate procedure to balance the need for intimate mixing with the desire for process economy. For example, one or more polyolefin component can be in the form of pellets or reactor granules, which are combined with the NFP(s), filler(s), and optional additives by simple physical blending of constituent pellets and/or granules, since the forming of articles includes a (re)melting and mixing of the raw material(s). However, in some fabrication processes such as compression molding, little mixing of the raw material(s) occurs, and a pelletized melt blend would be preferred over simple physical blends of the constituent pellets and/or granules. In this case, the constituents are melt blended first, to provide a compounded product.
[0193] The polyolefin components may be in any physical form when blended with the NFP(s), filler(s), and optional additives. For example, they may be in the form of reactor granules (i.e., granules of polymer that are isolated from the polymerization reactor prior to any processing procedures), which typically have an average diameter of 50 μm to 5 mm, or in the form of pellets that are formed from melt extrusion of the reactor granules, which typically have an average diameter of from 1 to 10 mm.
[0194] The polyoiefin(s), NFP(s), filler(s), and optional additives can be blended by any suitable means. For example, they may be blended in a tumbler, static mixer, batch mixer, extruder, or a combination thereof that is sufficient to achieve an adequate dispersion of the components. More particularly, the components may be blended by any suitable means to form the polyolefin composition of the present invention, which is then suitable for further processing into useful articles.
[0195] Preferably, the composition is prepared by combining the components in a melt- blending (compounding) step and subsequently pelletizing the blend, using either an underwater pelletizer or a strand-cut approach (i.e., a water batch and dry pelletizer); these pellets are then used in a process to fabricate articles. This approach may involve an on-line "finishing" extruder associated with a polymerization unit, or it may involve an off-line "compounding" extruder dedicated to melt blending. Alternatively, the composition may be prepared by combining the components during a process used to fabricate articles, without first making a pelletized version of the composition; here, NFP is added to other components in a production extruder, such as the extruder on an injection molding machine or on a continuous extrusion line, and thereafter directly processed into a film, sheet, fiber, profile, etc. In either case, production rates may be between 5 and 3000 kg/hr. [0196] The blending may involve "dry blending" wherein the polyolefin(s) are combined with the NFP(s) without melting. For example, one method is to contact the components in a tumbler or bowl mixer, such as a high-speed Henschel mixer. The polyolefin(s) are preferably in the form of reactor granules (this works particularly well with ICPs and propylene polymers), but dry blending can also involve pellets. The dry blending step can then be followed, if desired, by melt blending in an extruder.
[0197] Another method of blending the components is to melt blend the polyolefin(s), either in pellet or granule form, with the NFP(s) and optionally with the filler(s) and/or additives in a batch mixer, such as a Banbury mixer. [0198] Another method of blending the components is to melt blend the polyolefin(s), either in pellet or granule form, with the NFP(s) and optionally the filler(s) and/or additives in an extruder, such as a single-screw extruder or a twin-screw extruder. Extrusion technology for polyolefins and polyolefin blends is well known in the art, and is described in more detail in, for example, PLASTICS EXTRUSION TECHNOLOGY, F. Hensen, Ed. (Hanser, 1988), p. 26-37 and in POLYPROPYLENE HANDBOOK, E. P. Moore, Jr. Ed., (Hanser, 1996), p. 304-348. Extruder melt mixing is a preferred method of blending when a high NFP loading is desired, or when large quantities of the polyolefin composition are desired. Typical extruder characteristics associated with blending NFP into polyolefin(s) include: an operating temperature profile within the range of 120 to 2800C (usually 160 to 2400C); a melt temperature at least 10-500C above Tm of the polyolefin having the highest Tn, (usually 140 to 2200C); an operating speed of 50 to 1200 rpm; and a specific energy input of 0.01 to 100 kWh/kg. The extruder may be set up with or without screen pack(s) for filtration, and with or without a melt gear pump.
[0199] NFP may be directly injected into the polymer melt using a liquid injection device at some point along the barrel, as in the case of a twin-screw extruder, or through an opening in a hollow screw shaft, as in the case of a single-screw extruder. NFP is preferably added downstream from the polymer melt zone, but alternatively the NFP can be added at a point where the polymer(s) have not fully melted yet. For example, in a twin-screw extruder, NFP can be injected after the first barrel section (preferably after the first third of the barrel, more preferably in the last third of the barrel). Preferably, NFP is added downstream of filler addition. An NFP addition point may be on top of conveying elements of screw, or on top of liquid mixing elements of screw, or prior to kneading elements of screw, or prior to liquid mixing elements of the screw. The extruder may have more than one (preferably two or three) NFP addition points along the barrel or screw shaft. Optionally, the NFP can be added via the extruder fed throat. [0200] Addition of NFP is preferably by controlled metering; e.g., using a loss-in-weight feeder or a calibrated flow-rate meter. Preferably NFP delivery is via a pump (such as a piston, gear, or diaphragm pump) capable of generating a delivery pressure of at least 5 bar (preferably at least 10 bar, preferably at least 20 bar, preferably at least 30 bar, preferably at least 40 bar). (1 bar = 100 kPa). [0201] Preferably, the extruder is a twin-screw extruder with a length to diameter ratio, L/D, of 20-80 (preferably 30-60, preferably 25-50, preferably 35-45) and/or a screw diameter of 20 to 200 mm. Preferably the screw design contains liquid mixing elements (gear-type elements) that create high surface renewal of the polymer, which promotes homogenization at high fluid concentrations. Such extruders are know in the art and are manufactured by Coperion Werner- Pfleiderer, Berstorff, Leistriz, and others. [0202] The components may also be blended by a combination of methods, such as dry blending followed by melt blending in an extruder, or batch mixing of some components followed by melt blending with other components in an extruder. One or more components may also be blended using a double-cone blender, ribbon blender, or other suitable blender, or in a Farrel Continuous Mixer (FCM). [0203] Blending may also involve a "masterbatch" approach, where the target NFP concentration is achieved by combining neat polyolefin(s) and optionally filler and/or additives with an appropriate amount of ρre-blended masterbatch (i.e. a blend of polymer, NFP, and optionally filler and additives that has been previously prepared at a higher concentration of NFP than desired in the final blend). This is a common practice in polymer processing, typically used for addition of color, additives, and fillers to final compositions. Dispersion (or "letdown") of the masterbatch may take place as part of a processing step used to fabricate articles, such as in the extruder on an injection molding machine or on a continuous extrusion line, or during a separate compounding step. [0204] The components may be blended in solution by any suitable means to form the polyolefin composition, by using one or more solvents that dissolve the polyolefϊn and NFP components to a significant extent. The blending may occur at any temperature or pressure where the NFP and the polyolefin remain in solution. Preferred conditions include blending at high temperatures, such as 200C or more above the melting point of the polymer. For example, iPP would typically be solution blended with the NFP at a temperature of 200°C or more. Such solution blending would be particularly useful in processes where the polymer is made by a solution process and the NFP is added directly to the finishing train, rather than added to the dry polymer in another blending step altogether. It would also be particularly useful in processes where the polymer is made in a bulk or high pressure process where the polymer and the NFP were soluble in the monomer, where the NFP may be added directly to the finishing train. Similarly, a filler could be added to the finishing train.
Applications
[0205] The compositions of this invention may be used in any known application involving molding or extrusion, including consumer goods, industrial goods, construction materials, packaging materials, and automotive parts. Articles may be made or formed by any useful discrete molding or continuous extrusion means for forming and shaping polyolefins known in the art, including: compression molding, injection molding, co-injection molding, gas-assisted injection molding, blow molding, multi-layer blow molding, injection blow molding, stretch blow molding, extrusion blow molding, transfer molding; cast molding, rotational molding, foam molding, slush molding, transfer molding, wet lay-up or contact molding, cast molding, cold forming matched-die molding, thermoforming, vacuum forming, film blowing, film or sheet casting, sheet extrusion, profile extrusion or co-extrusion, fiber spinning, fiber spunbonding, fiber melt blowing, lamination, calendering, coating, pultrusion, protrusion, draw reduction, foaming, or other forms of processing such as described in, for example, PLASTICS PROCESSING (Radian Corporation, Noyes Data Corp. 1986), or combinations thereof. Use of certain processes, such as film casting and thermoforming, allows for the possibility of benefits from uniaxial or biaxial orientation of the inventive material.
[0206] Non-limiting examples of desirable articles of manufacture made from compositions of the invention include films, tapes, sheets, fibers, tubing, pipes, coatings, fabrics (woven and nonwoven), tarps, agricultural barriers, packaging (durable and disposable), household appliances (washing machines, refrigerators, blenders, air conditioners, etc.), furniture (indoor and outdoor, such as tables, chairs, benches, shelving, etc.), sporting equipment (skis, surfboards, skateboards, skates, boots, sleds, scooters, kayaks, paddles, etc.), solid wheels, stadium seating, amusement park rides, personal protective equipment (safety helmets, shin guards, etc.), emergency response equipment, cookware, utensils, trays, pallets, carts, tanks, tubs, pond liners, storage containers (crates, pails, jars, bottles, etc.), toys, child car seats and booster chairs, medical devices, sportswear, luggage, tool housings (for drills, saws, etc.), electronics housings (for televisions, computers, phones, hand-held devices, media players, stereos, radios, clocks, etc.), building construction materials (flooring, siding, roofing, counter tops, electrical housings and connectors, etc.), lighting, gardening equipment (handles on shovels, wheelbarrows, etc.), playground equipment, motor housings, pump housings, battery housings, instrument housings, switches, knobs, buttons, handles, pet supplies, laboratory supplies, personal hygiene devices (razors, brushes, hairdryers, etc.), cleaning supplies (brooms, dust pans, etc.), musical instrument cases, statues, trophies, artwork, costume jewelry, picture frames, eyeglass frames, plant pots, firearm components, and automotive components.
[0207] Further non-limiting examples of desirable articles of manufacture made from compositions of the invention useful in vehicles (such as cars, trucks, buses, boats, all terrain vehicles, personal water craft, golf carts, snowmobiles, motorcycles, mopeds, tractors, mowers, wagons, bicycles, airplanes, helicopters, trains, military machines, gondolas, and the like) include: bumpers and bumper fascias; exterior body panels, door panels, and grills; exterior trim, including body side moldings, side cladding and molding, end caps, hoods, deck lids, mirror housings, roof racks, wheel covers, wheel liners, wheel flares, fender liners, hub caps, running boards, step pads, sill plates, air dams, splash shields, mud guards, bed liners, and rocker panels; fuel tanks; interior trim, including steering column covers, consoles, door panels, pillars, supports, knobs, buttons, handles, and safety screens; instrument panels and dash boards; knee bolsters; passenger side airbag covers; headliners; glove boxes, trays, cup holders, compartments, and lids; seat components, including backs, supports, and safety belt securing devices; under- hood applications, including battery trays and fan shrouds; electrical housings; cable bearings; and structural components, including door carriers, truck bed separators, load floors, and trunk dividers.
[0208] Preferably, the article made from compositions of the invention has at least one overall dimension, such as length, greater than 30 cm (preferably greater than 60 cm, preferably greater than 90 cm, preferably greater than 120 cm). More preferably, said article is an automotive part. Most preferably, said article is fabricated by an injection molding process. [0209] In alternate embodiments, this invention relates to:
1. A hetero-phase polyolefin composition comprising: a) 30 to 99.7 wt% of a polypropylene-based TPO comprising at least 50 wt% propylene and at least 10 wt% ethylene, and b) 0.1 to 20 wt% of one or more non-functionalized plasticizer(s), and c) 0.2 to 50 wt% of one or more fϊller(s); based upon the weight of the composition, and having: i) an MFR of 5 dg/min or more, and ii) a flexural modulus of 500 MPa or more, and iii) a notched Charpy impact strength at -300C of 1 kJ/m2 or more or a notched Izod impact strength at -18°C of 50 J/m or more.
2. The composition of paragraph 1 wherein the composition has an MFR of 10 dg/min or more. 3. The composition of paragraph 1 or 2 wherein the composition has an MFR of 15 to 400 dg/min.
4. The composition of any of paragraphs 1 to 3 wherein the composition has a flexural modulus of 800 MPa or more.
5. The composition of any of paragraphs 1 to 4 wherein the composition has a flexural modulus of 900 to 3500 MPa.
6. The composition of any of paragraphs 1 to 5 wherein the composition has a notched Charpy impact strength at -300C of 2 kJ/m2 or more and a notched Izod impact strength at -18°C of 50 J/m or more.
7. The composition of any of paragraphs 1 to 6 wherein the composition has a notched Charpy impact strength at -300C of 2.5 to 15 kJ/m2 or more and a notched Izod impact strength at -18°C of 50 J/m or more.
8. The composition of any of paragraphs 1 to 7 wherein the composition has a notched Charpy impact strength at -3O0C of 2 kJ/m2 or more and a notched Izod impact strength at -18°C of 60 J/m or more. 9. The composition of any of paragraphs 1 to 8 wherein the composition has a notched Charpy impact strength at -300C of 2 kJ/m2 or more and a notched Izod impact strength at -18°C of 70 to 500 J/m.
10. The composition of any of paragraphs 1 to 9 wherein the composition comprises 35 to 95 wt% of the polypropylene-based TPO. 11. The composition of any of paragraphs 1 to 10 wherein the composition comprises 40 to 90 wt% of the polypropylene-based TPO.
12. The composition of any of paragraphs 1 to 11 wherein the polypropylene-based TPO comprises at least 55 wt% propylene. 13. The composition of any of paragraphs 1 to 12 wherein the polypropylene-based TPO comprises at least 60 wt% propylene.
14. The composition of any of paragraphs 1 to 13 wherein the polypropylene-based TPO comprises at least 15 wt% ethylene.
15. The composition of any of paragraphs 1 to 14 wherein the polypropylene-based TPO comprises at least 20 wt% ethylene.
16. The composition of any of paragraphs 1 to 15 wherein the composition comprises 0.5 to 15 wt% of one or more non-functionalized plasticizer(s).
17. The composition of any of paragraphs 1 to 16 wherein the composition comprises 1 to 10 wt% of one or more non-functionalized plasticizer(s). 18. The composition of any of paragraphs 1 to 17 wherein the composition comprises 0.5 to 40 wt% of one or more filler(s).
19. The composition of any of paragraphs 1 to 18 wherein the composition comprises 1 to 30 wt% of one or more filler(s).
20. The composition of any of paragraphs 1 to 19 wherein the polypropylene-based TPO is a polypropylene impact copolymer.
21. The composition of any of paragraphs 1 to 20 wherein the polypropylene-based TPO comprises a homopolypropylene matrix.
22. The composition of any of paragraphs 1 to 21 wherein the polypropylene-based TPO comprises a propylene copolymer matrix. 23. The composition of any of paragraphs 1 to 22 wherein the polypropylene-based TPO comprises an isotactic polypropylene matrix.
24. The composition of any of paragraphs 1 to 23 wherein the polypropylene-based TPO comprises a matrix having a Tm of 110 0C or more.
25. The composition of any of paragraphs 1 to 24 wherein the polypropylene-based TPO comprises a matrix having a Tn, of 120 0C or more.
26. The composition of any of paragraphs 1 to 25 wherein the polypropylene-based TPO comprises a matrix having a Tm of 140 0C or more.
27. The composition of any of paragraphs 1 to 26 wherein the polypropylene-based TPO comprises a matrix having a Tm of 160 0C or more. 28. The composition of any of paragraphs 1 to 27 wherein the polypropylene-based TPO comprises a dispersed phase having a T8 of -20 0C or less.
29. The composition of any of paragraphs 1 to 28 wherein the polypropylene-based TPO comprises a dispersed phase having a Tg of -30 0C or less. 30. The composition of any of paragraphs 1 to 29 wherein the polypropylene-based TPO comprises a dispersed phase having a Tg of -40 0C or less.
31. The composition of any of paragraphs 1 to 30 wherein the polypropylene-based TPO comprises a dispersed phase having a Tg of -50 0C or less.
32. The composition of any of paragraphs 1 to 31 wherein the polypropylene-based TPO is an impact copolymer having a Tm of 1200C or more and a Tg of -30 0C or less.
33. The composition of any of paragraphs 1 to 32 wherein the polypropylene-based TPO is an impact copolymer having a matrix phase comprising polypropylene having a Tn, of 1200C or more and a dispersed phase comprising propylene copolymer having a Tg of -30 0C or less.
34. The composition of any of paragraphs 1 to 33 wherein the polypropylene-based TPO is an impact copolymer having a rubber content of 5 to 40 wt%, a melt flow rate of 5 to 150 dg/min, and a flexural modulus of 300 to 3000 MPa.
35. The composition of any of paragraphs 1 to 34 wherein the polypropylene-based TPO is an in-situ impact copolymer.
36. The composition of any of paragraphs 1 to 35 wherein the polypropylene-based TPO comprises two or more in-situ impact copolymers.
37. The composition of any of paragraphs 1 to 36 wherein the polypropylene-based TPO comprises two or more in-situ impact copolymers, where the combination of the impact copolymers comprises at least 50 wt% propylene and at least 10 wt% ethylene, based upon the weight of the impact copolymers. 38. The composition of any of paragraphs 1 to 37 where the composition further comprises 1 to 40 wt% of an ethylene copolymer.
39. The composition of any of paragraphs 1 to 38 wherein the polypropylene-based TPO is an impact copolymer present at 20 to 98.7 wt% and the composition further comprises 1 to 40 wt% of one or more ethylene copolymers). 40. The composition of any of paragraphs 1 to 39 wherein the polypropylene-based TPO is an in-situ impact copolymer present at 20 to 98.7 wt% and the composition further comprises 1 to 40 wt% of one or more ethylene copolymers) having a density of 0.90 g/cm3 or less. 41. The composition of any of paragraphs 1 to 40 where the composition further comprises 5 to 35 wt% of a copolymer of ethylene and one or more of propylene, butene, hexene, or octene, and the copolymer has a density of 0.85 to 0.90 g/cm3 and a melt index of 0.1 to 100 dg/min. 42. The composition of any of paragraphs 1 to 41 where the composition further comprises 5 to 35 wt% of a copolymer of ethylene and one or more of propylene, butene, hexene or octene, and the copolymer has a density of 0.85 to 0.88 g/cm3 and a melt index of 0.3 to 60 dg/min. 43. The composition of any of paragraphs 1 to 42 wherein the polypropylene-based TPO is an impact copolymer and the composition further comprises one or more EP Rubber(s). 44. The composition of any of paragraphs 1 to 43 wherein the polypropylene-based TPO is an impact copolymer present at 20 to 98.8 wt% and the composition further comprises 1 to 40 wt% of one or more EP Rubber(s). 45. The composition of any of paragraphs 1 to 44 wherein the polypropylene-based TPO is an in-situ impact copolymer present at 20 to 98.8 wt% and the composition further comprises 1 to 40 wt% of one or more EP Rubber(s) having an ethylene content of 25 to 80 wt% and a Mooney viscosity (ML 1+4, 125°C) of 10 to 100.
46. The composition of any of paragraphs 1 to 45 wherein the polypropylene-based TPO comprises at least one propylene polymer having a melting point of 1100C and at least one ethylene copolymer having a density of less than 0.90 g/cm .
47. The composition of any of paragraphs 1 to 46 wherein the polypropylene-based TPO comprises at least one propylene polymer having a melting point of 1100C and at least one EP Rubber having a density of less than 0.87 g/cm3. 48. The composition of any of paragraphs 1 to 47 wherein the polypropylene-based TPO comprises at least one propylene polymer and at least one ethylene copolymer having a density of less than 0.90 g/cm3 and at least one EP Rubber having a density of less than 0.87 g/cm3.
49. The composition of any of paragraphs 1 to 48 wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a flexural modulus of 900 to 3500 MPa; and the composition has one or both of the following properties: c) a notched Charpy impact strength at -3O0C of 1.5 to 15 kJ/m2 , and/or d) a notched Izod impact strength at -18°C of 60 to 500 J/m.
50. The composition of any of paragraphs 1 to 49 wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a flexural modulus of 900 to 3500 MPa ; and the composition has one or both of the following properties: c) a notched Charpy impact strength at -300C of 1.5 to 15 kJ/m2 , and/or d) a notched Izod impact strength at -18°C of 60 to 500 J/m; and the composition has one or more of the following properties: e) a notched Charpy impact strength at 230C of 20 kJ/m2 or more, and/or f) a notched Izod impact strength at 230C of 100 J/m or more, and/or g) a ductile failure in a multi-axial impact strength test at 230C, and/or h) a heat distortion temperature (HDT) of 60°C or more, and/or i) a tensile strength of 10 MPa or more, and/or j) shrinkage upon injection molding of 0.1 to 5%, and/or k) a fogging number of 70 or more.
51. The composition of any of paragraphs 1 to 49 wherein the composition has: a) a melt flow rate (MFR) of lO to 500 dg/min, and b) a fiexural modulus of 900 to 3500 MPa, and c) a notched Charpy impact strength at -30°C of 1.5 to 15 kJ/m2 , and d) a notched Izod impact strength at -18°C of 60 to 500 J/m, and e) a notched Charpy impact strength at 230C of 20 kJ/m2 or more. 52. The composition of any of paragraphs 1 to 49 wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a fiexural modulus of 900 to 3500 MPa, and c) a notched Charpy impact strength at -30°C of 1.5 to 15 kJ/m2 , and d) a notched Izod impact strength at -18°C of 60 to 500 J/m, and e) a notched Izod impact strength at 23°C of 100 J/m or more.
53. The composition of any of paragraphs 1 to 49 wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a fiexural modulus of 900 to 3500 MPa, and c) a notched Charpy impact strength at -30°C of 1.5 to 15 kJ/m2 , and d) a notched Izod impact strength at -18°C of 60 to 500 J/m, and e) a ductile failure in a multi-axial impact strength test at 23°C.
54. The composition of any of paragraphs 1 to 49 wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a fiexural modulus of 900 to 3500 MPa, and c) a notched Charpy impact strength at -300C of 1.5 to 15 kJ/m2 , and d) a notched Izod impact strength at - 18°C of 60 to 500 J/m, and e) a heat distortion temperature (HDT) of 600C or more.
55. The composition of any of paragraphs 1 to 49 wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a flexural modulus of 900 to 3500 MPa, and c) a notched Charpy impact strength at -3O0C of 1.5 to 15 kJ/m2 , and d) a notched Izod impact strength at -18°C of 60 to 500 J/m, and e) a tensile strength of 10 MPa or more. 56. The composition of any of paragraphs 1 to 49 wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a flexural modulus of 900 to 3500 MPa, and c) a notched Charpy impact strength at -30°C of 1.5 to 15 kJ/m2 , and d) a notched Izod impact strength at -18°C of 60 to 500 J/m, and e) shrinkage upon injection molding of 0.1 to 5%.
57. The composition of any of paragraphs 1 to 49 wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a flexural modulus of 900 to 3500 MPa, and c) a notched Charpy impact strength at -3O0C of 1.5 to 15 kJ/m2 , and d) a notched Izod impact strength at -18°C of 60 to 500 J/m, and e) a fogging number of 70 or more.
58. The composition of any of paragraphs 1 to 57 wherein the glass transition temperature (Tg) of at least one polymer component in the composition is depressed by at least 2°C for every 1 wt% of NFP present in the composition, while the peak melting temperature of the highest melting component remains within 50C of its value for the same composition absent the NFP.
59. The composition of any of paragraphs 1 to 58 wherein the melt flow rate (MFR) of the composition increases by at least 2% for every 1 wt% of NFP present in the composition as compared to the same composition absent the NFP.
60. The composition of any of paragraphs 1 to 59 wherein the NFP has a kinematic viscosity at 1000C of 4 cSt or more.
61. The composition of any of paragraphs 1 to 60 wherein the NFP has a kinematic viscosity at 100°C of6 cSt or more.
62. The composition of any of paragraphs 1 to 61 wherein the NFP has a kinematic viscosity at 1000C of 8 cSt or more. 63. The composition of any of paragraphs 1 to 62 wherein the NFP has a kinematic viscosity at 100°C of 10 cSt or more.
64. The composition of any of paragraphs 1 to 63 wherein the NFP has a kinematic viscosity at 100oC of6 to 5000 cSt.
65. The composition of any of paragraphs 1 to 64 wherein the NFP has a kinematic viscosity at 100oC of8 to 3000 cSt.
66. The composition of any of paragraphs 1 to 65 wherein the NFP has a kinematic viscosity at 100oC of l0 to l000 cSt.
67. The composition of any of paragraphs 1 to 66 wherein the NFP has a pour point of -200C or less.
68. The composition of any of paragraphs 1 to 61 wherein the NFP has a pour point of -300C or less.
69. The composition of any of paragraphs 1 to 68 wherein the NFP has a pour point of -400C or less. 70. The composition of any of paragraphs 1 to 69 wherein the NFP has a pour point of -300C or less and a kinematic viscosity at 400C of 20 to 600 cSt.
71. The composition of any of paragraphs 1 to 70 wherein the NFP has a Tg of -40 0C or less.
72. The composition of any of paragraphs 1 to 71 wherein the NFP has a viscosity index of 100 or more. 73. The composition of any of paragraphs 1 to 72 wherein the NFP has a viscosity index of 110 or more.
74. The composition of any of paragraphs 1 to 73 wherein the NFP has a viscosity index of 120 or more.
75. The composition of any of paragraphs 1 to 74 wherein the NFP has a viscosity index of 130 or more.
76. The composition of any of paragraphs 1 to 75 wherein the NFP has a viscosity index of 135 to 300.
77. The composition of any of paragraphs 1 to 76 wherein the NFP has a flash point of 2000C or more. 78. The composition of any of paragraphs 1 to 77 wherein the NFP has a flash point of 2100C or more.
79. The composition of any of paragraphs 1 to 78 wherein the NFP has a flash point of 2300C or more.
80. The composition of any of paragraphs 1 to 79 wherein the NFP has a specific gravity of 0.86 or less.
81. The composition of any of paragraphs 1 to 80 wherein the NFP has a specific gravity of 0.855 or less.
82. The composition of any of paragraphs 1 to 81 wherein the NFP has a viscosity index of 120 or more, a flash point of 2000C or more, and a pour point of -100C or less. 83. The composition of any of paragraphs 1 to 82 wherein the NFP has a kinematic viscosity at 1000C of 35 cSt or more, a specific gravity of 0.87 or less, and a flash point of 2000C or more.
84. The composition of any of paragraphs 1 to 83 wherein the NFP has a) a flash point of 2000C or more; b) a specific gravity of 0.86 or less; and cl) a pour point of -100C or less and a viscosity index of 120 or more, or c2) a pour point of -200C or less, or c3) a kinematic viscosity at 1000C of 35 cSt or more.
85. The composition of any of paragraphs 1 to 84 wherein the NFP has a) a specific gravity of 0.85 or less; and bl) a kinematic viscosity at 1000C of 3 cSt or more, and/or b2) a number- average molecular weight (Mn) of at least 280 g/mol. 86. The composition of any of paragraphs 1 to 85 wherein the NFP has a) a specific gravity of 0.86 or less; and bl) a kinematic viscosity at 1000C of 5 cSt or more, and/or b2) a number- average molecular weight (Mn) of at least 420 g/mol.
87. The composition of any of paragraphs 1 to 86 wherein the NFP has a) a specific gravity of 0.87 or less; and bl) a kinematic viscosity at 1000C of 10 cSt or more, and/or b2) a number- average molecular weight (Mn) of at least 700 g/mol.
88. The composition of any of paragraphs 1 to 87 wherein the NFP has a kinematic viscosity at 1000C of 3 to 100 cSt, and a number average molecular weight (Mn) of 300 to 3,000 g/mol.
89. The composition of any of paragraphs 1 to 88 wherein the non-functionalized plasticizer has a kinematic viscosity at 1000C of 5 cSt or more, a viscosity index of 100 or more, a pour point of -200C or less, a specific gravity less than 0.86, and a flash point greater than 2000C.
90. The composition of any of paragraphs 1 to 89 wherein the non-functionalized plasticizer comprises at least 50 weight% of Ce to C1So isoparaffins.
91. The composition of any of paragraphs 1 to 90 wherein the non-functionalized plasticizer has a pour point of -400C or less and a specific gravity of less than 0.85. 92. The composition of any of paragraphs 1 to 91 wherein the non-functionalized plasticizer comprises oligomers of C5 to Cn alpha-olefins.
93. The composition of any of paragraphs 1 to 92 wherein the non-functionalized plasticizer comprises oligomers of Ce to Ci4 alpha-olefins.
94. The composition of any of paragraphs 1 to 93 wherein the rion-functionalized plasticizer comprises oligomers of Cs to C12 alpha-olefins.
95. The composition of any of paragraphs 1 to 94 wherein the non-functionalized plasticizer comprises oligomers of decene.
96. The composition of any of paragraphs 1 to 95 wherein the non-functionalized plasticizer comprises oligomers of C3 to C24 linear alpha-olefins wherein C3 and C4 linear alpha-olefins are present at 10 wt% or less.
97. The composition of any of paragraphs 1 to 96 wherein the non-functionalized plasticizer comprises oligomers of two or more C3 to Ci8 linear alpha-olefins wherein C3 and C4 linear alpha-olefins are present at 10 wt% or less. 98. The composition of any of paragraphs 1 to 97 wherein the non-functionalized plasticizer comprises oligomers of C5 to Ci g linear alpha-olefins and has a branching ratio of 0.20 or less. 99. The composition of any of paragraphs 1 to 95 wherein the non-functionalized plasticizer comprises C15 to C1500 oligomers of alpha-olefins and has a kinematic viscosity at 100 0C of 3 cSt or more. 100. The composition of any of paragraphs 1 to 95 wherein the non-functionalized plasticizer comprises C20 to C 1000 oligomers of alpha-olefins and has a kinematic viscosity at 1000C of 5 cSt or more.
101. The composition of any of paragraphs 1 to 95 wherein the non-functionalized plasticizer comprises Ci 5 to Ci 500 oligomers of alpha-olefins and has a kinematic viscosity at 1000C of 8 cSt or more, a viscosity index of 120 or more, and a specific gravity of 0.86 or less.
102. The composition of any of paragraphs 1 to 95 wherein the non-functionalized plasticizer comprises C1S to Cisoo oligomers of alpha-olefins and has a kinematic viscosity of 10 cSt or more at 1000C and a viscosity index of 120 or more, and a specific gravity of 0.86 or less.
103. The composition of any of paragraphs 1 to 95 wherein the non-functionalized plasticizer comprises oligomers of C5 to Ci8 linear alpha-olefins and has a kinematic viscosity of 8 cSt or more at 1000C5 a viscosity index of 120 or more, and a pour point of -25°C or less.
104. The composition of any of paragraphs 1 to 89 wherein the non-functionalized plasticizer comprises: 1) a copolymer of a C4 olefins derived from a C4 raffmate stream or 2) a poly(n- butene) or 3) a copolymer of at least isobutylene derived units, 1-butene derived units, and 2- butene derived units; and has a pour point of -200C or less and a kinematic viscosity at 1000C of 6 to 15O cSt.
105. The composition of any of paragraphs 1 to 89 wherein the non-functionalized plasticizer comprises a mineral oil having a saturates levels of 90% or more, a sulfur content of less than 0.03%, and a VI of 120 or more. 106. The composition of any of paragraphs 1 to 89 wherein the non-functionalized plasticizer comprises a paraffinic process oil with
A) a viscosity index of 90 to 119, and
B) a Cp of 65% or more, and
C) a CA of 1% or less, and D) a kinematic viscosity at 40°C of 80 cSt or more, and
E) a pour point of -15°C or less .
107. The composition of any of paragraphs 1 to 89 wherein the non-functionalized plasticizer is a hydrocarbon fluid derived from a Gas-To-Liquids process comprising hydroisomerized Fischer- Tropsch waxes and having a pour point of about -20 to -600C and a kinematic viscosity of about 6 to 20 cSt.
108. The composition of any of paragraphs 1 to 89 wherein the non-functionalized plasticizer comprises a mixture of paraffins has two or more of the following properties:
1) a naphthenic content of less than 40 wt%, based on the total weight of the paraffin mixture; and/or
2) a normal paraffins content of less than 5 wt%, based on the total weight of the paraffin mixture; and/or
3) an aromatic content of 1 wt% or less, based on the total weight of the paraffin mixture; and/or 4) a saturates level of 90 wt% or higher; and/or
5) a percentage of carbons in chain-type paraffinic structures (Cp) of 80% or more; and/or
6) a branched paraffurnormal paraffin ratio greater than about 10:1; and/or
7) sidechains with 4 or more carbons making up less than 10% of all sidechains; and/or
8) sidechains with 1 or 2 carbons making up at least 50% of all sidechains; and/or 9) a sulfur content of 300 ppm or less (weight basis); and/or
10) a nitrogen content of 300 ppm or less (weight basis); and/or
11) a number-average molecular weight of 300 to 1800 g/mol; and/or
12) a kinematic viscosity at 400C of 10 cSt or more; and/or
13) a kinematic viscosity at 1000C ranging from 2 to 50 cSt; and/or 14) a viscosity index (VT) of 80 or greater; and/or
15) a pour point of -5°C or lower; and/or
16) a flash point of 2000C or more; and/or
17) a specific gravity of 0.86 or less; and/or
18) an aniline point of 1200C or more; and/or 19) a bromine number of 1 or less.
109. The composition of any of paragraphs 1 to 108 wherein the filler is selected from the group consisting of mineral aggregates (natural or synthetic), fibers, carbon black, graphite, wollastonite, natural and synthetic clays including nanoclays and organoclays, sand, and glass beads. 110. The composition of any of paragraphs 1 to 109 wherein the filler has a median particle diameter of 0.1-100 microns.
111. The composition of any of paragraphs 1 to 110 wherein the filler has an aspect ratio greater than 1.2. 112. The composition of any of paragraphs 1 to 111 wherein the filler has a specific surface area of 10 to 300 m2/cm3.
113. The composition of any of paragraphs 1 to 112 wherein the filler is selected from the group consisting of talc, mica, wollastonite, titanium dioxide, silicon carbide, silica, silicon dioxide and other oxides of silica (precipitated or not), calcium silicate, calcium and barium sulfates, calcium carbonate (calcite), lead carbonate, magnesium silicate, magnesium oxysulfates, antimony oxide, zinc white, lithopone, zircon, corundum, spinel, apatite, Barytes powder, magnesiter, dolomite, zinc borate, hydrotalcite compounds of the ions Mg, Ca, or Zn with Al, Cr or Fe and CO3 and/or HPO4 (hydrated or not), quartz powder, hydrochloric magnesium carbonate, alumina, chrome, phosphorous and brominated flame retardants, antimony trioxide, silicone, and blends thereof. 114. The composition of any of paragraphs 1 to 112 wherein the filler is selected from the group consisting of glass fibers (long or short), carbon fibers, and natural and synthetic polymer fibers.
115. The composition of any of paragraphs 1 to 112 wherein the filler is selected from the group consisting of polyethylene terephthalate (PET) fibers and rayon fibers.
116. The composition of any of paragraphs 1 to 112 wherein the filler is selected from the group consisting of clays comprising one or more of ammonium, primary alkylammonium, secondary alkylammonium, tertiary alkylammonium, quaternary alkylammonium, phosphonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines or sulfides or sulfonium derivatives of aliphatic, aromatic or arylaliphatic amines, phosphines or sulfides.
117. The composition of any of paragraphs 1 to 112 wherein the filler is selected from the group consisting of montmorillonite, sodium montrnorillonite, calcium montmorillonite, magnesium montmorillonite, nontronite, beidellite, volkonskoite, laponite, hectorite, saponite, sauconite, magadite, kenyaite, sobockite, svindordite, stevensite, vermiculite, halloysite, aluminate oxides, hydrotalcite, illite, rectorite, tarosovite, ledikite, and florine mica.
118. The composition of any of paragraphs 1 to 112 wherein the filler is a nano-clay with mean particle diameter of less than 1 micron.
119. The composition of any of paragraphs 1 to 118 wherein the composition further comprises a slip agent, present at 0.001 to 0.5 wt% based upon the weight of the composition.
120. The composition of any of paragraphs 1 to 119 wherein the composition further comprises a slip agent selected from the group consisting of magnesium stearate, calcium stearate, sodium stearate, zinc stearate, calcium oleate, zinc oleate, magnesium oleate, castor oil, corn oil, cottonseed oil, olive oil, rapeseed oil, soybean oil, sunflower oil, glycerol monostearate, pentaerythritol monooleate, oleamide, erucamide, linoleamide, Carbowax, adipic acid, sebacic acid, carnauba wax, microcrystalline wax, polyolefin waxes, polytetrafluoroethylene, fluorine oils, fluorine waxes, silicone oils, polydimethylsiloxane, amino-modified polydimethylsiloxane, palmitamide, stearamide, aracbidamide, behenamide, oleamide, erucamide, linoleamide, stearyl stearamide, palmityl palmitamide, stearyl arachidamide, stearamidoethylstearamide, stearamidoethylpalmitamide, palmitamido-ethylstearamide, ethylenebisstearamide, ethylenebisoleamide, stearylerucamide, erucamidoethylerucamide, oleamidoethyloleamide, erucamidoethyloleamide, oleamidoethylerucamide, stearamidoethylerucamide, erucamidoethylpalmitamide, palmitamidoethyloleamide, and N,N'-ethylenebisstearamide).
121. The composition of any of paragraphs 1 to 120 wherein the composition further comprises a tackifier, present at less than 10 wt% based upon the weight of the composition.
122. The composition of any of paragraphs 1 to 121 wherein the composition further comprises a nucleating agent, present at 0.01 to 1 wt% based upon the weight of the composition.
123. The composition of any of paragraphs 1 to 122 wherein the composition further comprises a nucleating agent selected from the group consisting of silica, kaolin, carbon black, and talc; sodium salts, lithium salts, potassium salts, phosphonic acid salts, carboxylate salts, and aromatic carboxylic-acid salts; sodium phosphates, phosphate esters, and phosphate ester salts, metal salts of suberic acid, metal salts of hexahydrophthalic acid; salts of disproportionated rosin esters; sorbitol, dibenzylidene sorbitol, sorbitol acetal, and sorbitol di-acetal,; quinacridone dyes, naphthalene carboxamide; benzenetrisamide, 1,3,5-benzenetrisamide, trimesic acid, poly(3- methyl-1-butene), poly(dimethylstyrene), poly(ethylene terephthalate), polyamides (nylons), and polycarbonates. 124. The composition of any of paragraphs 1 to 122 wherein the composition further comprises a nucleating agent selected from the group consisting of sodium benzoate, sodium naphthenoate, sodium 2,2'-methylenebis(4,6-di-tert-butylphenyl) phosphate, aluminum 2,2'-methylenebis(4,6- di-tert-butylphenyl) phosphate, di(p-tolylidene) sorbitol, dibenzylidene sorbitol, di(p- methylbenzylidene) sorbitol, di(p-ethylbenzylidene) sorbitol, bis(3,4-dimethylbenzylidene) sorbitol, N%N'-dicyclohexyl-2,6-naphthalenedicarboxamide, l,3:2,4-dibenzylidenesorbitol, 1 ,3 :2,4-bis-(p-methylbenzylidene)sorbitol, 1 ,3 :2,4-bis(3,4-dimethylbenzylidene)sorbitol, and 2.2.1-heptane-bicyclodicarboxylic acid, 2,2'-methylenebis(4,6-di-tertbutylphenol) phosphate salt, and 2,2'-methylenebis(4,6-di-tertbutylphenol) phosphate aluminum complex, l,3:2,4-bis-(p- ethylbenzylidene)sorbitol; N,N'-dicyclohexyl-2,6-naphathalene dicarboxamide], N,N'- dicyclohexyl-2,6-naphathalene diczroxamide, 1,3-2,4- dibenzylidenesorbitol, l,3:2,4-bis-(p- methyϊbenzylidene)sorbitol; (1,3:2,4) dimethyldibenylidene sorbitol, and sorbitol.
125. The composition of any of paragraphs 1 to 122 wherein the composition further comprises a nucleating agent selected from the group consisting of l,3:2,4-bis(3,4- dimethylbenzylidene)sorbitol, 2.2.1-heptane-bicyclodicarboxylic acid, l,3:2,4-bis-(p- methylbenzylidene)sorbitol, 2,2'-methylenebis(4,6-di-tertbutylphenol) phosphate salt, and sodium benzoate.
126. The composition of any of paragraphs 1 to 125 wherein naphthenic and aromatic mineral oils are substantially absent. 127. The composition of any of paragraphs 1 to 126 wherein paraffinic mineral oils with a kinematic viscosity at 400C of less than 80 cSt and a pour point of greater than -15°C are substantially absent.
128. The composition of any of paragraphs 1 to 127 wherein the composition has a flow mark visibility rating of 3 or less and the distance from the gate to the first visible flow mark is 5 in or more
129. The composition of any of paragraphs 1 to 128 wherein the composition has a scratch resistance rating of 3 N or more.
130. The composition of any of paragraphs 1 to 128 wherein the non-functionalized plasticizer comprises a mixture of paraffins has two or more of the following properties: 1) a naphthenic content of less than 40 wt%, based on the total weight of the paraffin mixture; and/or
2) a normal paraffins content of less than 5 wt%, based on the total weight of the paraffin mixture; and/or
3) an aromatic content of 1 wt% or less, based on the total weight of the paraffin mixture; and/or
4) a saturates level of 90 wt% or higher; and/or
5) a percentage of carbons in chain-type paraffinic structures (Cp) of 80% or more; and/or
6) a branched paraffin:normal paraffin ratio greater than about 10: 1 ; and/or
7) sidechains with 4 or more carbons making up less than 10% of all sidechains; and/or 8) sidechains with 1 or 2 carbons making up at least 50% of all sidechains; and/or
9) a sulfur content of 300 ppm or less (weight basis); and/or
10) a nitrogen content of 300 ppm or less (weight basis)
131. The composition of any of paragraphs 1 to 130 wherein the non-functionalized plasticizer comprises a mixture of paraffins has two or more of the following properties: 1) a number-average molecular weight of 300 to 1800 g/mol; and/or
2) a kinematic viscosity at 400C of 10 cSt or more; and/or
3) a kinematic viscosity at 1000C ranging from 2 to 50 cSt; and/or
4) a viscosity index (VI) of 80 or greater; and/or 5) a pour point of -5°C or lower; and/or
6) a flash point of 2000C or more; and/or
7) a specific gravity of 0.86 or less; and/or
8) an aniline point of 1200C or more; and/or
9) a bromine number of 1 or less. 132. An article comprising the composition of any of paragraphs 1 to 131.
133. A molded automotive part comprising the composition of any of paragraphs 1 to
134. The article of paragraph 132 where the article is selected from the group consisting of films, tapes, sheets, fibers, tubing, pipes, coatings, fabrics (woven and nonwoven), tarps, agricultural barriers, packaging (durable and disposable), household appliances, washing machines, refrigerators, blenders, air conditioners, furniture (indoor and outdoor), tables, chairs, benches, shelving, sporting equipment, skis, surfboards, skateboards, skates, boots, sleds, scooters, kayaks, paddles, solid wheels, stadium seating, amusement park rides, personal protective equipment, safety helmets, shin guards, emergency response equipment, cookware, utensils, trays, pallets, carts, tanks, tubs, pond liners, storage containers, crates, pails, jars, bottles, toys, child car seats and booster chairs, medical devices, sportswear, luggage, tool housings, electronics housings, building construction materials, flooring, siding, roofing, counter tops, electrical housings and connectors, lighting, gardening equipment, handles on shovels, handles on wheelbarrows, playground equipment, motor housings, pump housings, battery housings, instrument housings, switches, knobs, buttons, handles, pet supplies, laboratory supplies, personal hygiene devices, razors, brushes, hairdryers, cleaning supplies, brooms, dust pans, musical instrument cases, statues, trophies, artwork, costume jewelry, picture frames, eyeglass frames, plant pots, firearm components, and automotive components.
135. The article paragraph 132 where the article is selected from the group consisting of bumpers, bumper fascias; exterior body panels, door panels, grills, exterior trim, body side moldings, side cladding, side molding, end caps, hoods, deck lids, mirror housings, roof racks, wheel covers, wheel liners, wheel flares, fender liners, hub caps, running boards, step pads, sill plates, air dams, splash shields, mud guards, bed liners, and rocker panels; fuel tanks; interior trim, including steering column covers, consoles, door panels, pillars, supports, knobs, buttons, handles, safety screens, instrument panels, dash boards, knee bolsters; passenger side airbag covers, headliners, glove boxes, trays, cup holders, compartments, lids, seat components, backs, supports, safety belt securing devices, under-hood parts, battery trays, fan shrouds, electrical housings; cable bearings, structural components, door carriers, truck bed separators, load floors, and trunk dividers. 136. A vehicle comprising the composition of any of paragraphs 1 to 131 wherein the vehicle is selected from the group consisting of cars, trucks, buses, boats, all terrain vehicles, personal water craft, golf carts, snowmobiles, motorcycles, mopeds, tractors, mowers, wagons, bicycles, airplanes, helicopters, trains, military machines, and gondolas.
137. An article comprising the composition of any of paragraphs 1 to 131 wherein the article has at least one overall dimension greater than 30 cm.
138. An article comprising the composition of any of paragraphs 1 to 131 wherein the article has as a length greater than 30 cm.
139. An automotive part comprising the composition of any of paragraphs 1 to 131 wherein the article has as a length greater than 30 cm. 140. A process to prepare the composition of any of paragraphs 1 to 131 by combining the components in an extruder.
141. A process to prepare a molded part comprising heating the composition of any of paragraphs 1 to 131, then introducing the heated composition into a mold and thereafter cooling the composition and removing it from the mold. 142. A vehicle replacement part comprising the composition of any of paragraphs 1 to 131.
EXPERIMENTAL METHODS
[0210] Unless otherwise noted, physical and chemical properties described herein are measured using the following test methods:
Polvolefin Test Methods
Melt Index (MI) ASTM D 1238 (190°C/2.16 kg)
Melt Flow Rate (MFR) ASTM D 1238 (230°C/2.16 kg)
Mooney Viscosity ASTM D 1646
Density ASTM D 1505
Glass Transition Temperature (Tg) DMA (see below)
Melting Temperature (Tn,) DSC (see below)
Crystallization Temperature (Tc) DSC (see below)
Heat of Fusion (Hf) DSC (see below)
% Crystallinity DSC (see below)
Mn, Mw, and Mw/Mn SEC (see below)
Branching Index (g1) SEC (see below)
Composition Distribution Breadth Index (CDBI) See below
Intrinsic Viscosity ASTM D 1601 (135°C in decalin)
Injection.Molding ASTM D 4101 Test Specimen Conditioning ASTM D 618, Procedure A
Tensile Properties (e.g., Young's modulus, yield ASTM D 638 (Type I bar, 5 cm/min) stress & strain, break stress & strain) 1% Secant Flexural Modulus ASTM D 790 (A, 1.3 mm/min) Heat Deflection Temperature ASTM D 648 (0.45 MPa) Vicat Softening Temperature ASTM D 1525 (20O g) Gardner Impact Strength ASTM D 5420 (GC) Notched Izod Impact Strength ASTM D 256 (Method A, or Method E if
"reverse notch" noted)
Notched Charpy Impact Strength ASTM D 6110 Multi- Axial Impact Strength ASTM D 3763 (15 MPH) Shore (Durometer) Hardness ASTM D 2240 (A or D, 15 sec delay) Shrinkage upon injection molding ISO 2577 Flow Marks See below Scratch Resistance See below
Fluid Test Methods
Kinematic Viscosity (KV) ASTM D 445
Viscosity Index (VI) ASTM D 2270
Pour Point ASTM D 97
Specific Gravity and Density ASTM D 4052 (15.6/15.6°C)
Flash Point ASTM D 92
Mn GC or GPC (see below)
Glass Transition Temperature (Tg) ASTM D 1356
Boiling / Distillation Range ASTM D 1160
Carbon Type Composition (CA, CN, and Cp) ASTM D 2140 (see below)
Saturates Content ASTM D 2007
Sulfur Content ASTM D 2622
Nitrogen Content ASTM D 4629
Bromine Number ASTM D 1159 (or ASTM D 2710 if so directed by ASTM D 1159)
Aniline Point ASTM D 611 Color ASTM D 1209 (see below)
Composition Test Methods
Polypropylene tacticity 13C-NMR (see below)
Olefin content in ethylene or propylene copolymers 13C-NMR (see below)
Ethylene content of EP Rubbers ASTM D 3900
NFP content See below
Permanence See below
Filler content ISO 3451-1 (A)
Hetero-phase morphology Multiple domains by AFM and/or multiple Tg' s by DMA (see below)
Dynamic Mechanical Analysis (DMA)
[0211] The glass transition temperature (Tg) is measured using dynamic mechanical analysis. This test provides information about the small-strain mechanical response of a sample as a function of temperature over a temperature range that includes the glass transition region and the visco-elastic region prior to melting. Specimens are tested using a commercially available DMA instrument (e.g., TA Instruments DMA 2980 or Rheometrics RSA) equipped with a dual cantilever test fixture. The specimen is cooled to -1300C then heated to 6O0C at a heating rate of 2°C/min while subjecting to an oscillatory deformation at 0.1% strain and a frequency of 1 rad/sec. The output of these DMA experiments is the storage modulus (E') and loss modulus (E"). The storage modulus measures the elastic response or the ability of the material to store energy, and the loss modulus measures the viscous response or the ability of the material to dissipate energy. The ratio of E"/E', called Tan-delta, gives a measure of the damping ability of the material; peaks in Tan-delta are associated with relaxation modes for the material. Tg is defined to be the peak temperature associated with the β-relaxation mode, which typically occurs in a temperature range of -80 to +200C for polyolefms. In a hetero-phase blend, separate β- relaxation modes for each blend component may cause more than one Tg to be detected for the blend; assignment of the Tg for each component are preferably based on the Tg observed when the individual components are similarly analyzed by DMA (although slight temperature shifts are possible). Differential Scanning Calorimetry (DSC)
[0212] Crystallization temperature (Tc) and melting temperature (or melting point, Tm) are measured using Differential Scanning Calorimetry (DSC) on a commercially available instrument (e.g., TA Instruments 2920 DSC). Typically, 6 to 10 mg of molded polymer or plasticized polymer are sealed in an aluminum pan and loaded into the instrument at room temperature. Melting data (first heat) is acquired by heating the sample to at least 300C above its melting temperature, typically 2200C for polypropylene, at a heating rate of 10°C/min. The sample is held for at least 5 minutes at this temperature to destroy its thermal history. Crystallization data are acquired by cooling the sample from the melt to at least 500C below the crystallization temperature, typically -500C for polypropylene, at a cooling rate of 20°C/min. The sample is held at this temperature for at least 5 minutes, and finally heated at 10°C/min to acquire additional melting data (second heat). The endothermic melting transition (first and second heat) and exothermic crystallization transition are analyzed according to standard procedures. The melting temperatures reported are the peak melting temperatures from the second heat unless otherwise specified. [0213] For polymers displaying multiple peaks, the melting temperature is defined to be the peak melting temperature from the melting trace associated with the largest endothermic calorimetric response (as opposed to the peak occurring at the highest temperature). Likewise, the crystallization temperature is defined to be the peak crystallization temperature from the crystallization trace associated with the largest exothermic calorimetric response (as opposed to the peak occurring at the highest temperature).
[0214] Areas under the DSC curve are used to determine the heat of transition (heat of fusion,
Hf, upon melting or heat of crystallization, H0, upon crystallization), which can be used to calculate the degree of crystallinity (also called the percent crystallinity). The percent crystallinity (X%) is calculated using the formula: [area under the curve (in J/g) / H° (in J/g)] *
100, where H° is the ideal heat of fusion for a perfect crystal of the homopolymer of the major monomer component. These values for H° are to be obtained from the Polymer Handbook,
Fourth Edition, published by John Wiley and Sons, New York 1999, except that a value of 290
J/g is used for H°(polyethylene), a value of 140 J/g is used for H° (polybutene), and a value of 207 J/g is used for H°(polypropylene).
Size-Exclusion Chromatography (SEC)
[0215] Molecular weight (weight-average molecular weight, Mw, number-average molecular weight, Mn, and molecular weight distribution, Mw/Mn or MWD) are determined using a commercial High Temperature Size Exclusion Chromatograph (e.g., from Waters Corporation or Polymer Laboratories) equipped with three in-line detectors: a differential refractive index detector (DRI), a light scattering (LS) detector, and a viscometer.
[0216] The following approach is used for polyolefins. Details not described, including detector calibration, can be found in Macromolecules 34, 6812-6820 (2001). Column set: 3 Polymer Laboratories PLgel 10mm Mixed-B columns Flow rate: 0.5 mL/min
Injection volume: 300 μL
Solvent: 1,2,4-trichlorobenzene (TCB), containing 6 g of butylated hydroxy toluene dissolved in
4 liters of Aldrich reagent grade TCB Temperature: 135°C [0217] The various transfer lines, columns, DRI detector and viscometer are contained in an oven maintained at 135°C. The TCB solvent is filtered through a 0.7 μm glass pre-filter and subsequently through a 0.1 μm Teflon filter, then degassed with an online degasser before entering the SEC. Polymer solutions are prepared by placing dry polymer in a glass container, adding the desired amount of TCB, then heating the mixture at 1600C with continuous agitation for about 2 hours. AU quantities are measured gravimetrically. The TCB densities used to express the polymer concentration in mass/volume units are 1.463 g/mL at room temperature and 1.324 g/mL at 135°C. Injection concentration range from 1.0 to 2.0 nαg/mL, with lower concentrations being used for higher molecular weight samples. Prior to running a set of samples, the DRI detector and injector are purged, the flow rate increased to 0.5 ml/min, and the DRI allowed to stabilize for 8-9 hours; the LS laser is turned on 1 hr before running samples. [0218] The concentration, c, at each point in the chromatogram is calculated from the baseline-subtracted DRI signal, IQRI, using the following equation: c = KDRilDRi/(dn/dc) where KDRI is a constant determined by calibrating the DRI, and (dn/dc) is the same as described below for the light scattering (LS) analysis. Units on parameters throughout this description are such that concentration is expressed in g/mL, molecular weight is expressed in g/mol, and intrinsic viscosity is expressed in dL/g. [0219] The LS detector is a Wyatt Technology High Temperature mini-DAWN. The molecular weight, M, at each point in the chromatogram is determined by analyzing the LS output using the Zimm model for static light scattering (M.B. Huglin, LIGHT SCATTERING FROM POLYMER SOLUTIONS, Academic Press, 1971):
— ^r = ^ + 2Ax
ΛR(θ) MP(θ) 2 [0220] Here, ΔR(Θ) is the measured excess Rayleigh scattering intensity at scattering angle θ, c is the polymer concentration determined from the DRI analysis, A2 is the second virial coefficient [for purposes of this invention, A2 = 0.0006 for propylene polymers and 0.001 otherwise], P(θ) is the form factor for a monodisperse random coil, and K0 is the optical constant for the system: „ _ 4πV(dn/dc)2 λ4NA where NA is Avogadro's number, and (dn/dc) is the refractive index increment for the system. The refractive index, n = 1.500 for TCB at 135°C and λ = 690 nm. For purposes of this invention and the claims thereto (dn/dc) = 0.104 for propylene polymers and 0.1 otherwise. [0221] A high temperature Viscotek Corporation viscometer, which has four capillaries arranged in a Wheatstone bridge configuration with two pressure transducers, is used to determine specific viscosity. One transducer measures the total pressure drop across the detector, and the other, positioned between the two sides of the bridge, measures a differential pressure. The specific viscosity, ηs, for the solution flowing through the viscometer is calculated from their outputs. The intrinsic viscosity, [η], at each point in the chromatogram is calculated from the following equation: ηs = c[η] + 0.3(c[η])2 where c is concentration and was determined from the DRI output.
[0222] The branching index (g1) is calculated using the output of the SEC-DRI-LS-VIS method as follows. The average intrinsic viscosity, [ηjavg, of the sample is calculated by:
Figure imgf000075_0001
where the summations are over the chromotographic slices, i, between the integration limits. The branching index g* is defined as:
Figure imgf000075_0002
where, for puφose of this invention and claims thereto, α = 0.695 for ethylene, propylene, and butene polymers; and k = 0.000579 for ethylene polymers, k = 0.000262 for propylene polymers, and k = 0.000181 for butene polymers. Mv is the viscosity-average molecular weight based on molecular weights determined by LS analysis. Composition Distribution Breadth Index (CDBD
[0223] CDBI is a measure of the composition distribution of monomer within the polymer chains. It is measured as described in WO 93/03093, with the modification that any fractions having a weight-average molecular weight (Mw) below 20 kg/mol are ignored in the calculation.
13C-NMR Spectroscopy on Polvolefins [0224] Polypropylene microstructure is determined by 13C-NMR spectroscopy, including the concentration of isotactic and syndiotactic diads ([m] and [r]), triads ([mm] and [rr]), and pentads ([mmmm] and [rrrr]). The designation "m" or "r" describes the stereochemistry of pairs of contiguous propylene groups, "m" referring to meso and "r" to racemic. Samples are dissolved in d2-l,l,2,2-tetrachloroethane, and spectra recorded at 125°C using a 100 MHz (or higher) NMR spectrometer. Polymer resonance peaks are referenced to mmmm = 21.8 ppm. Calculations involved in the characterization of polymers by NMR are described by F. A. Bovey in POLYMER CONFORMATION AND CONFIGURATION (Academic Press, New York 1969) and J. Randall in POLYMER SEQUENCE DETERMINATION, 13C-NMR METHOD (Academic Press, New York, 1977). [0225] The "propylene tacticity index", expressed herein as [m/r], is calculated as defined in H.N. Cheng, Macromolecules, 17, 1950 (1984). When [m/r] is 0 to less than 1.0, the polymer is generally described as syndiotactic, when [m/r] is 1.0 the polymer is atactic, and when [m/r] is greater than 1.0 the polymer is generally described as isotactic.
[0226] The "mm triad tacticity index" of a polymer is a measure of the relative isotacticity of a sequence of three adjacent propylene units connected in a head-to-tail configuration. More specifically, in the present invention, the mm triad tacticity index (also referred to as the "mm Fraction") of a polypropylene homopolymer or copolymer is expressed as the ratio of the number of units of meso tacticity to all of the propylene triads in the copolymer: _ . PPP(mm) mm Fraction- 5 —
PPP(mm)+ PPP(mr)+ PPP(rr) where PPP(mm), PPP(mr) and PPP(rr) denote peak areas derived from the methyl groups of the second units in the possible triad configurations for three head-to-tail propylene units, shown below in Fischer projection diagrams:
Figure imgf000076_0001
PPP ?((πrτ):
Figure imgf000076_0002
[0227] The calculation of the mm Fraction of a propylene polymer is described in U.S. Patent 5,504,172 (homopolymer: column 25, line 49 to column 27, line 26; copolymer: column 28, line 38 to column 29, line 67). For further information on how the mm triad tacticity can be determined from a 13C-NMR spectrum, see 1) J. A. Ewen, CATALYTIC POLYMERIZATION OF OLEFINS: PROCEEDINGS OF THE INTERNATIONAL SYMPOSIUM ON FUTURE ASPECTS OF OLEFIN POLYMERIZATION, T. Keii and K. Soga, Eds. (Elsevier, 1986), pp. 271-292; and 2) U.S. Patent Application US2004/054086 (paragraphs [0043] to [0054]). [0228] Ethylene content in ethylene copolymers is determined by ASTM D 5017-96, except that the minimum signal-to-noise should be 10,000:1. Propylene content in propylene copolymers is determined by following the approach of Method 1 in Di Martino and Kelchermans, J. Appl. Polym. ScL 56, 1781 (1995), and using peak assignments from Zhang, Polymer 45, 2651 (2004) for higher olefin comonomers. Fluid Molecular Weight
[0229] The number-average molecular weight (Mn) is determined by one of two methods:
1. For samples having a kinematic viscosity at 1000C of 10 cSt or less use Gas Chromatography (GC) with a mass spectrometer detector, as generally described in MODERN PRACTICE OF GAS CHROMATOGRAPHY, 3RD ED., R.L. Grob and E.F. Barry (Wiley-Interscience, 1995); or
2. For samples having a kinematic viscosity at 100°C of more than 10 cSt use Gel Permeation Chromatography (GPC), as generally described in MODERN SIZE EXCLUSION LIQUID CHROMATOGRAPHS, W.W. Yan, JJ. Kirkland, and D.D. BIy, (J. Wiley & Sons, 1979), calibrated using polystyrene standards. Fluid Carbon Type Composition
[0230] Carbon type composition is determined by ASTM D 2140, and gives the percentage of aromatic carbons (CA), naphthenic carbons (CN), and paraffinic carbons (Cp) in the fluid. Specifically, CA is the wt% of total carbon atoms in the fluid that are in aromatic ring-type structures; CN is the wt% of total carbon atoms in the fluid that are in saturated ring-type structures; and Cp is the wt% of total carbon atoms in the fluid that are in paraffinic chain-type structures. ASTM D 2140 involves calculating a "Viscosity Gravity Constant" (VGC) and "Refractivity Intercept" (RI) for the fluid, and determining the carbon type composition from a correlation based on these two values. However, this method is known to fail for highly paraffinic oils, because the VGC and RI values fall outside the correlation range. Therefore, for purposes of this invention, the following protocol is used: If the calculated VGC (ASTM D 2140) for a fluid is 0.800 or greater, the carbon type composition including Cp is determined by ASTM D 2140. If the calculated VGC (ASTM D 2140) is less than 0.800, the fluid is considered to have CP of at least 80%. If the calculated VGC (ASTM D 2140) is less than 0.800 but greater than 0.765, then ASTM D 3238 is used to determine the carbon type composition including Cp. If application of ASTM D 3238 yields unphysical quantities (e.g., a negative CA value), then Cp is defined to be 100%. If the calculated VGC (ASTM D 2140) for a fluid is 0.765 or less, then CP is defined to be 100%.
Fluid Color
[0231 ] Color is determined on the APHA scale by ASTM D 1209. Note that an APHA color of 100 corresponds to a Saybolt color (ASTM D 156) of about +10; an APHA color of 20 corresponds to a Saybolt color of about +25; and an APHA color of 0 corresponds to a Saybolt color of about +30.
13C-NMR Spectroscopy on Hydrocarbon Fluids
[0232] The composition and branching characteristics of paraffinic hydrocarbon fluids is determined by 13C-NMR spectroscopy, following the general procedures and peak assignments outlined in Breitmaier and Voelter, CARBON-13 NMR SPECTROSCOPY, 3RD ED. (VCH, 1986). NFP Content
[0233] The preferred method to determine the NFP content (weight percent basis) in a polyolefin composition is the Extraction Method. Alternatively, the NMR Method can be used. In event of conflict, the Extraction Method shall control. [0234] The Extraction Method involves Soxhlet extraction, wherein at least a majority of the NFP is extracted with refluxing n-heptane. Analysis of the base polymer is also required because it may contain low molecular weight and/or amorphous material that is soluble in refluxing n- heptane. The level of NFP in the blend is determined by correcting its extractables level, in weight percent, by the extractables level for the base polymer, as described below. [0235] The Soxhlet extraction apparatus consists of a 400 mL Soxhlet extractor, with a widened overflow tube (to prevent siphoning and to provide constant flow extraction); a metal screen cage fitted inside the main Soxhlet chamber; a Soxhlet extraction thimble (Whatman, single thickness, cellulose) placed inside the screen cage; a condenser with cooling water and drain; and a one-neck 1000 mL round bottom flask with appropriately sized stir bar and heating mantle.
[0236] The procedure is as follows. Dry the soxhlet thimbles in a 95°C oven for 60 min. Weigh the dry thimble directly after removal from oven; record this weight as A in g. Weigh out 15-20 g of sample (either in pellet or ground pellet form.) into the thimble; record as B in g. Place the thimble containing the polymer in the Soxhlet apparatus. Pour 300 mL of HPLC-grade n- heptane into the round bottom flask with stir bar and secure the flask on the heating mantle. Connect the round bottom flask, the soxhlet, and the condenser in series. Pour more n-heptane down through the center of the condenser into the Soxhlet main chamber until the solvent level is just below the top of the overflow tube. Turn on the cooling water to the condenser. Turn on the heating mantle and adjust the setting to generate a rolling boil in the round bottom flask and maintain a good reflux. Allow to reflux for 16 hrs. Turn the heat off but leave the cooling system on. Allow the system to cool down to room temperature. Disassemble the apparatus. Remove the thimble and rinse with a small amount of fresh n-heptane. Allow to air dry in the laboratory hood, followed by oven drying at 95°C for 90 min. Weigh the thimble containing the polymer directly after removal from oven; record as C in g.
[0237] The quantity of extract is determined by calculating the weight loss from the sample, W = (A+B-C), in g. The extractables level, E, in weight percent, is then calculated by E = 100(W/B). The NFP content in the blend, P, in weight percent, is calculated by P = E(blend) - E(base polymer). [0238] The NMR Method requires constructing a model based on a calibration curve (or set of calibration curves) of measured parameter(s) as a function of NFP concentration. The calibration blends are prepared using the same polymer and NFP as the blend(s) under investigation but at known NFP concentrations. This set of calibrants must number at least five, and include the neat polymer as well as at least one NFP concentration above the maximum for the blend(s) under investigation but not greater than 50 wt% NFP. The blend(s) under investigation are analyzed under the same conditions as the calibrants, and the NFP content determined by applying the model.
[0239] Specifically, the NMR Method involves high-temperature solution-phase 13C-nuclear magnetic resonance (HTS-CNMR). The composition is determined using the reference spectra of the neat polymer and neat NFP, as well as spectra for a set of calibration blends (i.e., prepared from the neat polymer and NFP at known wt% NFP). The spectra are analyzed to determine a set of one or more diagnostic resonances or clusters of resonances that increase or decrease in strength monotonically with increasing NFP content. The corresponding peaks are integrated and their fractional contribution to the total integral calculated as a function of NFP content (weight %) to generate a set of calibration curves. A chemometrics model is developed using these calibration curves to provide a method to calculate the NFP content. The number of diagnostic resonances is chosen to allow the model to predict NFP content with a precision of 1 wt% or better over the calibration range. For a general description of chemometrics and how to develop a chemometrics model, see CHEMOMETRIC TECHNIQUES FOR QUANTITATIVE ANALYSIS, Richard Kramer (Marcel Dekker, 1998). The blend(s) of unknown concentration are then run following the same HTS-CNMR procedure as used for the calibrants, and the results analyzed according to the model to determine the wt% NFP. [0240] A typical HTS-CNMR procedure is as follows. Samples are prepared in 1,1,2,2- tetrachloroethane-^, with chromium acetylacetonate [Cr(acac)3] added as a relaxation agent to accelerate data acquisition. The Cr(acac)3 concentration in the stock solvent is approximately 15 mg/ml. Sample concentrations are between 10 and 15 wt%. Free induction decays of 15,000 transients are accumulated at a temperature of 1200C on a Varian UnityPlus 500 instrument using a 10 mm broadband probe. Spectra are acquired with a 90° carbon excitation pulse, and inverse- gated WALTZ-16 proton decoupling. An acquisition time of approximately 1 second and recycle delay of 3.5 seconds are used to allow quantitative integration. Solvent choice and sample concentration may be adjusted to accommodate different solubility and to minimize spectral interference based on the specific composition of the blend. See CARBON-13 NMR SPECTROSCOPY: HIGH-RESOLUTION METHODS AND APPLICAΉONS IN ORGANIC CHEMISTRY AND BIOCHEMISTRY, 3rd Ed., Eberhard Breitmaier and Wolfgang Voelter (VCH, 1990) for a general description of CNMR techniques.
Permanence
[0241] Permanence of the NFP is determined by ASTM D 1203, by measuring the weight loss from the plasticized composition in the form of a 0.25 mm thick sheet, after 300 hours in dry 700C oven. Permanence is 100% minus the Corrected %weight loss, where Corrected %weight loss = (%weight loss for the plasticized composition) - (%weight loss for the unplasticized composition under the same test conditions), % weight loss — 10Ox(W-Wo)AVo, W = weight after drying and Wo is the weight before drying. The unplasticized composition is the same composition as the plasticized composition but without NFP added. Atomic Force Microscopy (AFM)
[0242] AFM is used to determine if a polyolefm blend is a hetero-phase blend. AFM "phase images" acquired using the "tapping-mode" method provide a morphological map of the sample based primarily on modulus, which is a strong function of crystallinity for polyolefins. Therefore, if the sample is a hetero-phase blend, distinct domains will be observed if they have different crystallinity, as is the case for domains of EP Rubber and/or ethylene copolymer in a polypropylene matrix. Other factors that influence the tapping-mode AFM signal, such as adhesion and electrostatic charge, will generally not affect the ability to determine if a polyolefm blend is a hetero-phase blend. [0243] A smooth surface for analysis is prepared by cryofacing a representative sample of the blend using a cryo-ultramicrotome equipped with a diamond knife and operated at a temperature of -130 to -150°C. The typical scan size is 20 microns by 20 microns, but smaller or larger scan sizes can be used depending on the size scale of the morphological features. The minimum size scale for a domain detectable by AFM is about 0.1 micron. [0244] In tapping-mode AFM, a cantilever (equipped with a tip and housed in a scanner head) is oscillated at or slightly below its resonant frequency, which ensures repulsive contacts (i.e., positive phase shifts). Typical frequencies used are 50-100 kHz, but will vary depending on the actual stiffness of the assembly. During the imaging scan, the tip intermittently strikes the sample as the scanner head moves over the surface. A feedback loop maintains a constant oscillation amplitude of the cantilever based on the signal acquired by a photodiode detector that measures the intensity of light reflected from a laser aimed at the cantilever, which varies as the cantilever deflects. This constant oscillation amplitude insures a constant tip-sample interaction so features seen in the image are due to tip response to the sample and not factors driving the cantilever. The height image is determined by the vertical (z position) of the scanner at any (x, y) position on the surface. The phase image is determined by the phase shift between the driving oscillation for the cantilever and the response oscillation at any point on the surface. Higher modulus (harder) regions absorb more energy and therefore yield a larger phase shift compared to lower modulus (softer) regions. Specific parameters used to set the response of the feedback loop (integral and proportional gains) and the oscillation amplitude set-point (which is a fraction of the free oscillation amplitude) are readily established by those familiar with tapping-mode AFM. Flow Marks
[0245] The tendency for a polyolefin material to exhibit flow marks (or "tiger striping") is evaluated by injection molding a plaque 14 in (35.6 cm), 5 in (12.7 cm) wide, 1 in (2.5 mm) thick at a melt temperature of 2200C, a mold temperature of 27°C, and a fixed injection speed. Prior to injection molding, carbon black is added to the test composition via a masterbatch to give a final carbon black treat rate of about 1 wt%. The severity of any visible flow marks is judged by a trained operator and assigned a "visibility rating" according to the following scale: 0 = none, 1 = very slight, 2 = slight, 3 = moderate, 4 = severe. The tendency to exhibit flow marks is judged by measuring the distance from the gate to the first visible flow mark.
Scratch Resistance
[0246] The tendency for a polyolefϊn material to resist visible damage when scratched is evaluated using the Ford 5-Figer Scratch Test on an injection-molded plaque with an embossed surface pattern, specifically the CPM493 Stipple. Prior to injection molding, carbon black is added to the test composition via a masterbatch to give a final carbon black treat rate of about 1 wt%. The scratch resistance rating is the maximum load on the scratch finger that does not yield visible damage, as judged by a trained operator.
EXAMPLES
[0247] The present invention, while not meant to be limited by, may be better understood by reference to the following examples and tables.
[0248] Blend components used to prepare the Example Blends are reported in Table 1; compositions of Example (E) and Comparative (C) blends are reported in Tables 2a and 2b; evaluation results for Example (E) and Comparative (C) blends are reported in Tables 3a and 3b. [0249] Blends were prepared by melt-mixing all components on a ZSK-30 twin-screw extruder (30 mm diameter) with underwater pelletizer, using loss-in-weight feeders for adding components through the extruder feed-throat. Example blends were prepared by melt-mixing a masterbatch composition with other components to yield the final composition, again using the ZSK-30 twin- screw extruder and feed-throat addition of all components except wollastonite, which was added using a side feeder. Two masterbatch (MB) compositions were prepared on a ZSK-25 twin-screw extruder (25 mm diameter, 44 UD, 400 RPM) with underwater pelletizer, loss-in-weight feeders for addition of the solid components through the extruder feed-throat and for liquid injection of the NFP (injection point at barrel section 8 of 11):
MB-A: 72 wt% Plastomer-1 / 20 wt% PAO-2 / 8 wt% ICP-I MB-B: 72 wt% Plastomer-1 / 20 wt% PAO-I / 8 wt% ICP-I MB-C: 72 wt% Plastomer-2 / 20 wt% PAO-2 / 8 wt% ICP-l
[0250] Test specimens were injection molded, conditioned, and tested as described in the Experimental Methods section. Table 1
Component Description
ICP-I propylene/ethylene in-situ ICP (Ziegler-Natta catalyst) ethylene content ~ 9 wt%; EP Rubber content - 18 wt%; MFR ~ 35 dg/min; flexural modulus ~ 1270 MPa; nucleated
ICP-2 propylene/ethylene in-situ ICP (Ziegler-Natta catalyst) ethylene content ~ 4 wt%; EP Rubber content ~ 8 wt%; MFR ~ 80 dg/min; flexural modulus ~ 1660 MPa; nucleated
ICP-3 propylene/ethylene in-situ ICP (Ziegler-Natta catalyst) ethylene content ~ 16 wt%; EP Rubber content ~ 30 wt%; MFR ~ 15 dg/min; flexural modulus ~ 940 MPa; nucleated
Plastomer-1 ethylene/octene plastomer (metallocene catalyst)
MI ~ 5 dg/min; density ~ 0.87 g/cm3; Tn, ~ 65°C; flexural modulus ~ 13 MPa
Plastomer-2 ethylene/octene plastomer (metallocene catalyst)
MI ~ 3 dg/min; density ~ 0.86 g/cm3; Tm ~ 35°C; flexural modulus ~ 4 MPa
PAO-I octene/decene/dodecene PAO
KV @ 1000C ~ 10 cSt; VI ~ 137; pour point • -48°C; specific gravity ~ 0.835
PAO-2 octene/decene/dodecene PAO
KV @ 1000C ~ 100 cSt; VI ~ 170; pour point ~ -300C; specific gravity ~ 0.853
Talc median particle size ~ 1.5 micron
Wollastonite median particle size ~ 5 micron; aspect ratio (L/D) ~ 10:1
Table 2a
Example Cl El E2 E3 E4 E5 E6 E7 E8
ICP-I (wt%) 40.0 46.6 46.6 46.6 45.8 45.8 45.8 41.6 41.6
ICP-2 (wt%) 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0 15.0
Plastomer-1 (wt%) 25.0 14.4 14.4 14.4 17.2 17.2 — 19.4 —
Plastomer-2 (wt%) — — — — — — 17.2 « . 19.4
Talc (wt%) 20.0 20.0 20.0 — 20.0 — — 20.0 20.0
Wollastonite (wt%) — — — 20.0 — 20.0 20.0 — —
PAO-I (wt%) — — 4.0 — — — — 4.0 4.0
PAO-2 (wt%) — 4.0 — 4.0 2.0 2.0 2.0 — ~
Table 2b
Example C2 E9 ElO Ell E12 E13 E14 E15 E16
ICP-I (wt%) 15.0 21.6 21.6 21.6 20.8 20.8 20.8 16.6 16.6
ICP-2 (wt%) 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0 40.0
Plastomer-1 (wt%) 25.0 14.4 14.4 14.4 17.2 17.2 — 19.4 —
Plastomer-2 (wt%) — — — — — 17.2 — 19.4
Talc (wt%) 20.0 20.0 20.0 — 20.0 — — 20.0 20.0
Wollastonite (wt%) — — — 20.0 — 20.0 20.0 — —
PAO-I (wt%) — — 4.0 — — -- 4.0 4.0
PAO-2 (wt%) — 4.0 — 4.0 2.0 2.0 2.0 — —
- Sl - Table 2c
Example E17 E18 E19 E20 E21 E22 E23 E24
ICP-I (wt%) 0.8 0.8 50.0 30.0 30.0 — — —
ICP-2 (wt%) — — 15.0 35.0 15.0 — ~ —
ICP-3 (wt%) 75.0 75.0 — — -- 72.0 63.4 89.8
Plastomer-1 (wt%) 7.2 — — — — -- — —
Plastomer-2 (wt%) — 7.2 17.0 15.0 24.8 5.0 15.0 5.0
Talc (wt%) 15.0 15.0 15.0 17.0 30.0 20.0 20.0 5.0
PAO-I (wt%) 2.0 2.0 3.0 3.0 0.2 3.0 1.6 2.0
Table 3a
Example Cl El E2 E3 E4 E5 E6 E7 E8
MFR (dg/min) 23 36 36 51 29 34 31 34 31
Flexural Modulus (MPa) 149 132 125 155 129 161 148 126 125
0 8 6 2 6 5 1 9 2
Tensile Yield Strength (MPa) 18. 16. 16. 16. 17. 16. 15. 14.
2 7 2 2 6 9 3 4
Hardness, Sh D (15 sec) 57 55 55 55 57 57 55
HDT, 0.45 MPa (0C) 100 101 101 94 100 111 107 110 116
Notched Charpy, 23°C 57. 40. 38. 54. 43. 35. 44. 52. 60.
(kJ/m2) 5 6 6 5 8 7 1 0 5
Notched Charpy. -300C 4.4 2.8 2.7 3.4 2.2 2.7 4.0 4.5
(kJ/m2)
Multi-Axial Impact, -300C 26. 22. 19. 21. 22. 21. 21.
(J) 1 2 3 5 5 1 0
# Ductile failures 5 1 0 0 4 4 3
# Mixed-Mode failures 0 0 1 0 3 2 2
# Brittle failures 0 9 9 10 3 4 5
Flow Marks — visibility 3 3 2 4 3 3 3 2 rating 2.0 6.0 9.5 6.0 7.0 5.5 3.5 9.0 distance from gate (in)
Scratch Resistance (N) 3 3 3 3 5 5
Table 3b
Example C2 E9 ElO Ell E12 E13 E14 E15 E16
MFR (dg/min) 26 44 45 63 36 52 39 41 38
Flexural Modulus (MPa) 175 152 139 174 144 1779 175 163 147
4 0 0 7 1 1 4 4
Tensile Yield Strength 18. 18. 17. 17. 17.8 17. 17. 15.
(MPa) 9 2 2 3 6 6 8
Hardness, Sh D (15 sec) 60 58 58 57 59 58 58
HDT, 0.45 MPa (0C) 105 107 105 101 100 104 111 113 78
Notched Charpy. 23°C 53. 14. 23. 39. 36. 48.6 37. 40. 50.
(kJ/m2) 7 5 9 5 2 8 9 8
Notched Charpy, -300C 2.9 2.5 2.5 2.6 2.3 2.0 2.9 4.1
(kJ/m2)
Multi-Axial Impact, -300C 25. 12. 16. 17. 21. 21.5 21.
(J) 8 9 5 1 4 • 0 4
# Ductile failures 5 0 0 0 0 0 0
# Mixed-Mode failures 0 0 0 0 0 10 0 # Brittle failures O 10 10 10 10 10
Flow Marks - visibility 3 2 1 3 2 2.5 4 3 rating 5.0 8.0 11. 7.5 12.0 9.0 3.5 5.0 distance from gate (in) 5
Scratch Resistance (N) < 3 3 3 3 3 3 3
Table ! 3c
Example E17 E18 E19 E20 E21 E22 E23 E24
MFR (dg/min) 18 18 33 39 17 17 14 16
Flexural Modulus (MPa) 1075 1000 1300 1600 1540 1290 990 1010
Tensile Yield Strength (MPa) 15.1 14.6 16.3 18.3 14.1 15.1 12.3 16.8
Hardness, Sh D (15 sec) 53 52 54 58 52
HDT, 0.45 MPa (0C) 49 47 101 106 101 . 94 84 81
Notched Charpy, 230C (kJ/m2) 36.6 45.6 52.2 14.3 68.0
Notched Charpy, -300C 16.4 16.2 4.6 3.5 5.4
(kJ/m2)
Multi-Axial Impact, -300C (J) 21.8 21.1 24.3 22.8 23.4 29.6 21.8 28.3
# Ductile failures 9 9 8 7 10 10 10 10
# Mixed-Mode failures 1 1 2 3 0 0 0 O
# Brittle failures 0 0 0 0 0 0 0 0
Flow Marks — visibility rating 3 3 2 1 4 3 4 1 distance from gate (in) 5.0 5.0 7.0 7.0 2.5 3.5 2.5 7.5
[0251] AU documents described herein are incorporated by reference herein, including any priority documents and/or testing procedures to the extent they are not inconsistent with this text. As is apparent from the foregoing general description and the specific embodiments, while forms of the invention have been illustrated and described, various modifications can be made without departing from the spirit and scope of the invention. Accordingly, it is not intended that the invention be limited thereby. Likewise, the term "comprising" is considered synonymous with the term "including" for purposes of Australian law.
. si .

Claims

CLAIMSWhat Is Claimed Is:
1. A hetero-phase polyolefin composition comprising: a) 30 to 99.7 wt% of a polypropylene-based TPO comprising at least 50 wt% propylene and at least 10 wt% ethylene, and b) 0.1 to 20 wt% of one or more non-functionalized plasticizer(s), and c) 0.2 to 50 wt% of one or more filler(s); based upon the weight of the composition, and having: i) an MFR of 5 dg/min or more, and ii) a flexural modulus of 500 MPa or more, and iii) a notched Charpy impact strength at -300C of 1 kJ/m2 or more or a notched Izod impact strength at -18°C of 50 J/m or more.
2. The composition of claim 1, wherein the composition has an MFR of 10 dg/min or more.
3. The composition of any of claims 1 to 2, wherein the composition has a flexural modulus of 800 MPa or more.
4. The composition of any of claims 1 to 3, wherein the composition has a notched Charpy impact strength at -300C of 2 kJ/m2 or more and a notched Izod impact strength at -18°C of 50 J/m or more.
5. The composition of any of claims 1 to 4, wherein the composition comprises 35 to 95 wt% of the polypropylene-based TPO.
6. The composition of any of claims 1 to 5, wherein the polypropylene-based TPO comprises at least 55 wt% propylene.
7. The composition of any of claims 1 to 6, wherein the polypropylene-based TPO comprises at least 15 wt% ethylene.
8. The composition of any of claims 1 to 7, wherein the composition comprises 0.5 to 15 wt% of one or more non-functionalized plasticizer(s).
9. The composition of any of claims 1 to 8, wherein the composition comprises 0.5 to 40 wt% of one or more flller(s).
10. The composition of any of claims 1 to 9, wherein the polypropylene-based TPO is a polypropylene impact copolymer.
11. The composition of any of claims 1 to 10, wherein the polypropylene-based TPO comprises a homopolypropylene matrix.
12. The composition of any of claims 1 to 11, wherein the polypropylene-based TPO comprises a propylene copolymer matrix.
13. The composition of any of claims 1 to 12, wherein the polypropylene-based TPO comprises an isotactic polypropylene matrix.
14. The composition of any of claims 1 to 13, wherein the polypropylene-based TPO comprises a matrix having a Tm of 110 0C or more.
15. The composition of any of claims 1 to 14, wherein the polypropylene-based TPO comprises a dispersed phase having a Tg of -20 0C or less.
16. The composition of any of claims 1 to 15, wherein the polypropylene-based TPO is an impact copolymer having a rubber content of 5 to 40 wt%, a melt flow rate of 5 to 150 dg/min, and a flexural modulus of 300 to 3000 MPa.
17. The composition of any of claims 1 to 16, wherein the polypropylene-based TPO comprises two or more in-situ impact copolymers, where the combination of the impact copolymers comprises at least 50 wt% propylene and at least 10 wt% ethylene, based upon the weight of the impact copolymers.
18. The composition of any of claims 1 to 17, wherein the composition further comprises 1 to 40 wt% of an ethylene copolymer.
19. The composition of any of claims 1 to 18, wherein the composition further comprises 5 to 35 wt% of a copolymer of ethylene and one or more of propylene, butene, hexene, or octene, and the copolymer has a density of 0.85 to 0.90 g/cm3 and a melt index of 0.1 to 100 dg/min.
20. The composition of any of claims 1 to 19, wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a flexural modulus of 900 to 3500 MPa; and the composition has one or both of the following properties: c) a notched Charpy impact strength at -300C of 1.5 to 15 kJ/m2 , and/or d) a notched Izod impact strength at -18°C of 60 to 500 J/m.
21. The composition of any of claims 1 to 20, wherein the composition has: a) a melt flow rate (MFR) of 10 to 500 dg/min, and b) a flexural modulus of 900 to 3500 MPa ; and the composition has one or both of the following properties: c) a notched Charpy impact strength at -300C of 1.5 to 15 kJ/m2 , and/or d) a notched Izod impact strength at -18°C of 60 to 500 J/m; and the composition has one or more of the following properties: e) a notched Charpy impact strength at 23CC of 20 kJ/m2 or more, and/or f) a notched Izod impact strength at 23°C of 100 J/m or more, and/or g) a ductile failure in a multi-axial impact strength test at 230C, and/or h) a heat distortion temperature (HDT) of 600C or more, and/or i) a tensile strength of 10 MPa or more, and/or j) shrinkage upon injection molding of 0.1 to 5%, and/or k) a fogging number of 70 or more.
22. The composition of any of claims 1 to 21, wherein the NFP has a kinematic viscosity at 1000C of 10 cSt or more.
23. The composition of any of claims 1 to 22, wherein the NFP has a pour point of -30°C or less.
24. The composition of any of claims 1 to 23, wherein the NFP has a viscosity index of 120 or more.
25. The composition of any of claims 1 to 24, wherein the NFP has a specific gravity of 0.855 or less.
26. The composition of any of claims 1 to 25, wherein the non-functionalized plasticizer comprises at least 50 weight% of Ce to C 150 isoparaffins.
27. The composition of any of claims 1 to 26, wherein the non-functionalized plasticizer comprises oligomers of C8 to C^ alpha-olefins.
28. The composition of any of claims 1 to 27, wherein the non-functionalized plasticizer comprises oligomers of decene.
29. The composition of any of claims 1 to 28, wherein the non-functionaiized plasticizer comprises oligomers of C5 to Ci g linear alpha-olefins and has a branching ratio of 0.20 or less.
30. The composition of any of claims 1 to 29, wherein the non-functionalized plasticizer comprises oligomers of C5 to C18 linear alpha-olefins and has a kinematic viscosity of 8 cSt or more at 1000C, a viscosity index of 120 or more, and a pour point of -25°C or less.
31. The composition of any of claims 1 to 30, wherein the non-functionalized plasticizer comprises a paraffinic process oil with a. a viscosity index of 90 to 119, and b. a Cp of 65% or more, and c. a CA of 1 % or less, and d. a kinematic viscosity at 40°C of 80 cSt or more, and e. a pour point of - 15°C or less .
32. The composition of any of claims 1 to 31, wherein the non-functionalized plasticizer is a hydrocarbon fluid derived from a Gas-To-Liquids process comprising hydroisomerized Fischer- Tropsch waxes and having a pour point of about -20 to -6O0C and a kinematic viscosity of about 6 to 20 cSt.
33. The composition of any of claims 1 to 32, wherein the non-functionalized plasticizer comprises a mixture of paraffins has two or more of the following properties:
1) a naphthenic content of less than 40 wt%, based on the total weight of the paraffin mixture; and/or
2) a normal paraffins content of less than 5 wt%, based on the total weight of the paraffin mixture; and/or
3) an aromatic content of 1 wt% or less, based on the total weight of the paraffin mixture; and/or
4) a saturates level of 90 wt% or higher; and/or
5) a percentage of carbons in chain-type paraffinic structures (Cp) of 80% or more; and/or
6) a branched paraffin:normal paraffin ratio greater than about 10:1; and/or
7) sidechains with 4 or more carbons making up less than 10% of all sidechains; and/or
8) sidechains with 1 or 2 carbons making up at least 50% of all sidechains; and/or
9) a sulfur content of 300 ppm or less (weight basis); and/or
10) a nitrogen content of 300 ppm or less (weight basis); and/or
11) a number-average molecular weight of 300 to 1800 g/mol; and/or
12) a kinematic viscosity at 400C of 10 cSt or more; and/or
13) a kinematic viscosity at 1000C ranging from 2 to 50 cSt; and/or
14) a viscosity index (VI) of 80 or greater; and/or 15) a pour point of -5°C or lower; and/or
16) a flash point of 2000C or more; and/or
17) a specific gravity of 0.86 or less; and/or
18) an aniline point of 1200C or more; and/or
19) a bromine number of 1 or less.
34. The composition of any of claims 1 to 33, wherein the non-functionalized plasticizer comprises a mixture of paraffins has two or more of the following properties:
1) a naphthenic content of less than 40 wt%, based on the total weight of the paraffin mixture; and/or
2) a normal paraffins content of less than 5 wt%, based on the total weight of the paraffin mixture; and/or
3) an aromatic content of 1 wt% or less, based on the total weight of the paraffin mixture; and/or
4) a saturates level of 90 wt% or higher; and/or
5) a percentage of carbons in chain-type paraffinic structures (Cp) of 80% or more; and/or
6) a branched paraffumormal paraffin ratio greater than about 10:1; and/or
7) sidechains with 4 or more carbons making up less than 10% of all sidechains; and/or
8) sidechains with 1 or 2 carbons making up at least 50% of all sidechains; and/or
9) a sulfur content of 300 ppm or less (weight basis); and/or
10) a nitrogen content of 300 ppm or less (weight basis)
35. The composition of any of claims 1 to 35, wherein the non-functionalized plasticizer comprises a mixture of paraffins has two or more of the following properties:
1) a number-average molecular weight of 300 to 1800 g/mol; and/or
2) a kinematic viscosity at 400C of 10 cSt or more; and/or
3) a kinematic viscosity at 1000C ranging from 2 to 50 cSt; and/or
4) a viscosity index (VT) of 80 or greater; and/or
5) a pour point of -5°C or lower; and/or
6) a flash point of 200°C or more; and/or
7) a specific gravity of 0.86 or less; and/or
8) an aniline point of 1200C or more; and/or
9) a bromine number of 1 or less.
36. An article comprising the composition of any of claims 1 to 35.
37. A molded automotive part comprising the composition of any of claims 1 to 36.
38. The article of claim 36 where the article is selected from the group consisting of films, tapes, sheets, fibers, tubing, pipes, coatings, fabrics (woven and nonwoven), tarps, agricultural barriers, packaging (durable and disposable), household appliances, washing machines, refrigerators, blenders, air conditioners, furniture (indoor and outdoor), tables, chairs, benches, shelving, sporting equipment, skis, surfboards, skateboards, skates, boots, sleds, scooters, kayaks, paddles, solid wheels, stadium seating, amusement park rides, personal protective equipment, safety helmets, shin guards, emergency response equipment, cookware, utensils, trays, pallets, carts, tanks, tubs, pond liners, storage containers, crates, pails, jars, bottles, toys, child car seats and booster chairs, medical devices, sportswear, luggage, tool housings, electronics housings, building, construction materials, flooring, siding, roofing, counter tops, electrical housings and connectors, lighting, gardening equipment, handles on shovels, handles on wheelbarrows, playground equipment, motor housings, pump housings, battery housings, instrument housings, switches, knobs, buttons, handles, pet supplies, laboratory supplies, personal hygiene devices, razors, brushes, hairdryers, cleaning supplies, brooms, dust pans, musical instrument cases, statues, trophies, artwork, costume jewelry, picture frames, eyeglass frames, plant pots, firearm components, and automotive components.
39. The article claim 36 where the article is selected from the group consisting of bumpers, bumper fascias; exterior body panels, door panels, grills, exterior trim, body side moldings, side cladding, side molding, end caps, hoods, deck lids, mirror housings, roof racks, wheel covers, wheel liners, wheel flares, fender liners, hub caps, running boards, step pads, sill plates, air dams, splash shields, mud guards, bed liners, and rocker panels; fuel tanks; interior trim, including steering column covers, consoles, door panels, pillars, supports, knobs, buttons, handles, safety screens, instrument panels, dash boards, knee bolsters; passenger side airbag covers, headliners, glove boxes, trays, cup holders, compartments, lids, seat components, backs, supports, safety belt securing devices, under-hood parts, battery trays, fan shrouds, electrical housings; cable bearings, structural components, door carriers, truck bed separators, load floors, and trunk dividers.
40. A vehicle comprising the composition of any of claims 1 to 39, wherein the vehicle is selected from the group consisting of cars, trucks, buses, boats, all terrain vehicles, personal water craft, golf carts, snowmobiles, motorcycles, mopeds, tractors, mowers, wagons, bicycles, airplanes, helicopters, trains, military machines, and gondolas.
41. An article comprising the composition of any of claims 1 to 40, wherein the article has at least one overall dimension greater than 30 cm.
42. An article comprising the composition of any of claims 1 to 41, wherein the article has as a length greater than 30 cm.
43. An automotive part comprising the composition of any of claims 1 to 42, wherein the article has as a length greater than 30 cm.
44. A process to prepare the composition of any of claims 1 to 43 by combining the components in an extruder.
45. A process to prepare a molded part comprising heating the composition of any of claims 1 to 44, then introducing the heated composition into a mold and thereafter cooling the composition and removing it from the mold.
46. A vehicle replacement part comprising the composition of any of claims 1 to 45.
PCT/US2007/015486 2006-08-15 2007-07-05 Plasticized hetero-phase polyolefin blends WO2008020925A1 (en)

Priority Applications (8)

Application Number Priority Date Filing Date Title
BRPI0715067-9A BRPI0715067A2 (en) 2006-08-15 2007-07-05 plasticized heterophase polyolefin compositions
AU2007285017A AU2007285017C1 (en) 2006-08-15 2007-07-05 Plasticized hetero-phase polyolefin blends
CN200780033057XA CN101511929B (en) 2006-08-15 2007-07-05 Plasticized hetero-phase polyolefin blends
EP07810207A EP2052028A1 (en) 2006-08-15 2007-07-05 Plasticized hetero-phase polyolefin blends
MX2009001661A MX2009001661A (en) 2006-08-15 2007-07-05 Plasticized hetero-phase polyolefin blends.
JP2009524596A JP5140670B2 (en) 2006-08-15 2007-07-05 Plasticized heterophasic polyolefin blends
CA002660532A CA2660532A1 (en) 2006-08-15 2007-07-05 Plasticized hetero-phase polyolefin blends
KR1020097002949A KR101161914B1 (en) 2006-08-15 2007-07-05 Plasticized hetero-phase polyolefin blends

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/504,447 2006-08-15
US11/504,447 US8003725B2 (en) 2002-08-12 2006-08-15 Plasticized hetero-phase polyolefin blends

Publications (1)

Publication Number Publication Date
WO2008020925A1 true WO2008020925A1 (en) 2008-02-21

Family

ID=37421198

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US2007/015486 WO2008020925A1 (en) 2006-08-15 2007-07-05 Plasticized hetero-phase polyolefin blends

Country Status (10)

Country Link
US (1) US8003725B2 (en)
EP (1) EP2052028A1 (en)
JP (1) JP5140670B2 (en)
KR (1) KR101161914B1 (en)
CN (1) CN101511929B (en)
AU (1) AU2007285017C1 (en)
BR (1) BRPI0715067A2 (en)
CA (1) CA2660532A1 (en)
MX (1) MX2009001661A (en)
WO (1) WO2008020925A1 (en)

Cited By (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2141200A1 (en) * 2008-07-03 2010-01-06 Total Petrochemicals Research Feluy Heterophasic propylene copolymer with improved properties for injection molding applications
EP2248853A1 (en) * 2006-08-16 2010-11-10 Dow Global Technologies Inc. Polymeric material and process for forming and using same
WO2010149549A1 (en) * 2009-06-22 2010-12-29 Borealis Ag Automotive interior article with reduced smell
US7862671B2 (en) 2007-01-11 2011-01-04 Dow Global Technologies Inc. Welding of a polymeric material and structures formed thereby
CN101265349B (en) * 2008-04-10 2011-04-20 汕头市贝斯特科技有限公司 Inorganic anti-sticking master batch used for BOPP thin film and producing technique thereof
WO2011131579A1 (en) * 2010-04-20 2011-10-27 Borealis Ag Automotive interior compound
US8529821B2 (en) 2009-01-30 2013-09-10 Dow Global Technologies Llc Polymeric compositions and filled TPO articles having improved aesthetics
RU2496807C2 (en) * 2009-06-22 2013-10-27 Бореалис Аг Mineral polypropylene compound with low content of volatile compounds
JP2013237784A (en) * 2012-05-15 2013-11-28 Bridgestone Corp Resin member for bicycle and child seat for bicycle
WO2016162359A1 (en) * 2015-04-10 2016-10-13 Borealis Ag Composition based on pp random copolymers and elastomers
EP2551299B1 (en) 2011-07-27 2017-03-15 Borealis AG Lightweight polypropylene resin with superior surface characteristics for use in automotive interior applications
US9770738B2 (en) 2013-07-17 2017-09-26 Hewlett-Packard Indigo B.V. Method of producing an electrostatic ink composition
WO2018019764A1 (en) * 2016-07-29 2018-02-01 Sabic Global Technologies B.V. Light diffusing article
WO2018024480A1 (en) * 2016-08-03 2018-02-08 Borealis Ag Fiber reinforced polypropylene composite
EP3333222A1 (en) * 2016-12-12 2018-06-13 SABIC Global Technologies B.V. Composition comprising heterophasic propylene copolymer
US10983452B2 (en) 2012-11-20 2021-04-20 Hp Indigo B.V. Methods of printing and electrostatic ink compositions
US11414526B2 (en) 2014-06-25 2022-08-16 Exxonmobil Chemical Patents Inc. High melt strength polypropylene and extrusion process for preserving melt strength

Families Citing this family (120)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7795366B2 (en) * 2002-08-12 2010-09-14 Exxonmobil Chemical Patents Inc. Modified polyethylene compositions
US7271209B2 (en) 2002-08-12 2007-09-18 Exxonmobil Chemical Patents Inc. Fibers and nonwovens from plasticized polyolefin compositions
US8003725B2 (en) 2002-08-12 2011-08-23 Exxonmobil Chemical Patents Inc. Plasticized hetero-phase polyolefin blends
CA2492839C (en) 2002-08-12 2011-02-01 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US7998579B2 (en) 2002-08-12 2011-08-16 Exxonmobil Chemical Patents Inc. Polypropylene based fibers and nonwovens
US8476360B2 (en) * 2002-08-12 2013-07-02 Exxonmobil Chemical Patents Inc. Calendered films of plasticized blends of plastomer and impact copolymer
US7531594B2 (en) 2002-08-12 2009-05-12 Exxonmobil Chemical Patents Inc. Articles from plasticized polyolefin compositions
US8466235B2 (en) * 2002-08-27 2013-06-18 Braskem America, Inc. Polypropylene blends for non-woven production
US8192813B2 (en) 2003-08-12 2012-06-05 Exxonmobil Chemical Patents, Inc. Crosslinked polyethylene articles and processes to produce same
US8389615B2 (en) 2004-12-17 2013-03-05 Exxonmobil Chemical Patents Inc. Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin
WO2007011530A2 (en) 2005-07-15 2007-01-25 Exxonmobil Chemical Patents, Inc. Elastomeric compositions
EP1857333A3 (en) * 2006-05-19 2008-06-25 Illinois Tool Works Inc. Fastener for air-bag curtain
US20080061468A1 (en) * 2006-09-07 2008-03-13 Frank Li Fiber processing of high ethylene level propylene-ethylene random copolymers by use of nucleators
US7737571B2 (en) * 2006-12-22 2010-06-15 Genedics Clean Energy, Llc System and method for creating a networked infrastructure distribution platform of fixed hybrid solar wind energy generating devices
CN101547944B (en) * 2006-12-27 2013-07-24 三菱化学株式会社 Process for production of polyolefins, polyolefins, and 1-hexene to be used as raw material in producing linear low-density polyethylene
US20080178489A1 (en) * 2007-01-15 2008-07-31 Roger Dionne Shaver saver
US7615589B2 (en) * 2007-02-02 2009-11-10 Exxonmobil Chemical Patents Inc. Properties of peroxide-cured elastomer compositions
DE102008006391B4 (en) * 2008-01-28 2016-11-17 Airbus Operations Gmbh Chromate-free composition, its use as corrosion protection and thus produced corrosion protection coating for fuel tanks
US8519033B2 (en) * 2008-02-22 2013-08-27 Sanc Salaam Corporation Polymer composition and molded products formed thereof
EP2177354B1 (en) * 2008-05-05 2012-08-08 A. Schulman, Inc. Layered backing structure
US20100010175A1 (en) * 2008-07-08 2010-01-14 Fina Technology, Inc. Additives for Polyolefin Extruder Start-Up
JP5254191B2 (en) * 2008-12-19 2013-08-07 三洋化成工業株式会社 Treatment agent for seat belt webbing
EP2377731B1 (en) * 2008-12-22 2013-11-20 Takata Corporation Seat belt device
US8308974B2 (en) * 2009-03-06 2012-11-13 Milliken & Company Liquid dispersion and thermoplastic compositions comprising the same
US8915993B2 (en) * 2009-06-10 2014-12-23 Xerox Corporation Solid or phase change inks with improved properties
US20110057402A1 (en) * 2009-09-09 2011-03-10 Keith Jewell Multi-functional and convertible hand truck
BR112012006518B1 (en) * 2009-09-22 2020-06-23 Basell Poliolefine Italia S.R.L. PROPYLENE POLYMER COMPOSITIONS
ES2385459T3 (en) * 2009-10-09 2012-07-25 Borealis Ag Fiberglass composite material with improved processability
US8557444B2 (en) * 2009-12-15 2013-10-15 E I Du Pont De Nemours And Company Multi-layer article comprising polyimide nanoweb
JP5606558B2 (en) * 2010-02-22 2014-10-15 ダウ グローバル テクノロジーズ エルエルシー Painted polyolefin articles
ES2369809B1 (en) * 2010-05-10 2012-10-15 Ctl-Th Packaging, S.L. Unipersonal FLEXIBLE MATERIAL TUBE, FLEXIBLE MATERIAL TUBE MANUFACTURING PROCEDURE, AND FORMULATION USED.
CN101845174B (en) * 2010-05-31 2013-02-27 江苏凯诺电缆集团有限公司 Sheath material of solar photovoltaic cable and cable
KR101180874B1 (en) * 2010-06-17 2012-09-07 호남석유화학 주식회사 Thermoplastic vulcanizates composition having improved foaming formability, and molded article manufactured therefrom
US9200147B2 (en) 2010-06-29 2015-12-01 Eastman Chemical Company Processes for making cellulose ester compositions
US9273195B2 (en) * 2010-06-29 2016-03-01 Eastman Chemical Company Tires comprising cellulose ester/elastomer compositions
US8557902B2 (en) 2010-08-25 2013-10-15 Exxonmobil Chemical Patents Inc. Functionalizable synthetic hydrocarbon fluids and integrated method for production thereof
CN101967243B (en) * 2010-09-29 2012-10-17 安徽兴源塑料包装有限公司 High-toughness and high-brightness polyethylene bottle cap and manufacturing method thereof
MX362519B (en) 2010-12-20 2019-01-21 Braskem America Inc Propylene-based compositions of enhanced appearance and excellent mold flowability.
US20140107274A1 (en) * 2010-12-20 2014-04-17 Braskem America, Inc. Propylene-based compositions of enhanced appearance and excellent mold flowability
WO2012112542A1 (en) * 2011-02-14 2012-08-23 Mayzo, Inc. Supported crystal nucleating agent for polypropylene
ES2750378T3 (en) 2011-03-25 2020-03-25 Exxonmobil Chemical Patents Inc Amine-functionalized polyolefin and methods for its preparation
WO2012145359A1 (en) * 2011-04-21 2012-10-26 Pactiv LLC Disposable lid having polymer composite of polyolefin and mineral filler
US20130089747A1 (en) 2011-05-20 2013-04-11 William Maxwell Allen, Jr. Fibers of Polymer-Wax Compositions
US9109106B2 (en) 2011-05-25 2015-08-18 Braskem America, Inc. Impact copolymer compositions for use in corrugated board
WO2012174106A2 (en) * 2011-06-13 2012-12-20 Fiber Composites, Llc Composites utilizing polymeric capstocks and methods of manufacture
AU2012363114B2 (en) 2011-06-17 2016-10-06 Berry Plastics Corporation Insulated sleeve for a cup
WO2012174567A2 (en) 2011-06-17 2012-12-20 Berry Plastics Corporation Process for forming an insulated container having artwork
GB2539589B (en) 2011-06-17 2017-04-19 Berry Plastics Corp Insulated container
US8883280B2 (en) 2011-08-31 2014-11-11 Berry Plastics Corporation Polymeric material for an insulated container
JP6047964B2 (en) * 2011-07-12 2016-12-21 三菱化学株式会社 Resin composition for release film and release film
CN102382365A (en) * 2011-08-09 2012-03-21 常熟市慧丰塑料制品有限公司 Plastic formula
US20130150495A1 (en) 2011-12-07 2013-06-13 Eastman Chemical Company Process for dispersing cellulose esters into elastomeric compositions
US8664461B2 (en) 2012-03-19 2014-03-04 Exxonmobil Chemical Patents Inc. Catalysts for producing polyalpha-olefins and processes related thereto
JP2013199551A (en) * 2012-03-23 2013-10-03 Adeka Corp Method for producing olefin resin composition for home electronic material and automobile interior material
JP6072787B2 (en) * 2012-06-20 2017-02-01 日本碍子株式会社 Porous plate filler for heat insulation, coating composition, heat insulation film, and heat insulation film structure
EP2880139B1 (en) * 2012-08-01 2019-01-09 Shell International Research Maatschappij B.V. Optical fiber cable comprising cable fill composition
US9713906B2 (en) 2012-08-07 2017-07-25 Berry Plastics Corporation Cup-forming process and machine
CN104736630B (en) * 2012-09-19 2019-01-01 沙特基础工业公司 The method for being used to prepare the composition comprising heterogeneous propylene copolymer and talcum
CN104870601A (en) 2012-10-26 2015-08-26 比瑞塑料公司 Polymeric material for an insulated container
AR093943A1 (en) 2012-12-14 2015-07-01 Berry Plastics Corp EDGE OF A THERMAL PACK
AR093944A1 (en) 2012-12-14 2015-07-01 Berry Plastics Corp PUNCHED FOR PACKAGING
US9840049B2 (en) 2012-12-14 2017-12-12 Berry Plastics Corporation Cellular polymeric material
US9957365B2 (en) 2013-03-13 2018-05-01 Berry Plastics Corporation Cellular polymeric material
CA2905085A1 (en) 2013-03-14 2014-09-25 Berry Plastics Corporation Container
WO2014172901A1 (en) * 2013-04-26 2014-10-30 The Procter & Gamble Company A glossy container
WO2014172903A1 (en) * 2013-04-26 2014-10-30 The Procter & Gamble Company A glossy container
US9751654B2 (en) 2013-08-16 2017-09-05 The Procter & Gamble Company Thermoplastic containers with improved aesthetics
TW201522445A (en) 2013-08-16 2015-06-16 Berry Plastics Corp Polymeric material for an insulated container
US9290646B2 (en) * 2013-10-04 2016-03-22 Equistar Chemicals, Lp Molded articles (including automobile parts) and related filled thermoplastic polyolefin compositions
WO2015076317A1 (en) * 2013-11-19 2015-05-28 日本碍子株式会社 Heat-insulating film and heat-insulating film structure
CN103665917A (en) * 2013-11-29 2014-03-26 南宁市日建塑料包装有限责任公司 Novel plastic formula
TWI490108B (en) 2013-12-20 2015-07-01 Ind Tech Res Inst Composite and method for preparing the same
JP2017502148A (en) * 2013-12-23 2017-01-19 ブラスケム アメリカ インコーポレイテッドＢｒａｓｋｅｍ Ａｍｅｒｉｃａ，Ｉｎｃ． Propylene-based composition with improved appearance and excellent fluidity
US10259927B2 (en) * 2014-04-02 2019-04-16 Sabic Global Technologies B.V. Polymer composition having low sensory impression of smell
JP6397215B2 (en) * 2014-04-25 2018-09-26 出光興産株式会社 Thermoplastic elastomer composition
HUE059173T2 (en) 2014-09-10 2022-10-28 Procter & Gamble Nonwoven web
US9758655B2 (en) 2014-09-18 2017-09-12 Berry Plastics Corporation Cellular polymeric material
RU2581057C1 (en) * 2014-10-03 2016-04-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования Московский авиационный институт (национальный исследовательский университет) (МАИ) Method of continuous cutting carbon fiber and device for its implementation
US10513589B2 (en) 2015-01-23 2019-12-24 Berry Plastics Corporation Polymeric material for an insulated container
KR101669933B1 (en) * 2015-03-06 2016-10-28 새한프라텍 주식회사 Container having an improved impact strength at low temperature and producing process thereof
WO2016196331A1 (en) 2015-06-05 2016-12-08 Exxonmobil Chemical Patents Inc. Supported metallocene catalyst systems for polymerization
US10570219B2 (en) 2015-06-05 2020-02-25 Exxonmobil Chemical Patents Inc. Production of heterophasic polymers in gas or slurry phase
WO2016197037A1 (en) 2015-06-05 2016-12-08 Exxonmobil Chemical Patents Inc. Catalyst system comprising supported alumoxane and unsupported alumoxane particles
BR112017028373B1 (en) 2015-06-30 2023-04-11 Exxonmobil Chemical Patents Inc LUBRICANT COMPOSITIONS COMPRISING DIOL FUNCTIONAL GROUPS AND METHODS OF MANUFACTURING AND USING THEM
CN105086064A (en) * 2015-08-12 2015-11-25 杨栩楷 EPM composite and preparation method thereof
US11161966B2 (en) 2016-01-18 2021-11-02 The Procter And Gamble Company Article with visual effects
US10077342B2 (en) 2016-01-21 2018-09-18 Eastman Chemical Company Elastomeric compositions comprising cellulose ester additives
CA3017187A1 (en) 2016-03-09 2017-09-14 The Procter & Gamble Company Absorbent article with activatable material
GB2549504B (en) * 2016-04-19 2020-03-04 Njc Europe Ltd Method for identifying a blend of nucleators useful for preparing a nucleated polyolefin material
WO2017191537A1 (en) * 2016-05-06 2017-11-09 Universidad Eafit Method for producing industrial clay
US10450491B2 (en) 2016-08-08 2019-10-22 Ticona Llc Thermally conductive polymer composition for a heat sink
EP3309212B1 (en) * 2016-10-17 2018-12-12 Borealis AG Fiber reinforced polypropylene composite
CN106496787A (en) * 2016-11-02 2017-03-15 无锡艾科瑞思产品设计与研究有限公司 A kind of preparation technology of PP composite material draw-bar box
WO2018165511A1 (en) 2017-03-09 2018-09-13 The Procter & Gamble Company Thermoplastic polymeric materials with heat activatable compositions
KR101893089B1 (en) * 2017-03-20 2018-08-29 한국건설기술연구원 Seat for Railway Vehicles Using Incombustible Plastic, And Method for Manufacturing the Same
KR101893069B1 (en) * 2017-03-20 2018-08-29 한국건설기술연구원 Interior Member for Railway Vehicles Using Incombustible Plastic Panel, And Method for Manufacturing the Same
KR101893066B1 (en) * 2017-03-20 2018-08-29 한국건설기술연구원 Gangway Bellows for Railway Vehicles Using Incombustible Plastic, And Method for Manufacturing the Same
US11214429B2 (en) 2017-08-08 2022-01-04 Berry Global, Inc. Insulated multi-layer sheet and method of making the same
CN107573587A (en) * 2017-08-29 2018-01-12 东莞市亨嘉橡塑科技有限公司 One kind is used for polypropylene dedicated composite of safety cap and preparation method thereof
US10808121B2 (en) 2017-10-12 2020-10-20 Exxonmobil Chemical Patents Inc. Polyolefin-based elastomer modified polyethylene terephthalate blends with enhanced notched impact strength
USD834276S1 (en) 2017-11-22 2018-11-20 Rubbermaid Commercial Products Llc Debris pan
US10966589B2 (en) 2017-11-22 2021-04-06 Rubbermaid Commercial Products Llc Debris pan and associated assemblies
PL3578384T3 (en) * 2018-06-05 2022-02-28 Akzenta Paneele + Profile Gmbh Substrate based on a plastic composition and solid composition on mineral basis for decorated wall or floor panels
CN109735118B (en) * 2019-01-05 2023-10-24 青岛马基泰商贸有限公司 Environment-friendly color sealing wax and preparation method and application thereof
EP3722364B1 (en) * 2019-04-12 2024-01-24 Thai Polyethylene Co., Ltd. High flow and high stiffness impact copolymer polypropylene
AR118648A1 (en) * 2019-04-24 2021-10-20 Dow Global Technologies Llc IMPROVED TEAR RESISTANCE MULTI-LAYER STRETCH FILM
WO2020225803A1 (en) * 2019-05-08 2020-11-12 Plasan Sasa Ltd. Running boards and processes for the production thereof
KR102288821B1 (en) * 2020-03-02 2021-08-12 전면근 Catalloy modified resin composition for coating wall fabrics used for manufacturing air floating structures, and preparing method of wall fabrics used for manufacturing air floating structures using the same
CN111560141A (en) * 2020-04-18 2020-08-21 嘉兴市韶华塑胶新材料有限公司 Antistatic high-impact polypropylene mine car bearing end cover and preparation method thereof
US20230242745A1 (en) 2020-06-03 2023-08-03 Exxonmobil Chemical Patents Inc Process for Production of Thermoplastic Vulcanizates using Supported Catalyst Systems and Compositions Made Therefrom
EP4247825A1 (en) 2020-11-23 2023-09-27 ExxonMobil Chemical Patents Inc. Metallocene polypropylene prepared using aromatic solvent-free supports
CN112708174B (en) * 2020-12-07 2022-08-09 中策橡胶集团股份有限公司 Rubber composition, screening method thereof and tire adopting composition
KR102578326B1 (en) * 2020-12-28 2023-09-14 롯데케미칼 주식회사 Thermoplastic resin composition and article produced therefrom
KR102446141B1 (en) * 2021-03-12 2022-09-22 (주)우성정공 method for manufacturing injection molded product coated dissimilar material
US11613604B2 (en) 2021-06-28 2023-03-28 Covestro Llc Isocyanate-reactive compositions, polyurethane foams formed therefrom, multi-layer composite articles that include such foams, and methods for their preparation
WO2023034889A1 (en) 2021-09-02 2023-03-09 Exxonmobil Chemical Patents Inc. C1 symmetric metallocene catalysts tailored for production of vinyl-terminated polypropylene oligomers and macromonomers
CN116063789A (en) * 2021-11-01 2023-05-05 中国石油化工股份有限公司 Heterophasic polypropylene composition, and preparation method and application thereof
WO2024036052A1 (en) 2022-08-09 2024-02-15 Exxonmobil Chemical Patents Inc. Methods for preparing diphenylsilane bridged c1 symmetric catalysts and polymers made therefrom
WO2024072545A1 (en) 2022-09-29 2024-04-04 Exxonmobil Chemical Patents Inc. Foamable branched polypropylene compositions and foamed products produced therefrom
CN117603523A (en) * 2024-01-23 2024-02-27 青州市鲁冠塑料有限公司 Diffuse scattering resin composition and application thereof in scattering film

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4132698A (en) * 1974-03-20 1979-01-02 Exxon Research & Engineering Co. Elastomeric thermoplastics
WO1998044041A1 (en) * 1997-04-02 1998-10-08 Upofloor Oy Plastic-based material
WO2003048252A1 (en) * 2001-12-05 2003-06-12 Dsm Ip Assets B.V. Thermoplastic elastomer with improved properties
US20040054040A1 (en) * 2002-08-12 2004-03-18 Lin Chon Yie Plasticized polyolefin compositions
US20040186214A1 (en) * 2002-08-12 2004-09-23 Wen Li Fibers and nonwovens from plasticized polyolefin compositions

Family Cites Families (680)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2567016A (en) 1947-10-21 1951-09-04 Standard Oil Dev Co Hydrocarbon rubber plasticized with a polyvinyl compound
US2817693A (en) 1954-03-29 1957-12-24 Shell Dev Production of oils from waxes
DE1769723U (en) 1956-05-26 1958-07-03 Walter Wischnewsky PIVOT BEARINGS, IN PARTICULAR FOR METALLIC REVERSIBLE AND PIVOTING PANEL WINDOWS.
FR1167244A (en) 1957-02-26 1958-11-21 Pechiney Plasticizer for polymers
DE2756458A1 (en) 1976-12-21 1978-06-22 Gen Electric DRIP-RETARDED, PLASTICIZED THERMOPLASTIC COMPOSITION
NL260367A (en) 1960-01-23
US3201364A (en) 1960-08-26 1965-08-17 Monsanto Co Polypropylene plasticized with mineral oil
US3235529A (en) 1960-09-06 1966-02-15 Dow Chemical Co Free flowing polystyrene powders containing 10-40% plasticizer
BE609239A (en) 1960-10-17
US3228896A (en) 1961-05-16 1966-01-11 Phillips Petroleum Co Method of making microporous polyolefin articles and product therefrom
NL280822A (en) 1961-07-11
US3318835A (en) 1961-11-15 1967-05-09 Eastman Kodak Co Compositions containing polypropylene and an ester plasticizer
GB1044028A (en) 1962-07-24 1966-09-28 Grace W R & Co Improvements relating to filled polyolefine
US3541039A (en) 1962-08-27 1970-11-17 Pennwalt Corp Flexible polymeric vinylidene fluoride compositions
NL296509A (en) 1962-09-10
US3239478A (en) 1963-06-26 1966-03-08 Shell Oil Co Block copolymer adhesive compositions and articles prepared therefrom
US3281390A (en) 1963-08-06 1966-10-25 Container Corp Polypropylene plasticized with petrolatum
US3308086A (en) 1963-08-30 1967-03-07 Union Carbide Corp Ethylene copolymers with vinyl esters plasticized with phosphate and carboxylic esters
GB1089907A (en) 1963-09-27 1967-11-08 Union Carbide Corp Plasticized ethylene-acrylic acid copolymers
FR86048E (en) 1964-03-06 1965-11-26 Ethylene Plastique Sa Plasticized polyolefin compositions
GB1044503A (en) 1964-03-23 1966-10-05 Grace W R & Co Cold-worked polyolefin compositions
US3439088A (en) 1964-06-16 1969-04-15 Exxon Research Engineering Co Cosmetic preparations-wax rouge and foundation make-up
DE1264054B (en) 1964-09-14 1968-03-21 Rexall Drug Chemical Process for mixing lubricants and anti-stick agents into polyolefins
NL130672C (en) 1965-04-09
DE1921649U (en) 1965-04-26 1965-08-19 Wilhelm Kirschner FALL PROTECTION NET.
DE1961981U (en) 1965-08-02 1967-06-08 Henkel & Cie Gmbh DEVICE FOR HANGING FILTER HOSES IN FILTER SYSTEMS OF ATOMIZING DRYERS.
DE1248927B (en) 1965-08-19 1967-08-31 Chemische Werke Hüls Aktiengesellschaft, Mari Use of dibenzylbenzenes as plasticizers for polyamides
FR1496048A (en) 1965-10-07 1967-09-22 Politechnika Warszawska A method of making a material which serves as a separable coating for corrosion protection
DE1669020B2 (en) 1966-02-03 1973-10-18 Politechnika Warszawska, Warschau Process for the production of a tear-off corrosion protection coating material
US3299568A (en) 1966-03-01 1967-01-24 Research Corp Compositions plasticized with sulphur
US3475368A (en) 1966-03-09 1969-10-28 Nypel Of Delaware Inc Plasticized nylon composition and process for making the same
US3945975A (en) 1966-05-23 1976-03-23 Protective Treatments, Inc. Sealing adhesive strands and compositions therefor
US3338778A (en) 1966-09-28 1967-08-29 Eastman Kodak Co Thermoplastic adhesive of polypropylene, cellulose ester, polyvinyl acetate, sucrose acetate isobutyrate, and polyalkylene glycol
US3551943A (en) 1966-12-19 1971-01-05 Exxon Research Engineering Co Controlled degradation
FR1536425A (en) 1967-07-06 1968-08-16 Rhone Poulenc Sa 6-oxo-phthalate heptyl
US3415925A (en) 1967-08-01 1968-12-10 Grace W R & Co Process for preparing permeable polyethylene film
AT309789B (en) 1967-11-20 1973-09-10 Buss Ag Mixing and kneading device for plastic masses
US3536796A (en) 1967-11-29 1970-10-27 Grace W R & Co Process for reducing shrinkage in preparing porous plastic sheet
FR1566388A (en) 1968-02-20 1969-05-09
DE1769062A1 (en) 1968-03-28 1971-08-12 Huels Chemische Werke Ag Plasticized polyamides
FR1580539A (en) 1968-07-25 1969-09-05
US3563934A (en) 1969-04-22 1971-02-16 Gen Electric Stabilized,plasticized polyphenylene oxide compositions
DE1921649A1 (en) 1969-04-28 1970-11-19 Arbrisseau Sa Adhesives and similar compositions
US3590528A (en) 1969-09-25 1971-07-06 Princeton Chemical Res Inc Decomposable polybutene-1 agricultural mulch film
GB1352311A (en) 1970-01-20 1974-05-08 Du Pont Coated yarns
DE2013826A1 (en) 1970-03-23 1971-10-07 Exxon Chemie Gmbh Back coating compounds for carpet tiles
DE2019945A1 (en) 1970-04-24 1971-11-04 Basf Ag Polystyrene moulding materials for prepnof foam bodies
FR2194767B1 (en) 1972-08-04 1975-03-07 Shell France
FR2133524B2 (en) 1970-06-05 1975-10-10 Shell Berre Raffinage
US3935344A (en) 1970-10-15 1976-01-27 Owens-Corning Fiberglas Corporation Sizing composition and glass fibers treated therewith
FR2094870A5 (en) 1970-12-28 1972-02-04 Ouest Indle Comprimes
US3686385A (en) 1971-02-05 1972-08-22 Mobil Oil Corp Formation of elastic and high-tenacity fibers from butene-1 homopolymers and copolymers
DE2108293A1 (en) 1971-02-20 1972-08-31 Metallgesellschaft Ag Polyolefine - base articles - plasticised in presence of pvc
US3925504A (en) 1971-05-06 1975-12-09 Union Carbide Corp Poly(hydroxy ether) polymers blended with cyclic ester polymers
GB1390359A (en) 1971-05-13 1975-04-09 Shell Int Research Process for the preparation of lubricating oil with high viscosity index
US3818105A (en) 1971-08-23 1974-06-18 Exxon Research Engineering Co Composition and process for lubricating the skin
US3828105A (en) 1971-11-04 1974-08-06 Alexandre Soc Hairdressing composition and process for preparation thereof
CA1003778A (en) 1972-04-06 1977-01-18 Peter Ladeur Hydrocarbon conversion process
US3999707A (en) 1972-05-05 1976-12-28 Danfoss A/S Air inlet means for air conditioning installations or the like
US4169822A (en) 1972-05-25 1979-10-02 The Norton Company Hot melt sealants
US3925947A (en) 1972-06-26 1975-12-16 Novagard Corp Automobile window sealing
DE2254128C3 (en) 1972-11-04 1975-08-14 Chemische Werke Huels Ag, 4370 Marl Thermoplastic molding compound made from polybutene-I
BE805417A (en) 1972-12-29 1974-01-16 Hardwicke Chemical Co LIQUID MIXTURE OF N-BUTYL-SULFONAMIDES AND THEIR USE FOR THE PLASTIFICATION OF A SYNTHETIC RESIN
IT981300B (en) 1973-03-12 1974-10-10 Snam Progetti SYNTHETIC LUBRICANT OILS FROM THERMAL CRACKING OF VERY HIGH VISCOSITY POLYMERS
GB1452911A (en) 1973-03-17 1976-10-20 Dunlop Ltd Adhesives
SU455976A1 (en) 1973-03-30 1975-01-05 Всесоюзный Научно-Исследовательский Институт Медицинского Приборостроения Polymer composition
US3896245A (en) 1973-04-04 1975-07-22 Protective Treatments Pressure sensitive adhesive strips and sheets
US4207373A (en) 1973-04-25 1980-06-10 Allied Chemical Corporation Highly filled polyolefin compositions
FR2233339B1 (en) 1973-06-12 1976-07-23 Mitsui Petrochemical Indus
US3888949A (en) 1973-06-21 1975-06-10 Du Pont Blends of propylene-alpha-olefin copolymers and polypropylene
US3882197A (en) 1973-06-21 1975-05-06 Du Pont Alpha-olefin copolymer blends
US3839261A (en) 1973-06-22 1974-10-01 Itt Esters of phenylindan used as plasticizers and crosslinking agents
US4038238A (en) 1973-08-29 1977-07-26 The Dow Chemical Company Low density rapid-setting polyurethanes
JPS5634017B2 (en) 1973-09-13 1981-08-07
US3821148A (en) 1973-09-28 1974-06-28 Exxon Research Engineering Co Plasticized thermoplastic block copolymers
ZA747886B (en) 1973-12-29 1975-12-31 British Industrial Plastics Improvements in or relating to plasticized aminoplast resin compositions
US4206101A (en) 1974-01-03 1980-06-03 E. I. Du Pont De Nemours And Company Melt extrudable cold water-soluble films
US4041002A (en) 1974-03-19 1977-08-09 Asahi Kasei Kogyo Kabushiki Kaisha Thermoplastic resin composition
US3988276A (en) 1974-04-12 1976-10-26 Novagard Corporation Solid polysulfide containing hot melt sealants, adhesives and the like
DE2424681C3 (en) 1974-05-21 1980-10-23 Basf Ag, 6700 Ludwigshafen Thermoplastic polyamide or copolyamide compositions containing plasticizers
JPS5122740A (en) 1974-08-16 1976-02-23 Kenzo Hamada
US4010127A (en) 1974-10-15 1977-03-01 Showa Yuka Kk Polyethylene composition
US4113802A (en) 1974-11-14 1978-09-12 Montedison S.P.A. Process for preparing polypropylene compositions having high impact strength at low temperatures
US4006115A (en) 1974-12-26 1977-02-01 Monsanto Company Phthalate ester containing nylon composition
JPS5423378B2 (en) 1975-01-31 1979-08-13
US4063002A (en) 1975-04-14 1977-12-13 Wilson Jr Floyd Insulated glass and sealant therefor
GB1516420A (en) 1975-08-28 1978-07-05 Mitsubishi Chem Ind Tacky polyolefin films
US4094850A (en) 1975-10-06 1978-06-13 Monsanto Company Flame retardant composition
US4153594A (en) 1976-04-08 1979-05-08 Wilson Jr Floyd Insulated glass and sealant therefore
CS187003B1 (en) 1976-04-30 1979-01-31 Rudolf Puffr Process for preparing polyamides
US4097543A (en) 1976-05-12 1978-06-27 Mobil Oil Corporation Selective disproportionation of toluene
US4092282A (en) 1976-05-24 1978-05-30 Cities Service Company Hot melt sealant composition
US4041103A (en) 1976-06-07 1977-08-09 Shell Oil Company Blends of certain hydrogenated block copolymers
US4038237A (en) 1976-06-17 1977-07-26 Shell Oil Company Fire retardant wire coating
DE2632957A1 (en) 1976-07-22 1978-01-26 Bayer Ag Polyamide moulding compsn. contg. nitrile rubber - which acts as plasticiser, giving flexible high impact strength body
US4110185A (en) 1976-11-10 1978-08-29 Becton, Dickinson And Company Irradiation sterilization of semi-crystalline polymers
US5206276A (en) 1976-12-21 1993-04-27 Lee Jr Gim F Flame retardant flexibilized polyphenylene ether compositions
US4684682A (en) 1980-10-17 1987-08-04 General Electric Company Flame retardant flexibilized polyphenylene ether compositions
US4104216A (en) 1977-03-07 1978-08-01 Gulf Oil Corporation Copolymers containing an alpha-olefin and an alpha, beta-ethylenically unsaturated carboxylic acid plasticized with long-chain fatty acid
US4369284A (en) 1977-03-17 1983-01-18 Applied Elastomerics, Incorporated Thermoplastic elastomer gelatinous compositions
US4399248A (en) 1977-05-04 1983-08-16 Rohm And Haas Company Plasticizer, plasticized resin composition and process for preparation thereof
US4136072A (en) 1977-05-24 1979-01-23 Arco Polymers, Inc. Thermoplastic polyolefin film compositions
JPS5846142B2 (en) 1977-07-05 1983-10-14 三菱電線工業株式会社 Poly 4-methylpentene-1 composition
US4147831A (en) 1977-08-31 1979-04-03 Johnson & Johnson Pressure-sensitive adhesive compositions
US4154712A (en) 1977-09-30 1979-05-15 General Electric Company Low molecular weight polyphenylene ether compositions
US4311628A (en) 1977-11-09 1982-01-19 Monsanto Company Thermoplastic elastomeric blends of olefin rubber and polyolefin resin
US4154244A (en) 1977-11-21 1979-05-15 Baxter Travenol Laboratories, Inc. Balloon-type catheter
US4153588A (en) 1977-11-29 1979-05-08 Exxon Research & Engineering Co. Metal neutralized sulfonated EPDM terpolymers and compositions thereof
US4157992A (en) 1977-11-29 1979-06-12 Exxon Research & Engineering Co. Elastomeric blend compositions having improved weathering stability
US4175069A (en) 1977-11-29 1979-11-20 Exxon Research & Engineering Co. Plasticization of neutralized sulfonated elastomeric polymer
US4118359A (en) 1977-11-29 1978-10-03 Exxon Research & Engineering Co. Plasticization of neutralized sulfonated elastomeric polymer
US4118362A (en) 1977-11-29 1978-10-03 Exxon Research & Engineering Co. Plasticization of neutralized sulfonated elastomeric polymer
US4131587A (en) 1977-11-29 1978-12-26 Exxon Research & Engineering Co. Plasticization of neutralized sulfonated elastomeric polymer
US4138378A (en) 1977-12-23 1979-02-06 Phillips Petroleum Company Liquid polyalkene in thermoplastic elastomer sealant formulation
US4210570A (en) 1978-01-06 1980-07-01 Eastman Kodak Company Blends of substantially amorphous olefin copolymers, compatible tackifying resins and plasticizing oils useful as hot melt, pressure-sensitive adhesives
US4189411A (en) 1978-01-19 1980-02-19 General Electric Company Modified polyphenylene ether compositions having lower melt viscosities
US4288480A (en) 1978-06-12 1981-09-08 Scott Paper Company Pressure sensitive adhesive composition and coated product
US4221887A (en) 1978-07-17 1980-09-09 Exxon Research & Engineering Co. Plasticization of quaternary phosphonium ion containing polymers
US4170586A (en) 1978-09-11 1979-10-09 Gulf Oil Corporation Plasticized butene-1 polymer compositions
US4229337A (en) 1978-10-02 1980-10-21 Exxon Research & Engineering Co. Aromatic amide plasticizer for ionic polymers
US4335034A (en) 1978-12-18 1982-06-15 J. P. Stevens & Co., Inc. Thermoplastic compositions and automotive carpeting backed therewith
US4237083A (en) 1979-02-13 1980-12-02 Evans Products Company Process of manufacturing a microporous sheet material
US4325850A (en) 1979-05-21 1982-04-20 W. R. Grace & Co. Processing and product enhancement additives for polyolefin film
JPS5856534B2 (en) 1979-08-28 1983-12-15 チッソ株式会社 Polyolefin resin composition
US4288358A (en) 1979-08-30 1981-09-08 Eastman Kodak Company Blends of propylene/1-butene or 1-pentene/higher α-olefin copolymers, compatible tackifying resins and plasticizing oils useful as hot-melt, pressure-sensitive adhesives
US4467065A (en) 1979-09-10 1984-08-21 Becton Dickinson And Company Semi-crystalline polymers stabilized for irradiation sterilization
US4274932A (en) 1979-09-10 1981-06-23 Becton Dickinson And Company Semi-crystalline polymers stabilized for irradiation sterilization
CA1150452A (en) 1979-10-22 1983-07-26 Kimberly-Clark Corporation Secretafacient device
FR2472000A1 (en) 1979-12-20 1981-06-26 Rhone Poulenc Ind PROCESS FOR IMPROVING COMPATIBILITY OF PLASTIFIERS AND LOADS IN POLYMERS
US4304713A (en) 1980-02-29 1981-12-08 Andrew Corporation Process for preparing a foamed perfluorocarbon dielectric coaxial cable
AU6831481A (en) 1980-03-28 1981-10-01 Imperial Chemical Industries Ltd. Plasticised chlorinated rubber composition
US4347332A (en) 1980-06-19 1982-08-31 American Can Company Polyamide/polyethylene copolymer film and method for producing
US4438228A (en) 1980-08-11 1984-03-20 E. I. Du Pont De Nemours And Company Filled and plasticized blends of linear low density polyethylene
US4403007A (en) 1980-08-11 1983-09-06 E. I. Du Pont De Nemours & Co. Filled thermoplastic compositions based on ethylene interpolymers and polyester, polyether and polyether ester plasticizers
US4592851A (en) 1980-09-02 1986-06-03 Exxon Research And Engineering Co. Lubricating oil composition and method for providing improved thermal stability
US4321334A (en) 1980-09-04 1982-03-23 Shell Oil Company Melt crystallization of butene-1 polymers
CS215313B1 (en) 1980-09-23 1982-08-27 Bohumil Kloboucek Hydroisolation thermoplastic material
US4358384A (en) 1980-10-06 1982-11-09 Smith International Inc. Composite grease for rock bit bearings
US4289668A (en) 1980-10-14 1981-09-15 The Standard Oil Company Polymer systems plasticized with hydroxy fatty acids
EP0050548B1 (en) 1980-10-16 1985-01-16 Rhone-Poulenc Specialites Chimiques Quick setting adhesives comprising an aqueous latex of plasticized polyvinyl acetate
US4327007A (en) 1980-12-22 1982-04-27 Allied Chemical Corporation Polyethylene terephthalate composition containing aliphatic plasticizer and nucleating agent
JPS599576B2 (en) 1981-01-06 1984-03-03 チッソ株式会社 Polyolefin resin composition
CA1198544A (en) 1981-02-12 1985-12-24 Barry L. Dickinson Plasticized polyarylate compositions
DE3105364A1 (en) 1981-02-13 1982-09-02 Bayer Ag, 5090 Leverkusen POLYAMIDE MOLDS
US4403005A (en) 1981-02-17 1983-09-06 Protective Treatments, Inc. Systems for protecting steel
US4542053A (en) 1981-02-17 1985-09-17 Protective Treatments, Inc. Bonding system for wear surfaces
JPS57141811A (en) 1981-02-25 1982-09-02 Furukawa Electric Co Ltd Polyolefin series electrically insulating film and method of producing same
US4335026A (en) 1981-03-27 1982-06-15 Johnson & Johnson Products Inc. Pressure-sensitive adhesive compositions having high shear and low peel resistance
US4552801A (en) 1981-04-01 1985-11-12 American Can Company Plasticized EVOH and process and products utilizing same
US4352823A (en) 1981-04-13 1982-10-05 Nabisco Brands, Inc. Coextruded chewing gum containing a soft non-SBR gum core portion
US4430289A (en) 1981-04-21 1984-02-07 The Dow Chemical Company Process for reducing block and increasing slip of linear low density polyethylene copolymer extrusion-blown films
US4452820A (en) 1981-06-05 1984-06-05 Nabisco Brands, Inc. Gum base and chewing gum containing same
US4387108A (en) 1981-06-12 1983-06-07 Warner-Lambert Company Non-stick chewing gum composition and method of preparation
US4451589A (en) 1981-06-15 1984-05-29 Kimberly-Clark Corporation Method of improving processability of polymers and resulting polymer compositions
DE3125062C2 (en) 1981-06-26 1984-11-22 Degussa Ag, 6000 Frankfurt Process for the production of abrasion-resistant coated catalysts and the use of a catalyst obtained in this way
WO1983000697A1 (en) 1981-08-21 1983-03-03 Ethyl Corp Polyester composition
DE3277772D1 (en) 1981-09-09 1988-01-14 Sumitomo Naugatuck Thermoplastic composition
US4379169A (en) 1981-11-09 1983-04-05 Nabisco Brands, Inc. New gum base and chewing gum containing same
US4399251A (en) 1981-12-07 1983-08-16 General Electric Company Compositions comprising a thermoplastic resin and an olefin mold release agent
US4497926A (en) 1981-12-28 1985-02-05 Raychem Corporation Elastomer based adhesive compositions
EP0083049A3 (en) 1981-12-28 1984-02-22 General Electric Company Composition of ppe and ps-grafted epdm and plasticizer
US4434258A (en) 1982-01-15 1984-02-28 E. I. Du Pont De Nemours And Company Organic acid containing filled and plasticized thermoplastic compositions based on ethylene interpolymers
US4749734A (en) 1982-02-23 1988-06-07 Becton, Dickinson And Company Radiation stabilization of polymeric material
CA1207481A (en) 1982-02-23 1986-07-08 Joel L. Williams Radiation stabilization of polymeric material
US4774277A (en) 1982-03-26 1988-09-27 Exxon Research & Engineering Co. Blends of polyolefin plastics with elastomeric plasticizers
JPS58185632A (en) 1982-04-23 1983-10-29 Iic Kagaku Kogyo Kk Polyolefin resin composition
US4460729A (en) 1982-05-13 1984-07-17 Ethyl Corporation Polyester composition
US4483886A (en) 1982-05-27 1984-11-20 Exxon Research & Engineering Co. Method for making free-flowing, melt-coated rubber pellets
US4440829A (en) 1982-06-29 1984-04-03 Protective Treatments, Inc. Coated bonding tapes having improved peel strength combined with low temperature flexibility
CA1205236A (en) 1982-06-30 1986-05-27 Bp Corporation North America Inc. Plasticized thermoplastic polymer
US4532305A (en) 1982-06-30 1985-07-30 Union Carbide Corporation Thermoplastic polymer plasticized with a poly(aryl ether)
US4469770A (en) 1982-12-27 1984-09-04 Xerox Corporation Styrene butadiene plasticizer toner composition blends
US4459311A (en) 1983-01-03 1984-07-10 Nabisco Brands, Inc. Process for preparing gum base
US4461872A (en) 1983-02-22 1984-07-24 E. I. Du Pont De Nemours And Company Blends of a propylene/α-olefin copolymer with isotactic prolypropylene
US4450250A (en) 1983-03-28 1984-05-22 Eastman Kodak Company Polyester adhesives
US4897178A (en) 1983-05-02 1990-01-30 Uop Hydrocracking catalyst and hydrocracking process
US4518615A (en) 1983-08-23 1985-05-21 Warner-Lambert Company Non-adhesive chewing gum base composition
US4504604A (en) 1983-11-25 1985-03-12 The Goodyear Tire & Rubber Company Energy absorbing rubber composition
DE3347075A1 (en) 1983-12-24 1985-07-04 Bayer Ag, 5090 Leverkusen SOFTENED POLYVINYL ALCOHOL
FR2560884B1 (en) 1984-03-06 1986-10-03 Inst Francais Du Petrole VINYLIDENE POLYFLUORIDE COMPOSITIONS WITH IMPROVED FLEXIBILITY AND THEIR USE, IN PARTICULAR IN THE MANUFACTURE OF FLEXIBLE TUBES
DK165628C (en) 1984-03-09 1993-05-24 Fuji Kagaku Shikogyo RURAL TAPE FOR MULTIPLE USE
NL8401253A (en) 1984-04-18 1985-11-18 Shell Int Research PROCESS FOR PREPARING HYDROCARBONS.
CA1216119A (en) 1984-05-16 1987-01-06 Mitsui Chemicals, Incorporated Process for producing stretched article of ultrahigh- molecular weight polyethylene
US4536537A (en) 1984-06-21 1985-08-20 Shell Oil Company Rubberless high impact polypropylene
US4542122A (en) 1984-06-29 1985-09-17 Exxon Research And Engineering Co. Cobalt catalysts for the preparation of hydrocarbons from synthesis gas and from methanol
US4568663A (en) 1984-06-29 1986-02-04 Exxon Research And Engineering Co. Cobalt catalysts for the conversion of methanol to hydrocarbons and for Fischer-Tropsch synthesis
CA1268875A (en) 1984-07-09 1990-05-08 Takashi Nagai Polyester composition
US4764535A (en) 1984-08-06 1988-08-16 Q'so, Inc. Thermally applied sealants and process
US4665130A (en) 1984-08-31 1987-05-12 Shell Oil Company Packaging film and sheet capable of forming peelable seals with good optics
FR2572417B1 (en) 1984-10-30 1987-05-29 Atochem ADHESIVE COMPOSITIONS BASED ON POLYPROPYLENE MODIFIED BY Grafting of an Unsaturated Monomer
US4551507A (en) 1984-12-17 1985-11-05 Allied Corporation Polyester composition containing tertiary and quaternary amine carboxylate salts
US4579901A (en) 1984-12-21 1986-04-01 General Electric Company Modified polyphenylene ether compositions having improved flow
EP0194808B1 (en) 1985-03-08 1989-05-17 Unitika Ltd. Polyester resin composition for forming an impact resistant article
US4666968A (en) 1985-03-19 1987-05-19 Caschem, Inc. Ester plasticizers for polyarethane compositions
JPS61252254A (en) 1985-04-30 1986-11-10 Idemitsu Kosan Co Ltd Polyolefin resin composition
US4670341A (en) 1985-05-17 1987-06-02 W. R. Grace & Co. Hollow fiber
US4645791A (en) 1985-06-24 1987-02-24 Ford Motor Company Environmentally durable elastomer composition with excellent low temperature dynamic properties
US4921594A (en) 1985-06-28 1990-05-01 Chevron Research Company Production of low pour point lubricating oils
US4616052A (en) 1985-07-05 1986-10-07 Becton, Dickinson And Company High temperature creep resistant thermoplastic elastomer compositions
US4745143A (en) 1985-07-12 1988-05-17 Allied-Signal Inc. Salt resistant polyamide composition
DE3675095D1 (en) 1985-07-19 1990-11-29 Asahi Chemical Ind HYDRATED BLOCK COPOLYMER COMPOSITIONS.
US4663220A (en) 1985-07-30 1987-05-05 Kimberly-Clark Corporation Polyolefin-containing extrudable compositions and methods for their formation into elastomeric products including microfibers
JPH072900B2 (en) 1985-08-01 1995-01-18 モンサント カンパニ− Polyester composition containing phthalimide ester
US4604322A (en) 1985-08-06 1986-08-05 Hercules Incorporated Metallizable polypropylene film
ATE66951T1 (en) 1985-08-16 1991-09-15 Dow Chemical Co EXPANDABLE POLYVINYL(IDEN)AROMATIC PARTICLES, PROCESS FOR THEIR PRODUCTION AND SHAPED ARTICLES.
GB8523460D0 (en) 1985-09-23 1985-10-30 Ici Plc Filamentary yarn & film
JPS6280289A (en) 1985-10-03 1987-04-13 Yamasa Shoyu Co Ltd Method for deoxidizing alcohol
EP0240563B1 (en) 1985-10-07 1990-05-09 BAXTER INTERNATIONAL INC. (a Delaware corporation) High temperature slip agent for polyolefin film
DE3536957A1 (en) 1985-10-17 1987-04-23 Basf Ag MIXTURES CROSS-LINKABLE BY PHOTOPOLYMERISATION
US4693838A (en) 1985-10-29 1987-09-15 Exxon Chemical Patents Inc. Multifunctional viscosity index improver
US4975177A (en) 1985-11-01 1990-12-04 Mobil Oil Corporation High viscosity index lubricants
US4908166A (en) 1985-11-22 1990-03-13 University Of Dayton Method for preparing polyolefin composites containing a phase change material
US4666959A (en) 1985-12-10 1987-05-19 El Paso Products Company Radiation sterilizable propylene polymer compositions and articles manufactured therefrom
FR2594126B1 (en) 1986-02-11 1988-08-05 Rhone Poulenc Chimie LOW HARDNESS SILICONE ELASTOMERIC SUPPORT FOR ELASTOFORMING STAMPING
LU86345A1 (en) 1986-03-06 1987-11-11 Oreal NOVEL BENZOFURAN DERIVATIVES, PROCESSES FOR THEIR PREPARATION AND DRUG AND COSMETIC COMPOSITIONS CONTAINING THEM
US5254378A (en) 1986-05-08 1993-10-19 Minnesota Mining And Manufacturing Company Radiation resistant polypropylene articles and method for preparing same
DE3617318A1 (en) 1986-05-23 1987-11-26 Centralen Inst Khim Promisleno MASS FOR THE PRODUCTION OF MICROPOROUS SEPARATORS AND METHOD FOR THE PRODUCTION THEREOF
GB8613161D0 (en) 1986-05-30 1986-07-02 Exxon Chemical Patents Inc Sealable films
FR2602515B1 (en) 1986-08-08 1988-12-02 Atochem VINYLIDENE POLYFLUORIDE SHEATH POLYAMIDE
CA1273415A (en) 1986-09-12 1990-08-28 Alvin Charles Levy Filled cables
US5028647A (en) 1986-10-24 1991-07-02 Allied-Signal Inc. Polyester composition containing an ester of an ethoxylated aromatic alcohol
US4726989A (en) 1986-12-11 1988-02-23 Minnesota Mining And Manufacturing Microporous materials incorporating a nucleating agent and methods for making same
US4827064A (en) 1986-12-24 1989-05-02 Mobil Oil Corporation High viscosity index synthetic lubricant compositions
JPS63202636A (en) 1987-02-17 1988-08-22 Toyo Tire & Rubber Co Ltd Rubber composition for tire tread
FR2613722B1 (en) 1987-04-07 1990-11-23 Bp Chimie Sa PROCESS FOR THE MANUFACTURE OF PROPYLENE HOMOPOLYMER OR COPOLYMER GRANULES
US5213744A (en) 1987-04-21 1993-05-25 Exxon Chemical Patents Inc. Process for making polyolefin films
IT1204529B (en) 1987-04-24 1989-03-03 Grace W R & Co MULTI-LAYER FILM FOR THE PACKAGING OF ITEMS IN CONTROLLED ATMOSPHERE
US4833172A (en) 1987-04-24 1989-05-23 Ppg Industries, Inc. Stretched microporous material
GB8715530D0 (en) 1987-07-02 1987-08-12 Ici Plc Microporous products
JPH0194261A (en) 1987-07-13 1989-04-12 Univ Tennessee Res Corp Amplification of signal utilizing liposome in homogeneous system for assay involving enzyme
US5149736A (en) 1987-07-13 1992-09-22 Raychem Corporation Heat resistant gel compositions
EP0299718A3 (en) 1987-07-13 1991-03-27 Raychem Corporation Heat-resistant gel compositions
US4833195A (en) 1987-07-20 1989-05-23 Bp Performance Polymers, Inc. High flow drapable polymer compositions
US4904731A (en) 1987-09-04 1990-02-27 Shell Oil Company Polymeric composition
FR2620079B1 (en) 1987-09-04 1990-01-19 Arjomari Prioux HIGH-MOULDABILITY REINFORCED THERMOPLASTIC SHEET
US4814375A (en) 1987-09-24 1989-03-21 The West Company High strength elastomers for pharmaceutical products
DE3735502A1 (en) 1987-10-20 1989-05-03 Rxs Schrumpftech Garnituren Crosslinkable plastic compound, in particular for use in scan regions of electron irradiation units
US4853428A (en) 1987-11-02 1989-08-01 Ford Motor Company Elastomer compositions with superior low temperature flexibility
US4845137A (en) 1987-11-05 1989-07-04 Becton, Dickinson And Company Polyolefin compositions of high clarity and resistance to oxidation
MY103793A (en) 1987-11-05 1993-09-30 Mitsui Petrochemical Ind Olefin resin composition for injection molding
US4824718A (en) 1987-12-04 1989-04-25 Minnesota Mining And Manufacturing Company Porous film
JPH072939B2 (en) 1987-12-07 1995-01-18 不易糊工業株式会社 Removable solid adhesive
US4937399A (en) 1987-12-18 1990-06-26 Exxon Research And Engineering Company Method for isomerizing wax to lube base oils using a sized isomerization catalyst
US4943672A (en) 1987-12-18 1990-07-24 Exxon Research And Engineering Company Process for the hydroisomerization of Fischer-Tropsch wax to produce lubricating oil (OP-3403)
US5093197A (en) 1987-12-21 1992-03-03 Entek Manufacturing Inc. Microporous filaments and fibers
US5230843A (en) 1987-12-21 1993-07-27 Entek Manufacturing Inc. Process of forming microporous fibers and filaments
ATE141343T1 (en) 1987-12-21 1996-08-15 Entek Mfg MICROPOROUS FILAMENTS OR FIBERS, METHOD FOR PRODUCING THE SAME AND ARTICLES MADE THEREFROM
EP0321868A2 (en) 1987-12-22 1989-06-28 Air Products And Chemicals, Inc. Water-based vinyl acetate-ethylene emulsion copolymer contact adhesive
FR2626005A1 (en) 1988-01-14 1989-07-21 Shell Int Research PROCESS FOR PREPARING A BASIC LUBRICATING OIL
US4827073A (en) 1988-01-22 1989-05-02 Mobil Oil Corporation Process for manufacturing olefinic oligomers having lubricating properties
US5264493A (en) 1988-02-19 1993-11-23 Fina Research, S.A. Process for the treatment of polypropylene
DE3809236A1 (en) 1988-03-18 1989-09-28 Lohmann Therapie Syst Lts USE OF KETOGROUPLED CYCLIC COMPOUNDS
US4833192A (en) 1988-05-12 1989-05-23 Baychem International, Inc. Compatible polymer blends useful as melt adhesives (II)
JPH01293102A (en) 1988-05-23 1989-11-27 Tokuyama Soda Co Ltd Microporous hollow yarn membrane and its production
BR8902321A (en) 1988-05-24 1990-01-09 Shell Oil Co PROCESS FOR THE PRODUCTION OF A COMPOSITION UNDERSTANDING A POLYMER OF BUT-1-ENO AND A POLYMER OF PROPYLENE AND ARTICLE
US4960820A (en) 1988-05-24 1990-10-02 Shell Oil Company Compositions and articles using high melt flow poly-1-butene and polypropylene blends
US6013727A (en) 1988-05-27 2000-01-11 Exxon Chemical Patents, Inc. Thermoplastic blend containing engineering resin
KR920003034B1 (en) 1988-06-21 1992-04-13 동양나이론 주식회사 Resin making material
US5105038A (en) 1988-06-23 1992-04-14 Mobil Oil Corporation Synthetic polyolefin lubricant blends
US5624986A (en) 1988-06-30 1997-04-29 H. B. Fuller Licensing & Financing Inc. Hot melt adhesive having controlled property change
KR100197327B1 (en) 1988-07-15 1999-06-15 치어즈 엠. 노우드 Syndiotactic polypropylene
US5026756A (en) 1988-08-03 1991-06-25 Velsicol Chemical Corporation Hot melt adhesive composition
US5091454A (en) 1988-08-03 1992-02-25 Velsicol Chemical Corporation Hot melt adhesive composition
US4996094A (en) 1988-09-26 1991-02-26 Mobil Oil Corporation One-sided cling/one-sided slip stretch wrap films
JPH02107270A (en) 1988-10-18 1990-04-19 Terumo Corp Gasket and medical instrument using the same
US4863785A (en) 1988-11-18 1989-09-05 The James River Corporation Nonwoven continuously-bonded trilaminate
US4952457A (en) 1988-12-05 1990-08-28 Monsanto Company Laminated safety glass and polymeric laminate for use therein
IT1227893B (en) 1988-12-14 1991-05-14 Himont Inc Centerville Road Ne POLYPROPYLENE COMPOSITIONS WITH GOOD TRANSPARENCY AND IMPROVED IMPACT RESISTANCE
US5075269A (en) 1988-12-15 1991-12-24 Mobil Oil Corp. Production of high viscosity index lubricating oil stock
KR900009719A (en) 1988-12-16 1990-07-05 엠. 데이비드 레오나이드 New Ethylene-Propylene Copolymer
US4923588A (en) 1988-12-16 1990-05-08 Exxon Research And Engineering Company Wax isomerization using small particle low fluoride content catalysts
EP0389695A1 (en) 1989-03-28 1990-10-03 Neste Oy Gastight material
CA2012729C (en) 1989-04-07 1997-05-20 Takashi Kuroda Dulled stretched molding and process for producing the same
DE3911725C2 (en) 1989-04-11 1997-09-25 Basf Ag Process for the production of tack-free, highly elastic, multifilament polyurethane elastomer threads, elastomer threads produced by this process and their use
DE3912949A1 (en) 1989-04-20 1990-10-25 Huels Chemische Werke Ag MELT ADHESIVE AND COATING
IT1230133B (en) 1989-04-28 1991-10-14 Himont Inc PLASTIC-ELASTIC POLYPROPYLENE COMPOSITIONS
US4957958A (en) 1989-05-23 1990-09-18 Ethyl Corporation Aromatic bis sulfonamide-containing nylon or polyester
US5264474A (en) 1989-05-23 1993-11-23 Mtm Americas Inc. Polymer compositions
US5171628A (en) 1989-05-25 1992-12-15 Exxon Chemical Patents Inc. Low creep polypropylene textiles
US4959402A (en) 1989-06-08 1990-09-25 Becton, Dickinson And Company High clarity radiation stable polymeric compostion and articles therefrom
US4994552A (en) 1989-06-08 1991-02-19 Becton, Dickinson And Company High clarity radiation stable polymeric composition and articles therefrom
JPH0321611A (en) 1989-06-19 1991-01-30 Nippon Unicar Co Ltd Formable kneaded resin mixture
US5258419A (en) 1989-06-26 1993-11-02 Minnesota Mining And Manufacturing Company Methods of preparing radiation resistant heat sealable polymer blends
JP2544994B2 (en) 1989-06-28 1996-10-16 日本石油化学株式会社 Injection molding materials and vehicle exterior materials
JPH0783758B2 (en) 1989-07-20 1995-09-13 株式会社ニッショー Platelet storage bag and composite bag using the same
US6025448A (en) 1989-08-31 2000-02-15 The Dow Chemical Company Gas phase polymerization of olefins
JPH0731780B2 (en) 1989-09-08 1995-04-10 日本碍子株式会社 Method for manufacturing core for magnetic head
US5049605A (en) 1989-09-20 1991-09-17 Milliken Research Corporation Bis(3,4-dialkylbenzylidene) sorbitol acetals and compositions containing same
JP3015967B2 (en) 1989-10-02 2000-03-06 旭化成工業株式会社 Multilayer packaging film and method for producing the same
US5442004A (en) 1989-10-05 1995-08-15 Raychem Limited Gels
US5036034A (en) 1989-10-10 1991-07-30 Fina Technology, Inc. Catalyst for producing hemiisotactic polypropylene
FR2654109B1 (en) 1989-11-08 1992-12-31 Norsolor Sa THERMOPLASTIC ELASTOMER BASED ON POLYNORBORNENE AND VINYL POLYCHLORIDE.
US4948840A (en) 1989-11-14 1990-08-14 Himont Incorporated Thermoplastic elastomer of propylene polymer material and crosslinked ethylene-propylene rubber
FR2654433B1 (en) 1989-11-16 1992-01-17 Norsolor Sa THERMOPLASTIC COMPOSITIONS WITH ELASTIC MEMORY AND PREPARATION METHOD THEREOF.
JP2977595B2 (en) 1989-11-20 1999-11-15 三井化学株式会社 Syndiotactic polypropylene molded article and method for producing the same
JP2894823B2 (en) 1989-12-06 1999-05-24 三井化学株式会社 Method for producing radiation-resistant polypropylene resin composition and radiation-resistant molded article
US4995884A (en) 1989-12-08 1991-02-26 Henkel Corporation Polyalphaolefin emulsions for fiber and textile applications
US5389711A (en) 1990-02-14 1995-02-14 Shell Oil Company Plasticisers for salt functionalized polyvinyl aromatics
US5076988A (en) 1990-03-09 1991-12-31 Union Carbide Chemicals And Plastics Technology Corporation Process for the extrusion of low density polyethylene
JP2537690B2 (en) 1990-03-16 1996-09-25 豊田合成株式会社 Ethylene propylene rubber compound
US5080942A (en) 1990-05-23 1992-01-14 Minnesota Mining And Manufacturing Company High stretch elastomeric pre-stretched tubes
FR2662638B1 (en) 1990-05-31 1997-09-05 Nok Corp COLD RESISTANT LAMINATED SHEET GAS BARRIER, BLADDER FOR ACCUMULATOR AND ACCUMULATOR COMPRISING SAME.
AU636487B2 (en) 1990-06-18 1993-04-29 Kimberly-Clark Worldwide, Inc. A nonwoven web with improved barrier properties
US5157067A (en) 1990-06-27 1992-10-20 Ferro Corporation Liquid colorant/additive concentrate for incorporation into plastics
AU640490B2 (en) 1990-07-05 1993-08-26 Mobil Oil Corporation Production of high viscosity index lubricants
AU638336B2 (en) 1990-07-05 1993-06-24 Mobil Oil Corporation Production of high viscosity index lubricants
US5106447A (en) 1990-07-17 1992-04-21 National Starch And Chemical Investment Holding Corporation Bonding method employing hot melt adhesives for insulation assembly
US5051478A (en) * 1990-07-26 1991-09-24 Advanced Elastomer Systems, L. P. Ethylene copolymer - modified dynamically vulcanized alloys
US5415791A (en) 1990-08-02 1995-05-16 Oiles Corporation Lubricating composition and a sliding member comprising the composition
US5143978A (en) 1990-08-28 1992-09-01 Himont Incorporated Dynamically partially crosslinked thermoplastic elastomer containing polybutene-1
US5331019A (en) 1990-09-04 1994-07-19 Becton, Dickinson And Company Lubricious radiation stable polymeric composition and articles therefrom
JP3169376B2 (en) 1990-09-20 2001-05-21 大日本インキ化学工業株式会社 Granular colorant and method for producing the same
DE4030563A1 (en) 1990-09-27 1992-04-02 Hoechst Ag MOLDS BASED ON POLYETHYLENE WITH A MEDIUM MOLE WEIGHT OF AT LEAST 500,000 G / MOL
US5162436A (en) 1990-10-04 1992-11-10 Bridgestone/Firestone, Inc. Heat weldable roof sheeting and method for coating roofs
US5124384A (en) 1990-11-16 1992-06-23 Air Products And Chemicals, Inc. Transparent caulks containing fumed silica
US5256717A (en) 1990-12-19 1993-10-26 National Starch And Chemical Investment Holding Corporation Hot melt adhesives useful in temporary bonding operations
US5106899A (en) 1990-12-19 1992-04-21 General Electric Company Plasticized polyphenylene ether compositions
US5114763A (en) 1990-12-28 1992-05-19 Exxon Chemical Patents Inc. Tackified polyethylene layers in stretch/cling films
EP0513470A3 (en) 1991-05-13 1993-03-17 Monsanto Company Adipate compositions
DE59209897D1 (en) 1991-05-27 2001-04-26 Targor Gmbh Process for the production of polyolefins with a broad molar mass distribution
US5308904A (en) 1991-07-23 1994-05-03 Mitsubishi Kasei Corporation Resin composition, porous film or sheet
US5116626A (en) 1991-07-25 1992-05-26 Wm. Wrigley Jr. Company Transparent base and gum composition
US5264277A (en) 1991-09-09 1993-11-23 Mobil Oil Corp. Multi-layer opaque film structures of reduced surface friction and process for producing same
KR930006226A (en) 1991-09-30 1993-04-21 원본미기재 Elastic composite nonwoven fabrics and methods of making the same
US5173317A (en) 1991-10-29 1992-12-22 Wm. Wrigley Jr. Company Gum compositions containing vinyl laurate/vinyl acetate copolymer
TW209877B (en) 1991-11-04 1993-07-21 Shell Internat Res Schappej B V
IT1250045B (en) 1991-11-07 1995-03-30 Butterfly Srl PROCEDURE FOR THE PRODUCTION OF PLASTICIZED POLYVINYL ALCOHOL AND ITS USE FOR THE PREPARATION OF BIODEGRADABLE STARCH-BASED THERMOPLASTIC COMPOSITIONS.
US5171908A (en) 1991-11-18 1992-12-15 Mobil Oil Corporation Synthetic polyolefin lubricant oil
US5180865A (en) 1991-12-06 1993-01-19 Pennzoil Products Company Base oil for shear stable multi-viscosity lubricants and lubricants therefrom
AT401775B (en) 1991-12-18 1996-11-25 Semperit Ag VEHICLE TIRES
US6153703A (en) 1991-12-20 2000-11-28 Exxon Research And Engineering Company Semicrystalline polymer blend compositions with enhanced interspherulitic and interlamellar strength
US5624627A (en) 1991-12-27 1997-04-29 Mitsui Petrochemical Industries, Ltd. Process for preparing surface-modified biaxially oriented film of high molecular weight polyethylene
US5437877A (en) 1992-03-03 1995-08-01 Wm. Wrigley Jr. Company Wax-free chewing gum with initial soft bite
US5462754A (en) 1992-03-03 1995-10-31 Wm. Wrigley Jr. Company Abhesive chewing gum with improved sweetness profile
US5286500A (en) 1992-03-03 1994-02-15 Wm. Wrigley Jr. Company Wax-free chewing gum base
US6245870B1 (en) 1992-03-20 2001-06-12 Fina Technology, Inc. Process for producing syndiotactic/isotactic block polyolefins
US6184326B1 (en) 1992-03-20 2001-02-06 Fina Technology, Inc. Syndiotactic polypropylene
JP3193446B2 (en) 1992-04-07 2001-07-30 大日精化工業株式会社 Olefin-based thermoplastic elastomer composition
DE69327192T2 (en) 1992-05-11 2000-04-27 Fuji Photo Film Co Ltd Shaped articles for light-sensitive photographic materials
US5356709A (en) 1992-05-14 1994-10-18 Baxter International, Inc. Non-PVC coextruded medical grade port tubing
US5424080A (en) 1992-06-30 1995-06-13 Wm. Wrigley Jr. Company Wax-free chewing gum base
DE4226081A1 (en) 1992-08-06 1994-02-10 Henkel Kgaa Thermoplastic hot melt adhesive
ES2110051T5 (en) 1992-08-18 2002-10-01 Shell Int Research PROCEDURE FOR PREPARATION OF HYDROCARBON FUELS.
US7134236B2 (en) 1994-04-19 2006-11-14 Applied Elastomerics, Inc. Gelatinous elastomer compositions and articles for use as fishing bait
US6867253B1 (en) 1994-04-19 2005-03-15 Applied Elastomerics, Inc. Tear resistant, crystalline midblock copolymer gels and articles
US5356986A (en) 1992-08-28 1994-10-18 E. I. Du Pont De Nemours And Company Plasticized fluoropolymers
US5376716A (en) 1992-08-31 1994-12-27 Rexene Products Company Radiation resistant polypropylene resins
WO1994006859A1 (en) 1992-09-15 1994-03-31 The Dow Chemical Company Impact modification of thermoplastics
US5736197A (en) 1992-11-30 1998-04-07 Poly-Wall International, Inc. Method of waterproofing rigid structural materials
BE1006477A3 (en) 1992-12-07 1994-09-06 Solvay Thermoplastic composition, method of preparation and use.
CA2109360A1 (en) 1992-12-21 1994-06-22 Mitsubishi Chemical Corporation Porous film or sheet, battery separator and lithium battery
IT1256260B (en) 1992-12-30 1995-11-29 Montecatini Tecnologie Srl ATACTIC POLYPROPYLENE
BE1006614A3 (en) 1993-01-25 1994-11-03 Solvay Polymer compositions intended for the manufacture of pipes for the transportation of hydrocarbons and products containing same.
US5331047A (en) 1993-02-17 1994-07-19 Himont Incorporated Olefin polymer films
KR970011464B1 (en) 1993-03-12 1997-07-11 주식회사 유공 Polypropylene resin component
ATE141938T1 (en) 1993-03-23 1996-09-15 Atochem Elf Sa COMPOSITION CONSISTING OF AN UNSATURATED ELASTOMER AND A PLASTICIZER FROM THE POLYPHENYLMETHANE FAMILY
EP0618261B1 (en) 1993-04-02 1998-06-03 Shell Internationale Researchmaatschappij B.V. Conveyor belts derived from hot melt compositions, based on hydrogenated block copolymers derived from a vinyl aromatic and a conjugated diene
US5290886A (en) 1993-04-20 1994-03-01 Advanced Elastomer Systems, L.P. Thermoplastic elastomers having improved low temperature properties
CA2119600A1 (en) 1993-04-22 1994-10-23 Francis A. Schurb Compounded latex saturants for porous backings
AU680263B2 (en) 1993-05-25 1997-07-24 Exxon Chemical Patents Inc. Novel polyolefin fibers and their fabrics
DE4317655A1 (en) 1993-05-27 1994-12-01 Basf Ag Multi-phase block copolymers of propylene
GB2278363B (en) 1993-05-28 1996-10-30 Chaloke Pungtrakul A method for the prevention of blocking in linear low density polyethylene films
EP0812854B2 (en) 1993-06-07 2011-04-20 Mitsui Chemicals, Inc. Novel transition metal compound, olefin polymerization catalyst comprising said compound, process for olefin polymerization using said catalyst and propylene homo- and copolymer
EP0629631B1 (en) 1993-06-07 2002-08-28 Mitsui Chemicals, Inc. Novel transition metal compound, and polymerization catalyst containing it
DE4322145C2 (en) 1993-07-02 2002-07-18 Benecke Ag J H Film or molded body made of a multi-phase plastic and its use for the production of composite films
CA2128920C (en) 1993-07-28 1999-06-01 Akihiko Yamamoto Propylene polymer compositions
US5360868A (en) 1993-08-30 1994-11-01 Himont Incorporated Polyolefin compositions having a high balance of stiffness and impact strength
DE4333128A1 (en) 1993-09-29 1995-03-30 Hoechst Ag Process for the preparation of polyolefins
EP0723571B1 (en) 1993-10-12 1998-12-02 H.B. Fuller Licensing &amp; Financing, Inc. Polystyrene-ethylene/butylene-polystyrene hot melt adhesive
FI945974A (en) 1993-12-22 1995-06-23 Shell Int Research Free flowing powder composition, process for preparing it and a homogeneous layer derived from this
US5489646A (en) 1994-01-10 1996-02-06 Koch Industries, Inc. Lower alkyl biphenyls as plasticizers
CA2140096C (en) 1994-01-24 2001-07-24 Joel L. Williams Polyolefin composition of improved ductility and article therefrom
JP3325376B2 (en) 1994-02-01 2002-09-17 三菱樹脂株式会社 Porous film or sheet and method for producing the same
JP3325377B2 (en) 1994-02-01 2002-09-17 三菱樹脂株式会社 Porous film or sheet and method for producing the same
EP0743960B1 (en) 1994-02-04 1998-05-13 Exxon Chemical Patents Inc. Dual donor catalyst system for the polymerization of olefins
US5747573A (en) 1994-02-07 1998-05-05 H. B. Fuller Licensing & Financing, Inc. High heat resistant hot melt adhesive
FR2715948B1 (en) 1994-02-09 1996-04-12 Peaudouce Coated nonwoven material, process for obtaining it and its use in a disposable absorbent hygiene article.
US5489473A (en) 1994-04-07 1996-02-06 Borden, Inc. Biaxially and monoaxially oriented polypropylene cold seal release film
AT406683B (en) 1994-04-14 2000-07-25 Semperit Ag RUBBER BLEND
JP2886107B2 (en) 1994-04-19 1999-04-26 三菱化学株式会社 Thermoplastic elastomer sheet molding
DE4417191C1 (en) 1994-05-17 1995-08-31 Frisetta Gmbh Kunststoffwerke Plasticiser system free from highly volatile cpds., useful in plastics, esp. polyamide
US5614297A (en) 1994-05-19 1997-03-25 Viskase Corporation Polyolefin stretch film
EP0760744A1 (en) 1994-05-24 1997-03-12 Exxon Chemical Patents Inc. Fibers and fabrics incorporating lower melting propylene polymers
DE4420991A1 (en) 1994-06-16 1995-12-21 Danubia Petrochem Deutschland Polypropylene for thermo-forming
US5492943A (en) 1994-06-20 1996-02-20 Hollister Incorporated Adhesive skin barrier composition for ostomy appliance
JP3380043B2 (en) 1994-06-30 2003-02-24 三菱樹脂株式会社 Stretch film for food packaging
US5552489A (en) 1994-07-22 1996-09-03 Exxon Chemical Patents Inc. Tackifiers and a process to obtain tackifiers
IT1274606B (en) 1994-08-09 1997-07-18 Spherilene Srl MIXTURES OF ATACTIC POLYPROPYLENE AND SYNDIOTACTIC POLYPROPYLENE
TW383277B (en) 1994-08-30 2000-03-01 Shell Int Research Comoulded multi-layer polymer blend system, and air bag covers derived therefrom
EP0699519A3 (en) 1994-08-30 1998-04-22 Shell Internationale Researchmaatschappij B.V. Co moulded multi-layer polymer blend system, and shaped articles derived therefrom
GB9418352D0 (en) 1994-09-12 1994-11-02 Bp Chem Int Ltd Plasticizer composition
CA2160618A1 (en) 1994-10-19 1996-04-20 Yasuhiro Nohara Propylene resin composition, molded articles thereof and propylene resin laminate
US5610217A (en) 1994-10-31 1997-03-11 The Gates Corporation Ethylene-alpha-olefin belting
TW337532B (en) 1994-11-16 1998-08-01 Shell Int Research A chemical resistant composition and its use
US5747592A (en) * 1994-12-16 1998-05-05 Exxon Chemical Patents, Inc. Thermoplastic polymer compositions and their production and use
US5601858A (en) 1994-12-29 1997-02-11 Warner-Lambert Company Non-stick chewing gum
WO1996023042A1 (en) 1995-01-25 1996-08-01 Findley Adhesives, Inc. Hot melt adhesive having improved wet strength properties
JPH08208963A (en) 1995-02-02 1996-08-13 New Japan Chem Co Ltd Polyester resin composition
DE19504425A1 (en) 1995-02-10 1996-08-14 Hella Kg Hueck & Co Hot melt adhesives for vehicle lights and vehicle headlights
US5663230A (en) 1995-02-15 1997-09-02 Concrete Sealants, Inc. Water stop composition and methods of preparing same
US5594074A (en) 1995-02-21 1997-01-14 Shell Oil Company Process for improving processability of ultra low melt viscosity polymer
TR199600222A2 (en) 1995-03-24 1996-10-21 Shell Int Research Compositions containing monovinyl aromatic block copolymer and microgranules and powders derived therefrom, suitable for use in rotary molding and similar processes.
DE69633420T2 (en) 1995-03-31 2005-09-29 Basell North America Inc. High energy radiation resistant polyolefin compositions and articles made therefrom
US5728760A (en) 1995-04-11 1998-03-17 Great Lakes Chemical Corporation Use of ring-brominated benzoate compounds as flame retardants and/or plasticizers
AU5487796A (en) 1995-05-22 1996-12-11 Minnesota Mining And Manufacturing Company Protective adhesive article
US5728754A (en) 1995-06-05 1998-03-17 The International Group, Inc. Cable filling and flooding compounds
US5569693A (en) 1995-06-05 1996-10-29 Borden Inc. High stretch film for pallet wrapping
US5789529A (en) 1995-06-13 1998-08-04 Ube Industries, Ltd. Polyamide resin composition and tubular molding comprising the same
US5698650A (en) 1995-06-14 1997-12-16 Exxon Chemical Patents Inc. Elastomeric vehicle brake parts and power transmission belts
JP3474677B2 (en) 1995-06-19 2003-12-08 花王株式会社 Porous sheet and absorbent article using the same
CA2181616A1 (en) 1995-07-21 1997-01-22 Mahmoud R. Rifi Process for the extrusion of polyethylene
CA2181607A1 (en) 1995-07-21 1997-01-22 Mahmoud R. Rifi Process for the extrusion of polyethylene
US5869560A (en) 1995-07-27 1999-02-09 Taisei Corporation Sealing materials and building components useful for clean rooms
WO1997008259A2 (en) 1995-08-22 1997-03-06 Blue Coral, Inc. Universal auto lotion
EP0847420B1 (en) 1995-08-29 2000-02-16 Exxon Chemical Patents Inc. Radiation tolerant polypropylene and its useful articles
JP4139437B2 (en) 1995-09-06 2008-08-27 スリーエム カンパニー Epihalohydrin electrical stress control material
US5552482A (en) 1995-09-08 1996-09-03 Montell North America Inc. Thermoplastic elastomers with improved extrusion performance
US5741563A (en) 1995-09-18 1998-04-21 Exxon Chemical Patents Inc. Shrink films from propylene polymers
GB2307206B (en) 1995-11-15 1999-06-09 Courtaulds Films Polymeric films
JP3792724B2 (en) 1995-11-16 2006-07-05 エイチ・ビー・フラー・ライセンシング・アンド・ファイナンシング・インコーポレイテッド Pellet polymer composition
US6037384A (en) 1995-11-28 2000-03-14 Dainippon Ink And Chemicals, Inc. Expanded material and laminate
US5833839A (en) 1995-12-08 1998-11-10 Exxon Research And Engineering Company High purity paraffinic solvent compositions, and process for their manufacture
FR2742444B1 (en) 1995-12-13 1998-01-16 Atochem Elf Sa POLYOL-BASED PLASTIC COMPOSITION HAVING CONTROLLED VISCOSITY
US6902786B2 (en) 1996-01-04 2005-06-07 Nichiban Company, Limited Pressure-sensitive adhesive compositions for surface-protecting films
US6797765B2 (en) 1996-02-14 2004-09-28 Edizone, Lc Gelatinous elastomer
US5749111A (en) 1996-02-14 1998-05-12 Teksource, Lc Gelatinous cushions with buckling columns
ID17196A (en) 1996-03-14 1997-12-11 Dow Chemical Co ADHESIVE INGREDIENTS THAT CONTAIN OLEFIN POLYMER
EP0886669B1 (en) 1996-03-15 2000-05-10 Amoco Corporation Stiff, strong, tough glass-filled olefin polymer
US5916959A (en) 1996-03-29 1999-06-29 H.B. Fuller Licensing & Financing, Inc. Radial styrene-isoprene-styrene based hot melt pressure sensitive adhesive
AT406684B (en) 1996-04-09 2000-07-25 Danubia Petrochem Polymere USE OF POLYPROPYLENE TO IMPROVE STABILITY TO IONIZING RADIATION
CN1077924C (en) 1996-04-25 2002-01-16 智索公司 Polyolefin fibers and nonwoven fabric produced using the same
US5929147A (en) 1996-06-18 1999-07-27 Montell North America Inc. Embrittlement-resistant polyolefin composition and flexible articles therefrom
DE69626526T2 (en) 1996-06-20 2003-11-20 Yokohama Rubber Co Ltd METHOD FOR PRODUCING A RUBBER COMPOSITION
US6380292B1 (en) 1996-06-21 2002-04-30 Bostik Findley, Inc. Hydrophilic hot melt adhesive
JP3951144B2 (en) 1996-06-26 2007-08-01 チバ スペシャルティ ケミカルズ ホールディング インコーポレーテッド Polymer degradation using NOR-HALS compounds
US5741840A (en) 1996-07-03 1998-04-21 H.B. Fuller Licensing & Financing, Inc. Cohesively failing hot melt pressure sensitive adhesive
EP0818475A1 (en) 1996-07-11 1998-01-14 Fina Research S.A. Syndiotactic/atactic block polyolefins, catalysts and processes for producing the same
DE69707681D1 (en) 1996-07-12 2001-11-29 Fuller H B Licensing Financ "HOT-MELT" WITH EXCELLENT RESISTANCE TO HEAT AND COLD FOR A LOW APPLICATION TEMPERATURE
US6297301B1 (en) 1996-08-06 2001-10-02 Exxonmobil Chemical Patents Inc. Thermoplastic elastomer compositions having improved processing properties
CN1227581A (en) 1996-08-06 1999-09-01 埃克森化学专利公司 Method of processing polyethylene
BE1010655A3 (en) 1996-09-30 1998-11-03 Ucb Sa Compositions polyamides plasticized.
US6086996A (en) 1996-10-11 2000-07-11 Illinois Tool Works Inc. Ethylene-propylene copolymer low noise film additive
US5948557A (en) 1996-10-18 1999-09-07 Ppg Industries, Inc. Very thin microporous material
US6786994B2 (en) 1996-11-04 2004-09-07 Foto-Wear, Inc. Heat-setting label sheet
DE19648895A1 (en) 1996-11-26 1998-05-28 Clariant Gmbh Polar modified polypropylene waxes
EP1241224A1 (en) 1996-11-29 2002-09-18 Riken Technos Corporation Thermoplastic elastomeric resin composition
US6245856B1 (en) 1996-12-17 2001-06-12 Exxon Chemical Patents, Inc. Thermoplastic olefin compositions
US5739200A (en) 1996-12-17 1998-04-14 The Dow Chemical Company Plasticizied α-olefin/vinylidene aromatic monomer of hindered aliphatic or cycloaliphatic vinylidene monomer interpolymers
US6362252B1 (en) 1996-12-23 2002-03-26 Vladimir Prutkin Highly filled polymer composition with improved properties
US6114457A (en) 1997-02-07 2000-09-05 Exxon Chemical Patents Inc. High melt strength polyethylene compositions
JP2001511215A (en) 1997-02-07 2001-08-07 エクソン・ケミカル・パテンツ・インク Propylene polymer incorporating polyethylene macromer
AT408229B (en) 1997-02-11 2001-09-25 Borealis Ag USE OF THERMOPLASTIC ELASTOMERS TO IMPROVE THE STABILITY OF POLYOLEFINS TO IONIZING RADIATION
KR20000075770A (en) 1997-02-28 2000-12-26 후지타 기요시 p-Hydroxybenzoic Esters, Plasticizer Containing the Same, Polyamide Resin Composition, and Molded Objects
US5994482A (en) 1997-03-04 1999-11-30 Exxon Chemical Patents, Inc. Polypropylene copolymer alloys and process for making
US6080818A (en) 1997-03-24 2000-06-27 Huntsman Polymers Corporation Polyolefin blends used for non-woven applications
US6107240A (en) 1997-03-26 2000-08-22 Engelhard Corporation Catalyst composition containing an intimately mixed oxide of cerium and praseodymium
US5783531A (en) 1997-03-28 1998-07-21 Exxon Research And Engineering Company Manufacturing method for the production of polyalphaolefin based synthetic greases (LAW500)
US5869562A (en) 1997-03-28 1999-02-09 H. B. Fuller Licensing & Financing, Inc. Hot melt pressure sensitive adhesive designed for use on high density spun polyolefin film
US6342320B2 (en) 1997-04-23 2002-01-29 Valence Technology, Inc. Electrochemically stable plasticizer
US6340703B1 (en) 1997-05-01 2002-01-22 Novogen, Inc. Treatment or prevention of osteoporosis
JP3387775B2 (en) 1997-05-22 2003-03-17 株式会社大協精工 Sealing stopper for syringe and prefilled syringe
US5849806A (en) 1997-05-23 1998-12-15 Shell Oil Company Resilient polyurethane foams of polydiene diols and tackifying resin
AU8020498A (en) 1997-05-27 1998-12-30 Akzo Nobel N.V. Cross-linking compositions
US6207754B1 (en) 1997-05-29 2001-03-27 Exxon Chemical Patents, Inc. Low modulus thermoplastic olefin compositions
DE19729833A1 (en) 1997-07-11 1999-01-14 Clariant Gmbh Polypropylene wax
DE19730425A1 (en) 1997-07-16 1999-01-21 Henkel Teroson Gmbh Heat-curing laundry-resistant shell sealant
US6027557A (en) 1997-07-17 2000-02-22 Marathon Ashland Petroleum Llc Oxidized blends of asphalt and paraffinic base stock fluxing component having improved low temperature properties
US5925707A (en) 1997-07-30 1999-07-20 Shell Oil Company Oil gel formulations containing high vinyl content hydrogenated styrene-butadiene-styrene block copolymers
US5969021A (en) 1997-08-07 1999-10-19 Fina Technology, Inc. Method of improving crystallization rate and temperature of syndiotactic polypropylene and compositions and products made therefrom
US6635715B1 (en) 1997-08-12 2003-10-21 Sudhin Datta Thermoplastic polymer blends of isotactic polypropylene and alpha-olefin/propylene copolymers
US6525157B2 (en) 1997-08-12 2003-02-25 Exxonmobile Chemical Patents Inc. Propylene ethylene polymers
US6921794B2 (en) 1997-08-12 2005-07-26 Exxonmobil Chemical Patents Inc. Blends made from propylene ethylene polymers
US6017615A (en) 1997-08-25 2000-01-25 Huntsman Polymers Corporation Film product comprising novel polyolefins
US6019735A (en) 1997-08-28 2000-02-01 Visco Technologies, Inc. Viscosity measuring apparatus and method of use
JP2001516136A (en) 1997-09-09 2001-09-25 エヌケイティ リサーチ センター アクティーゼルスカブ ELECTRICALLY INSULATING MATERIAL, PROCESS FOR PRODUCING THE SAME, AND INSULATING OBJECT COMPRISING THE MATERIAL
US6316068B1 (en) 1997-09-10 2001-11-13 Asahi Kasei Kabushiki Kaisha Elastomer composition
US6165599A (en) 1997-09-15 2000-12-26 Applied Extrusion Technologies, Inc. Biaxially oriented film prepared from metallocene catalyzed polypropylene
US6497965B1 (en) 1997-10-09 2002-12-24 Applied Extrusion Technologies, Inc. Slip agents and polypropylene films prepared therefrom
US6042902A (en) 1997-10-20 2000-03-28 Hoechst Celanese Corporation Adhesives for making multilayer films comprising liquid crystalline polymers and poly(ethylene terephthalate) or polycarbonate
US6090989A (en) 1997-10-20 2000-07-18 Mobil Oil Corporation Isoparaffinic lube basestock compositions
US6184327B1 (en) 1997-12-10 2001-02-06 Exxon Chemical Patents, Inc. Elastomeric propylene polymers
US6197910B1 (en) 1997-12-10 2001-03-06 Exxon Chemical Patents, Inc. Propylene polymers incorporating macromers
EP1041111A1 (en) 1997-12-11 2000-10-04 Sumitomo Chemical Company, Limited Thermoplastic elastomer composition, powder, pellets, and moldings
SE511215C2 (en) 1997-12-22 1999-08-23 Asea Brown Boveri Dielectric gelling composition, use thereof, insulated electric DC cable comprising such composition and process for making it
WO1999036471A1 (en) 1998-01-13 1999-07-22 The Yokohama Rubber Co., Ltd. Thermoplastic elastomer composition, process for producing the same, and pneumatic tire and hose made with the same
US6096420A (en) 1998-01-30 2000-08-01 Tredegar Corporation Thin plastic film
US5968455A (en) 1998-02-17 1999-10-19 Brickley; James Lawrence Ultraviolet air sterilization device and mobile unit incorporating sterilization device
US6300407B1 (en) 1998-03-06 2001-10-09 Rohm And Haas Company Polymeric (meth)acrylate plasticizers and processing aids for elastomers
US6207606B1 (en) 1998-05-15 2001-03-27 Univation Technologies, Llc Mixed catalysts and their use in a polymerization process
US6177190B1 (en) 1998-05-29 2001-01-23 3M Innovative Properties Company Radiation curable poly(1-alkene) based pressure-sensitive adhesives
US6027674A (en) 1998-06-03 2000-02-22 Yates; Paul M. Resilient cushion method of manufacture
KR100598192B1 (en) 1998-06-05 2006-07-07 닛폰 포리프로 가부시키가이샤 Propylene block copolymer and propylene resin composition
US6310134B1 (en) 1998-06-30 2001-10-30 Eastman Chemical Company Adhesion-promoting primer compositions for polyolefin substrates
US6288171B2 (en) 1998-07-01 2001-09-11 Advanced Elastomer Systems, L.P. Modification of thermoplastic vulcanizates using random propylene copolymers
KR100581789B1 (en) 1998-07-01 2006-05-23 엑손모빌 케미칼 패턴츠 인코포레이티드 Elastic blends comprising crystalline polymer and crystallizable polymers of propylene
BR9913647B1 (en) 1998-08-26 2008-11-18 branched polypropylene and process for producing the same.
EP1153069B1 (en) 1998-09-01 2004-11-17 KRATON Polymers Research B.V. Polymeric compound, use of that compound in a foam production process, a foaming process, foamed compounds and articles containing foamed compounds
US6165949A (en) 1998-09-04 2000-12-26 Exxon Research And Engineering Company Premium wear resistant lubricant
US6080301A (en) 1998-09-04 2000-06-27 Exxonmobil Research And Engineering Company Premium synthetic lubricant base stock having at least 95% non-cyclic isoparaffins
DE19841303A1 (en) 1998-09-10 2000-03-23 Hauke Malz Leak sealant for tanks and other vessels for hazardous substances comprises optionally plasticised thermoplastic or reactive plastic material which is molded to fit leak and sets after reasonable working time
US6197285B1 (en) 1998-09-16 2001-03-06 Exxon Chemical Patents Inc. Use of isoparaffin extenders for clear gel cosmetic compounds
EP0990675A1 (en) 1998-10-02 2000-04-05 Bridgestone/Firestone, Inc. Non-black, mineral-filled roof accessories
JP4023927B2 (en) 1998-10-09 2007-12-19 三菱化学株式会社 Thermoplastic elastomer composition
US6303067B1 (en) 1998-11-13 2001-10-16 3M Innovative Properties Company Method of stretching films according to an overbias or overstretch stretch profile
JP2000154281A (en) 1998-11-18 2000-06-06 Tokyo Printing Ink Mfg Co Ltd Polyolefin resin composition
US6084031A (en) 1998-11-30 2000-07-04 Advanced Elastomer Systems, L.P. TPV from hydrosilylation crosslinking of acrylic modified bromo XP-50 butyl rubber
US6294631B1 (en) 1998-12-15 2001-09-25 Exxonmobil Chemical Patents Inc. Hyperbranched polymers by coordination polymerization
US6258903B1 (en) 1998-12-18 2001-07-10 Univation Technologies Mixed catalyst system
US6503984B2 (en) 1998-12-22 2003-01-07 Advanced Elastomer Systems, L.P. TPE composition that exhibits excellent adhesion to textile fibers
US6583076B1 (en) 1999-01-08 2003-06-24 Kimberly-Clark Worldwide, Inc. Nonwoven fabrics prepared using visbroken single-site catalyzed polypropylene
US6228171B1 (en) 1999-01-29 2001-05-08 Tokyo Electron Ltd. Heat processing apparatus
JP3396178B2 (en) 1999-02-10 2003-04-14 住友ゴム工業株式会社 Low elastic modulus rubber composition
US6190769B1 (en) 1999-02-19 2001-02-20 E. I. Du Pont De Nemours And Company Abrasive filaments of plasticized polyamides
AU4047400A (en) 1999-04-01 2000-10-23 Foto-Wear, Inc. Polymeric composition and printer/copier transfer sheet containing the composition
FR2792321B1 (en) 1999-04-19 2003-12-12 Atochem Elf Sa PROCESS FOR PRODUCING POLYPROPYLENE RESIN WITH CONTROLLED RHEOLOGY
US6500563B1 (en) 1999-05-13 2002-12-31 Exxonmobil Chemical Patents Inc. Elastic films including crystalline polymer and crystallizable polymers of propylene
AU5007500A (en) 1999-05-13 2000-12-05 Exxon Chemical Patents Inc. Elastic fibers and articles made therefrom, including crystalline and crystallizable polymers of propylene
US6750284B1 (en) 1999-05-13 2004-06-15 Exxonmobil Chemical Patents Inc. Thermoplastic filled membranes of propylene copolymers
US6423800B1 (en) 1999-05-26 2002-07-23 Fina Technology, Inc. Pelletized polyolefin having ultra-high melt flow and its articles of manufacture
CA2310925C (en) 1999-06-11 2005-10-11 Kuraray Co., Ltd. Multilayered structure
EP1062930B1 (en) 1999-06-21 2006-08-16 Kao Corporation Absorbent article
BE1012775A3 (en) 1999-07-06 2001-03-06 Solvay Flexible polymer compositions propylene.
US6143818A (en) 1999-08-04 2000-11-07 Ato Findley, Inc. Hot melt adhesive based on ethylene-propylene rubber (EPR) and semicrystalline olefinic polymers
US6194498B1 (en) 1999-08-10 2001-02-27 Ppg Industries Ohio, Inc. Non-fogging plasticizer and its use in resinous compositions
JP2001049056A (en) 1999-08-12 2001-02-20 Mitsui Chemicals Inc Olefinic thermoplastic rubber composition
JP2001064523A (en) 1999-08-27 2001-03-13 Sumitomo Chem Co Ltd Plasticizer for theroplastic resin, theroplastic resin composition containing it and method for plasticizing thermoplastic resin using it
US6639020B1 (en) 1999-09-03 2003-10-28 Exxon Mobil Chemical Patents Inc. Plasticized polypropylene thermoplastics
DE60029471T3 (en) 1999-09-21 2012-02-16 Teknor Apex Co. THERMOPLASTIC VULCANISATE, WITH FOAM, AND FOAM MANUFACTURED THEREOF
US6191078B1 (en) 1999-09-21 2001-02-20 Exxonmobil Research And Engineering Company Part-synthetic, aviation piston engine lubricant
US6271323B1 (en) 1999-10-28 2001-08-07 Univation Technologies, Llc Mixed catalyst compounds, catalyst systems and their use in a polymerization process
JP2001131509A (en) 1999-11-09 2001-05-15 Yazaki Corp Non-halogenated resin composition for adhesive tape, film which is formed from the same and is used for adhesive tape, and adhesive tape
US6861143B2 (en) 1999-11-17 2005-03-01 Pirelli Cavi E Sistemi S.P.A. Cable with recyclable covering
EP1104783A1 (en) 1999-11-29 2001-06-06 Dunlop Tech GmbH Floor- and wall covering
US20010007896A1 (en) 1999-12-10 2001-07-12 Agarwal Pawan Kumar Propylene diene copolymers
ES2282158T3 (en) 1999-12-21 2007-10-16 Exxonmobil Chemical Patents Inc. ADHESIVE ALPHA-OLEFINE INTERPOLIMEROS.
US6231970B1 (en) 2000-01-11 2001-05-15 E. Khashoggi Industries, Llc Thermoplastic starch compositions incorporating a particulate filler component
EP1116747A1 (en) 2000-01-14 2001-07-18 Sumitomo Rubber Industries, Ltd. Low-modulus polymer composition and sealant using the same
DE60138657D1 (en) 2000-01-18 2009-06-18 Basell Polyolefine Gmbh Ligand for a metallocene catalyst for the polymerization of propylene and its production process
US6329468B1 (en) 2000-01-21 2001-12-11 Bostik Findley, Inc. Hot melt adhesive based on semicrystalline flexible polyolefins
US6384142B1 (en) 2000-02-08 2002-05-07 Exxonmobil Chemical Patents Inc. Propylene impact copolymers
EP1801153B1 (en) 2000-02-09 2020-04-08 Mitsui Chemicals, Inc. Low fogging thermoplastic elastomer composition and manufacturing method and use of same composition
JP2001226865A (en) 2000-02-10 2001-08-21 Idemitsu Unitech Co Ltd Nonwoven fabric, method for producing the same and sanitary material
JP2001233992A (en) 2000-02-21 2001-08-28 Ishizuka Glass Co Ltd Molding auxiliary, its manufcturing method, and polymeric composite compounded with holding auxiliary
US6372379B1 (en) 2000-02-25 2002-04-16 Abbas M. Samii Microporous membrane battery separator for silver zinc batteries
DE10010001A1 (en) 2000-03-02 2001-09-06 Celanese Ventures Gmbh Membranes useful in fuel cells comprise a blend of sulfonated aryl polymer, aminated or nitrated polyether(ether)sulfone and plasticizer
JP3394740B2 (en) 2000-03-16 2003-04-07 アイセロ化学株式会社 Packaging film
JP2001279031A (en) 2000-03-30 2001-10-10 Taiko Kk Polyolefin resin composition
US20020049276A1 (en) 2000-04-05 2002-04-25 Zwick Paul D. Thermoplastic elastomer gel compositions and method of making same
FR2807384B1 (en) 2000-04-07 2002-06-21 Look Cycle Int AUTOMATIC FIXING DEVICE AND CYCLIST PEDAL PROVIDED WITH SUCH A DEVICE
DE60120092T2 (en) 2000-04-07 2006-12-07 Mitsui Chemicals, Inc. THERMOPLASTIC ELASTOMER COMPOSITION WITH GREAT THERMAL STABILITY
US6342209B1 (en) 2000-05-04 2002-01-29 Revlon Consumer Products Corporation Cosmetic compositions containing film forming polymers plasticized with esters and malic acid
US6372847B1 (en) 2000-05-10 2002-04-16 Exxon Mobil Chemical Patents, Inc. Polyolefin compositions having improved low temperature toughness
KR100366569B1 (en) 2000-05-26 2003-01-09 주식회사 엘지씨아이 A composition of thermoplastic resin
JP3710993B2 (en) 2000-05-31 2005-10-26 株式会社大林組 Foam-type fireproof composition having water resistance
US6476135B1 (en) 2000-06-07 2002-11-05 Basell Poliolefine Italia S.P.A. Polyolefin composition containing low viscosity propylene homopolymer, fiber and extensible non-woven fabric prepared therefrom
US6932592B2 (en) 2000-06-22 2005-08-23 Exxonmobil Chemical Patents Inc. Metallocene-produced very low density polyethylenes
EP1179563B1 (en) 2000-08-11 2004-05-19 Japan Polychem Corporation Resin composition for heat-shrinkable polypropylene shrink label and film comprising same
US6858767B1 (en) 2000-08-11 2005-02-22 Uniroyal Chemical Company, Inc. Process for producing liquid polyalphaolefin polymer, metallocene catalyst therefor, the resulting polymer and lubricant containing same
GB0020080D0 (en) 2000-08-15 2000-10-04 Borealis Tech Oy Injection moulding
US6559232B2 (en) 2000-08-18 2003-05-06 Riken Technos Corporation Thermoplastic resin composition
NL1016055C2 (en) 2000-08-30 2002-03-01 Dsm Nv Thermoplastic elastomer with improved properties.
WO2002020528A2 (en) 2000-09-01 2002-03-14 Milliken & Company Fluorinated and alkylated alditol derivatives and polyolefin articles containing same
US6855422B2 (en) 2000-09-21 2005-02-15 Monte C. Magill Multi-component fibers having enhanced reversible thermal properties and methods of manufacturing thereof
US6399707B1 (en) 2000-09-29 2002-06-04 Exxonmobil Chemical Patents Inc. Impact copolymer and plastomer blend
EP1201406B1 (en) 2000-09-29 2002-10-30 Duo-Plast AG A multilayer strech film having cling properties, a method of preparation thereof and its use for strech wrapping operations
FI110157B (en) 2000-10-12 2002-12-13 Duraban Oy Antimicrobial polyalphaolefin composition and its use, process for the preparation of styrene-butadiene block copolymers containing thermoplastic elastomers and their use
US20060167184A1 (en) 2000-10-18 2006-07-27 Waddell Walter H Innerliners for use in tires
US7714043B2 (en) 2000-10-18 2010-05-11 Exxonmobil Chemical Patents Inc. Tire innerliners having improved cold temperature properties
US6509128B1 (en) 2000-10-25 2003-01-21 3M Innovative Properties Company Imagewise printing of adhesives and limited coalescence polymerization method
FR2815561A1 (en) 2000-10-25 2002-04-26 Yves Adelhanoff Recovery of polyolefin wastes, especially polyethylene and polypropylene for recycling, involves preparing waste for agglomeration and the addition of plasticizer or elastomer
EP1330479B2 (en) 2000-10-30 2015-01-21 ExxonMobil Chemical Patents Inc. Graft-modified polymers based on novel propylene ethylene copolymers
KR100387649B1 (en) 2000-11-01 2003-06-27 현대자동차주식회사 Composition of polypropylene resin
AU1705402A (en) 2000-12-06 2002-06-18 Pirelli Cavi E Sistemi Spa Process for producing a cable with a recyclable coating
US6657009B2 (en) 2000-12-29 2003-12-02 Kimberly-Clark Worldwide, Inc. Hot-melt adhesive having improved bonding strength
US6451915B1 (en) 2000-12-29 2002-09-17 Advanced Elastomer Systems, L.P. Thermoplastic elastomers having improved processing and physical property balance
US6388013B1 (en) 2001-01-04 2002-05-14 Equistar Chemicals, Lp Polyolefin fiber compositions
MXPA03006804A (en) 2001-01-31 2004-10-15 Bridgestone Corp Elastic members for inkjet recording apparatus, ink tanks and inkjet recording apparatus.
DE10104236A1 (en) 2001-01-31 2002-08-01 Bayer Ag Rubber compounds containing terpolymers
US20020156144A1 (en) 2001-02-09 2002-10-24 Williams Kevin Alan UV-curable, non-chlorinated adhesion promoters
US7056971B2 (en) 2001-02-13 2006-06-06 Gls Corporation Essentially gas-impermeable thermoplastic elastomer
US6531214B2 (en) 2001-02-14 2003-03-11 3M Innovative Properties Company Replacement for plasticized polyvinyl chloride
US6656385B2 (en) 2001-02-21 2003-12-02 The Procter & Gamble Company Functionalized cubic liquid crystalline phase materials and methods for their preparation and use
US20020155267A1 (en) 2001-02-22 2002-10-24 Bader Michael John Multi-layer hermetically sealable film
CA2338900A1 (en) 2001-02-28 2002-08-28 Bayer Inc. Articles for dynamic load applications
US6632385B2 (en) 2001-03-23 2003-10-14 First Quality Nonwovens, Inc. Condrapable hydrophobic nonwoven web and method of making same
JP3881271B2 (en) 2001-03-29 2007-02-14 三井化学株式会社 Thermoplastic elastomer composition and use thereof
US6632850B2 (en) 2001-04-04 2003-10-14 3M Innovative Properties Company Microporous materials and methods of making the same
US20030022977A1 (en) 2001-04-06 2003-01-30 Hall James E. Soft gel compatibilized polymer compound having low hysteresis
US6403692B1 (en) 2001-04-19 2002-06-11 Dow Global Technologies Inc. Filled thermoplastic composition
US20020168518A1 (en) 2001-05-10 2002-11-14 The Procter & Gamble Company Fibers comprising starch and polymers
US6653360B2 (en) 2001-05-23 2003-11-25 Chakra V. Gupta Flexible foamed polyethylene
WO2002100153A2 (en) 2001-06-08 2002-12-19 Texas Petrochemicals Lp Improved cling film with enhanced polyisobutylene tackifier
US7365137B2 (en) 2001-07-17 2008-04-29 Basell Polyolefine Gmbh Multistep process for the (co) polymerization of olefins
US6713529B2 (en) 2001-08-10 2004-03-30 Illinois Tool Works, Inc. Phase-change ink composition
US6583207B2 (en) 2001-08-30 2003-06-24 Velsicol Chemical Corporation Liquid benzoate ester compositions and aqueous polymer compositions containing same as plasticizers
US6653385B2 (en) 2001-10-18 2003-11-25 Bostik Findley, Inc. Hot melt adhesive composition based on a blend of amorphous poly-α-olefin and syndiotactic polypropylene
US6906160B2 (en) 2001-11-06 2005-06-14 Dow Global Technologies Inc. Isotactic propylene copolymer fibers, their preparation and use
US6960635B2 (en) 2001-11-06 2005-11-01 Dow Global Technologies Inc. Isotactic propylene copolymers, their preparation and use
WO2003040204A1 (en) 2001-11-09 2003-05-15 Japan Polypropylene Corporation Propylene block copolymer
JP3827561B2 (en) 2001-11-22 2006-09-27 三井化学株式会社 Olefinic thermoplastic elastomer and molded article thereof
US6900147B2 (en) 2001-11-28 2005-05-31 Kimberly-Clark Worldwide, Inc. Nonwoven webs having improved necking uniformity
US6849672B2 (en) 2002-01-15 2005-02-01 H.B. Fuller Licensing & Financing Inc. Superabsorbent thermoplastic composition and article including same
EP1331258A1 (en) 2002-01-23 2003-07-30 KRATON Polymers Research B.V. Pressure sensitive adhesive compositions
US20030144415A1 (en) 2002-01-29 2003-07-31 Dsm N.V. Process for the preparation of a thermoplastic elastomer comprising a partially vulcanized rubber concentrate
US20030181584A1 (en) 2002-02-07 2003-09-25 Kraton Polymers U.S. Llc Elastomeric articles prepared from controlled distribution block copolymers
ATE315612T1 (en) 2002-02-11 2006-02-15 Dsm Ip Assets Bv THERMOPLASTIC POLYMER COMPOSITION
AU2003223188A1 (en) 2002-03-22 2003-10-13 Exxonmobil Chemical Patents Inc. Adhesives
US6787593B2 (en) 2002-03-27 2004-09-07 Lear Corporation Sound-deadening composites of metallocene copolymers for use in vehicle applications
US20030204008A1 (en) 2002-04-24 2003-10-30 Campion Robert Paget Elastomers
US6706828B2 (en) 2002-06-04 2004-03-16 Crompton Corporation Process for the oligomerization of α-olefins having low unsaturation
US6753373B2 (en) 2002-06-20 2004-06-22 Kris W. Winowiecki Polyolefin compositions and method of use thereof in molded products
JP2004035623A (en) 2002-06-28 2004-02-05 Tonen Chem Corp Modified polypropylene and method for producing the same
CN1301293C (en) 2002-07-19 2007-02-21 国际壳牌研究有限公司 Composition comprising epdm and a paraffinic oil
AU2003259234A1 (en) 2002-07-31 2004-02-25 Exxonmobil Chemical Patents Inc. Silane crosslinkable polyethylene
GB0313018D0 (en) 2002-08-10 2003-07-09 Emtelle Uk Ltd Signal transmitting cable
US7652092B2 (en) 2002-08-12 2010-01-26 Exxonmobil Chemical Patents Inc. Articles from plasticized thermoplastic polyolefin compositions
US7531594B2 (en) 2002-08-12 2009-05-12 Exxonmobil Chemical Patents Inc. Articles from plasticized polyolefin compositions
US7652094B2 (en) 2002-08-12 2010-01-26 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US8003725B2 (en) 2002-08-12 2011-08-23 Exxonmobil Chemical Patents Inc. Plasticized hetero-phase polyolefin blends
US7998579B2 (en) 2002-08-12 2011-08-16 Exxonmobil Chemical Patents Inc. Polypropylene based fibers and nonwovens
US7629416B2 (en) 2002-08-12 2009-12-08 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US7662885B2 (en) 2002-08-12 2010-02-16 Exxonmobil Chemical Patents Inc. Method to make an article comprising polymer concentrate
US7795366B2 (en) 2002-08-12 2010-09-14 Exxonmobil Chemical Patents Inc. Modified polyethylene compositions
US7622523B2 (en) 2002-08-12 2009-11-24 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US6844381B2 (en) 2002-08-15 2005-01-18 Fina Technology, Inc. Modification of syndiotactic polypropylene with mineral oil
US6992146B2 (en) 2002-08-22 2006-01-31 Sunoco Inc. (R&M) Very low melt viscosity resin
US6855777B2 (en) 2002-08-22 2005-02-15 Sunoco, Inc. (R&M) Very low melt viscosity resin
US6905760B1 (en) 2002-08-29 2005-06-14 Asahi Kasei Life And Living Corporation Polypropylene-based wrap film
FR2844283B1 (en) 2002-09-11 2006-10-27 Soprema POLYRETHANE MODIFIED BITUMIN BINDER MIXTURE MEMBRANE AND PROCESS FOR PRODUCING THE SAME
ES2394304T3 (en) 2002-10-15 2013-01-30 Exxonmobil Chemical Patents, Inc. Multiple catalyst system for the polymerization of olefins and polymers produced from them
US7223822B2 (en) 2002-10-15 2007-05-29 Exxonmobil Chemical Patents Inc. Multiple catalyst and reactor system for olefin polymerization and polymers produced therefrom
US7700707B2 (en) 2002-10-15 2010-04-20 Exxonmobil Chemical Patents Inc. Polyolefin adhesive compositions and articles made therefrom
US7541402B2 (en) 2002-10-15 2009-06-02 Exxonmobil Chemical Patents Inc. Blend functionalized polyolefin adhesive
EP1573107B1 (en) 2002-10-24 2009-12-02 Dow Global Technologies Inc. Elastomeric multicomponent fibers, nonwoven webs and nonwoven fabrics
CN1717445A (en) 2002-11-27 2006-01-04 三菱化学株式会社 Release agent, layered pressure-sensitive adhesive product, and layered pressure-sensitive adhesive tape
US7312167B2 (en) 2002-12-23 2007-12-25 Kimberly-Clark Worldwide, Inc. Breathable multilayer films for use in absorbent articles
US7010641B2 (en) 2003-01-31 2006-03-07 Agilent Technologies, Inc. Integrated circuit routing resource optimization algorithm for random port ordering
JP4345327B2 (en) 2003-03-12 2009-10-14 富士ゼロックス株式会社 Biodegradable polymer, method for producing the same, and molded article
US6984696B2 (en) 2003-03-28 2006-01-10 Exxonmobil Chemical Patents Inc. Elastic blends of semicrystalline propylene polymers and high glass transition temperature materials
US7037989B2 (en) 2003-05-27 2006-05-02 Exxonmobil Chemical Patents Inc. Copolymers of ethylene and/or α-olefins and vicinally disubstituted olefins
US20040241309A1 (en) 2003-05-30 2004-12-02 Renewable Lubricants. Food-grade-lubricant
PT1560879E (en) * 2003-06-12 2006-09-29 Sued Chemie Ag PROCESS FOR THE PREPARATION OF NANOCOMPOSITE ADDITIVES WITH IMPROVED POLYMER DELAMINATION
US6946522B2 (en) 2003-06-30 2005-09-20 Advanced Elastomer Systems L.P. Thermoplastic elastomers with improved coring properties
CN100514509C (en) 2003-07-25 2009-07-15 普雷斯曼电缆及系统能源有限公司 Continuous process for manufacturing electric cables
US8192813B2 (en) 2003-08-12 2012-06-05 Exxonmobil Chemical Patents, Inc. Crosslinked polyethylene articles and processes to produce same
US7015283B2 (en) 2003-10-10 2006-03-21 Exxonmobil Chemical Patents Inc. Compositions of polypropylene and polyamide
WO2005049671A1 (en) 2003-11-14 2005-06-02 Exxonmobil Chemical Patents Inc. High strength propylene-based elastomers and uses thereof
US20050130544A1 (en) 2003-11-18 2005-06-16 Cheng Chia Y. Elastic nonwoven fabrics made from blends of polyolefins and processes for making the same
US20050106978A1 (en) 2003-11-18 2005-05-19 Cheng Chia Y. Elastic nonwoven fabrics made from blends of polyolefins and processes for making the same
US20050170117A1 (en) 2004-01-31 2005-08-04 Cleveland Rafael L. Multi-layered hose
US7308411B2 (en) 2004-04-01 2007-12-11 Leo Software, Inc. Method of presenting leasing arrangements
US7645829B2 (en) 2004-04-15 2010-01-12 Exxonmobil Chemical Patents Inc. Plasticized functionalized propylene copolymer adhesive composition
US7589145B2 (en) 2004-04-15 2009-09-15 Exxonmobil Chemical Patents Inc. Syndiotactic rich polyolefins
US7226977B2 (en) 2004-04-19 2007-06-05 Sunoco, Inc. ( R&M) High melt flow rate thermoplastic polyolefins produced in-reactor
CA2562429C (en) * 2004-05-05 2015-02-17 Dow Global Technologies Inc. Scratch resistant propylene polymer composition
US7294675B2 (en) 2004-06-09 2007-11-13 Advanced Elastomer Systems, L.P. Soft thermoplastic vulcanizate compositions
EP1607440A1 (en) 2004-06-18 2005-12-21 Borealis Technology OY Modified polypropylene composition
JP5060952B2 (en) 2004-08-13 2012-10-31 エクソンモービル・ケミカル・パテンツ・インク POLYMER COMPOSITION, USE THEREOF, AND PRODUCTION METHOD THEREOF
ATE455152T1 (en) 2004-10-08 2010-01-15 Exxonmobil Chem Patents Inc COMBINATION OF STICKER AND POLY-ALPHA-OLEFIN OIL
US7745526B2 (en) 2004-11-05 2010-06-29 Exxonmobil Chemical Patents Inc. Transparent polyolefin compositions
US7829623B2 (en) 2004-11-05 2010-11-09 Exxonmobil Chemical Patents Inc. Thermoplastic vulcanizates having improved fabricability
US8389615B2 (en) 2004-12-17 2013-03-05 Exxonmobil Chemical Patents Inc. Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin
CA2588770C (en) 2004-12-17 2010-03-23 Exxonmobil Chemical Patents Inc. Homogeneous polymer blend and articles therefrom
CN101111555B (en) 2004-12-17 2012-04-11 埃克森美孚化学专利公司 Heterogeneous polymer blends and molded articles therefrom
WO2006065649A1 (en) 2004-12-17 2006-06-22 Exxonmobil Chemical Patents Inc. Heterogeneous polymer blends and molded articles therefrom
JP2008524391A (en) 2004-12-17 2008-07-10 エクソンモービル・ケミカル・パテンツ・インク Films produced from polymer blends
EP1700895A1 (en) 2005-03-11 2006-09-13 National Starch and Chemical Investment Holding Corporation Peelable hot melt adhesive
US20060264557A1 (en) * 2005-05-17 2006-11-23 Arnold Lustiger In-line compounding and molding process for making fiber reinforced polypropylene composites
GB0511319D0 (en) 2005-06-03 2005-07-13 Exxonmobil Chem Patents Inc Polymeric compositions
GB0511320D0 (en) 2005-06-03 2005-07-13 Exxonmobil Chem Patents Inc Elastomeric structures
US7951872B2 (en) 2005-06-22 2011-05-31 Exxonmobil Chemical Patents Inc. Heterogeneous polymer blend with continuous elastomeric phase and process of making the same
WO2007011530A2 (en) 2005-07-15 2007-01-25 Exxonmobil Chemical Patents, Inc. Elastomeric compositions
WO2007084219A1 (en) 2006-01-17 2007-07-26 Exxonmobil Chemical Patents Inc. Process for making dynamically-loaded articles comprising propylene-based elastomers, composition for use in such processes, and article made using such processes
US7413784B2 (en) 2006-06-19 2008-08-19 Advanced Elastomer Systems, L.P. Thermoplastic vulcanizates for potable water applications
US8212098B2 (en) 2007-01-18 2012-07-03 Exxonmobil Research & Engineering Company HF alkylation process with internal acid regeneration
US7615589B2 (en) 2007-02-02 2009-11-10 Exxonmobil Chemical Patents Inc. Properties of peroxide-cured elastomer compositions
US20080234157A1 (en) 2007-03-20 2008-09-25 Yoon Beth A Alkylaromatic lubricant fluids
US7639915B2 (en) 2007-06-28 2009-12-29 Draka Comteq B.V. Optical fiber cable having a deformable coupling element
WO2009020706A1 (en) 2007-08-07 2009-02-12 Exxonmobil Chemical Patents Inc. Plasticized polyolefin compositions
US8013054B2 (en) 2008-08-08 2011-09-06 Exxonmobil Chemical Patents Inc. Elastomeric compositions having improved properties

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4132698A (en) * 1974-03-20 1979-01-02 Exxon Research & Engineering Co. Elastomeric thermoplastics
WO1998044041A1 (en) * 1997-04-02 1998-10-08 Upofloor Oy Plastic-based material
WO2003048252A1 (en) * 2001-12-05 2003-06-12 Dsm Ip Assets B.V. Thermoplastic elastomer with improved properties
US20040054040A1 (en) * 2002-08-12 2004-03-18 Lin Chon Yie Plasticized polyolefin compositions
US20040186214A1 (en) * 2002-08-12 2004-09-23 Wen Li Fibers and nonwovens from plasticized polyolefin compositions

Cited By (30)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2248853A1 (en) * 2006-08-16 2010-11-10 Dow Global Technologies Inc. Polymeric material and process for forming and using same
US8080607B2 (en) 2006-08-16 2011-12-20 Dow Global Technologies Llc Polymeric material and process for forming and using same
US8129465B2 (en) 2006-08-16 2012-03-06 Dow Global Technologies Llc Polymeric material and process for forming and using same
US7862671B2 (en) 2007-01-11 2011-01-04 Dow Global Technologies Inc. Welding of a polymeric material and structures formed thereby
CN101265349B (en) * 2008-04-10 2011-04-20 汕头市贝斯特科技有限公司 Inorganic anti-sticking master batch used for BOPP thin film and producing technique thereof
WO2010000792A1 (en) * 2008-07-03 2010-01-07 Total Petrochemicals Research Feluy Heterophasic propylene copolymer with improved properties for injection molding applications
EP2141200A1 (en) * 2008-07-03 2010-01-06 Total Petrochemicals Research Feluy Heterophasic propylene copolymer with improved properties for injection molding applications
US8529821B2 (en) 2009-01-30 2013-09-10 Dow Global Technologies Llc Polymeric compositions and filled TPO articles having improved aesthetics
RU2496807C2 (en) * 2009-06-22 2013-10-27 Бореалис Аг Mineral polypropylene compound with low content of volatile compounds
WO2010149549A1 (en) * 2009-06-22 2010-12-29 Borealis Ag Automotive interior article with reduced smell
RU2506288C2 (en) * 2009-06-22 2014-02-10 Бореалис Аг Article for car interior decoration having reduced odour
CN102803375A (en) * 2009-06-22 2012-11-28 北欧化工公司 Automotive Interior Article With Reduced Smell
EP2386602A1 (en) * 2010-04-20 2011-11-16 Borealis AG Automotive interior compound
WO2011131579A1 (en) * 2010-04-20 2011-10-27 Borealis Ag Automotive interior compound
US9206304B2 (en) 2010-04-20 2015-12-08 Borealis Ag Automotive interior compound
EP2551299B1 (en) 2011-07-27 2017-03-15 Borealis AG Lightweight polypropylene resin with superior surface characteristics for use in automotive interior applications
JP2013237784A (en) * 2012-05-15 2013-11-28 Bridgestone Corp Resin member for bicycle and child seat for bicycle
US10983452B2 (en) 2012-11-20 2021-04-20 Hp Indigo B.V. Methods of printing and electrostatic ink compositions
US9770738B2 (en) 2013-07-17 2017-09-26 Hewlett-Packard Indigo B.V. Method of producing an electrostatic ink composition
US11414526B2 (en) 2014-06-25 2022-08-16 Exxonmobil Chemical Patents Inc. High melt strength polypropylene and extrusion process for preserving melt strength
WO2016162359A1 (en) * 2015-04-10 2016-10-13 Borealis Ag Composition based on pp random copolymers and elastomers
WO2018019764A1 (en) * 2016-07-29 2018-02-01 Sabic Global Technologies B.V. Light diffusing article
CN109476892B (en) * 2016-08-03 2020-03-27 博里利斯股份公司 Fiber reinforced polypropylene composite
CN109476892A (en) * 2016-08-03 2019-03-15 博里利斯股份公司 Fibre-reinforced PP composite material
US10450452B2 (en) 2016-08-03 2019-10-22 Borealis Ag Fiber reinforced polypropylene composite
EA036419B1 (en) * 2016-08-03 2020-11-09 Бореалис Аг Process for preparation of composite for molded articles
WO2018024480A1 (en) * 2016-08-03 2018-02-08 Borealis Ag Fiber reinforced polypropylene composite
WO2018108932A1 (en) * 2016-12-12 2018-06-21 Sabic Global Technologies B.V. Composition comprising heterophasic propylene copolymer
EP3333222A1 (en) * 2016-12-12 2018-06-13 SABIC Global Technologies B.V. Composition comprising heterophasic propylene copolymer
US11603453B2 (en) 2016-12-12 2023-03-14 SABIC Global Technologies B.V Composition comprising heterophasic propylene copolymer

Also Published As

Publication number Publication date
AU2007285017C1 (en) 2010-12-16
KR20090029302A (en) 2009-03-20
AU2007285017B2 (en) 2010-06-24
KR101161914B1 (en) 2012-07-03
CN101511929A (en) 2009-08-19
MX2009001661A (en) 2009-04-16
BRPI0715067A2 (en) 2013-02-26
AU2007285017A1 (en) 2008-02-21
US8003725B2 (en) 2011-08-23
CA2660532A1 (en) 2008-02-21
JP5140670B2 (en) 2013-02-06
JP2010500468A (en) 2010-01-07
EP2052028A1 (en) 2009-04-29
CN101511929B (en) 2012-03-14
US20080045638A1 (en) 2008-02-21

Similar Documents

Publication Publication Date Title
AU2007285017C1 (en) Plasticized hetero-phase polyolefin blends
US7652092B2 (en) Articles from plasticized thermoplastic polyolefin compositions
EP2013282B1 (en) Articles from plasticized thermoplastic polylefin compositions
US8389615B2 (en) Elastomeric compositions comprising vinylaromatic block copolymer, polypropylene, plastomer, and low molecular weight polyolefin
US8513347B2 (en) Elastomeric compositions
CA2693908C (en) Plasticized polyolefin compositions
US7759415B2 (en) Method to make an article comprising polymer concentrate
CA2495019C (en) Plasticized polyolefin compositions
US8476360B2 (en) Calendered films of plasticized blends of plastomer and impact copolymer
JP2013035889A (en) Thermoplastic elastomer composition and air bag housing cover
EP3487927B1 (en) Stiff propylene composition with good dimensional stability and excellent surface appearance
KR101008821B1 (en) Plasticized polyolefin compositions

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200780033057.X

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 07810207

Country of ref document: EP

Kind code of ref document: A1

WWE Wipo information: entry into national phase

Ref document number: 482/DELNP/2009

Country of ref document: IN

WWE Wipo information: entry into national phase

Ref document number: 2007285017

Country of ref document: AU

WWE Wipo information: entry into national phase

Ref document number: 2660532

Country of ref document: CA

WWE Wipo information: entry into national phase

Ref document number: 1020097002949

Country of ref document: KR

Ref document number: MX/A/2009/001661

Country of ref document: MX

WWE Wipo information: entry into national phase

Ref document number: 2009524596

Country of ref document: JP

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 2007285017

Country of ref document: AU

Date of ref document: 20070705

Kind code of ref document: A

WWE Wipo information: entry into national phase

Ref document number: 2007810207

Country of ref document: EP

NENP Non-entry into the national phase

Ref country code: RU

ENP Entry into the national phase

Ref document number: PI0715067

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20090203