CN102971454A - Nonwoven fabrics made from polymer blends and methods for making same - Google Patents
Nonwoven fabrics made from polymer blends and methods for making same Download PDFInfo
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- CN102971454A CN102971454A CN2011800290418A CN201180029041A CN102971454A CN 102971454 A CN102971454 A CN 102971454A CN 2011800290418 A CN2011800290418 A CN 2011800290418A CN 201180029041 A CN201180029041 A CN 201180029041A CN 102971454 A CN102971454 A CN 102971454A
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- propylene
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/44—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds
- D01F6/46—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds as major constituent with other polymers or low-molecular-weight compounds of polyolefins
-
- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
- D01D5/00—Formation of filaments, threads, or the like
- D01D5/08—Melt spinning methods
- D01D5/098—Melt spinning methods with simultaneous stretching
- D01D5/0985—Melt spinning methods with simultaneous stretching by means of a flowing gas (e.g. melt-blowing)
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/541—Composite fibres, e.g. sheath-core, sea-island or side-by-side; Mixed fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/54—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving
- D04H1/56—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties by welding together the fibres, e.g. by partially melting or dissolving in association with fibre formation, e.g. immediately following extrusion of staple fibres
-
- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H13/00—Other non-woven fabrics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/60—Nonwoven fabric [i.e., nonwoven strand or fiber material]
- Y10T442/697—Containing at least two chemically different strand or fiber materials
Abstract
The present invention is directed to fabrics formed from the polymer blends. The polymer blends comprise from about 70 to about 99.9 wt%, based on the total weight of the composition, of a first propylene -based polymer and from about 0.1 to about 30 wt% of a second propylene based polymer. The first polymer has a melt flow rate of from about 100 to about 5,000 g/10 min, and the second polymer has a melt flow rate of from about 1 to about 500 g/min, and the second polymer has either a lower melt flow rate or a higher triad tacticity than the first polymer.
Description
Prioity claim
The application requires in the priority of the U.S. Provisional Application sequence number 61/354,882 of submission on June 15th, 2010, and the disclosure of described document is incorporated herein for reference fully.
Technical field
The application relates to supatex fabric and the manufacture method thereof of being made by blend polymer.
Background technology
Polyacrylic polymer and blend polymer are made with their in the art and are are non-wovenly melted and sprayed the application of fabric and be celebrated.This kind fabric has various application, for example is used for medical treatment and health product, clothes, filter medium and g. absorbent products, comprises designing those that are used for absorbing water, oil and other chemical substance.The importance of these fabrics in absorbent is used, is the bulkiness of described fabric especially, or the thickness under specific basic weight (basis weight), and wherein higher bulkiness is more desirable.The fabric that has minimum binding (that is, poor fiber separation) and take off fibre (linting) also is desirable.
Before this, this type of supatex fabric based on propylene is to use the polypropylene GRANULES that scribbles peroxide of ziegler-natta catalyzed to prepare with meltblowing method.The interpolation of peroxide is used for the acrylic polymers visbreaking, causes using desirable higher melt flow rate (MFR) and narrower molecular weight distribution for melting and spraying.Yet this type of peroxide coating also has shortcoming, for example increase of the complexity of meltblowing method and expense and form decomposition by-products, and this is to add peroxide be undesirable.
The polymer based on propylene of metallocene catalyst also is known in the art and has been used to form meltblown fabric.Referring to, for example, U.S. Patent number 6,010,588,7,081,299 and 7,319,122, they are incorporated herein for reference.Although prepared the polymer based on propylene with high melt flow rate (MFR) and Narrow Molecular Weight Distribution with this type of single-site catalysts, thereby have the advantage that does not require reactor post processing (post reactor treatment) (for example peroxide coating), but those polymer do not cause fabric to show that some absorbent and other use desirable bulkiness and anti-binding (resistance to roping).A kind of possible method that improves the fabric bulkiness is to make the water quenching with the fused fiber cooling with fabric.Yet this also is undesirable, because the high-caliber water quenching that produces gratifying bulkiness and sometimes need causes the residual water of excessive level in the fabric.
Therefore, exploitation preparation has high bulkiness and anti-binding and does not require the reactor post processing and make the polymer composition based on propylene of the minimized meltblown fabric of water quenching will be desirable.The present invention is by reaching these targets with a small amount of polymer based on propylene that has than low melt flow speed or higher level isotacticity with the polyblend based on propylene with metallocene catalyst of high melt flow rate (MFR).Have high loft and good anti-binding and take off fibre and low-level residual moisture by the supatex fabric of blend polymer of the present invention preparation.
Summary of the invention
Summary of the invention
The present invention relates to the blend polymer for nonwoven fabric applications, the fabric that is formed by described blend polymer and this kind fabric form method.In one or more embodiments, described blend polymer comprises the about 99.9wt% first of about 70-based on the polymer and the polymer of about about 30wt% second of 0.1-based on propylene of propylene, based on the gross weight of described composition.It is about 5 that described the first polymer has about 100-, the melt flow rate (MFR) of 000g/10min, and described the second polymer has the melt flow rate (MFR) of the about 500g/min of about 1-.In various embodiments, the MFR of described the first polymer can be higher than the MFR of described the second polymer and/or three unit group steric regularities (for example, degree of crystallinity) of described the second polymer can be higher than described the first polymer.In one embodiment, described the second polymer has three unit group steric regularities greater than about 0.94.In addition, the supatex fabric that is formed by blend polymer of the present invention, especially the melt-blown non-woven fabric provides the advantage with the polymer of metalloscene catalyst preparation, keep simultaneously with by based on the fabric of the polymers manufacturing of Z-N suitable bulkiness and anti-fibre or the binding property of taking off.These fabrics also have the low-level residual moisture that is caused by their manufacturing and are suitable for many commercial application, comprise absorbent article.In some applications, low-level " flash of light (shot) " and high liquid barrier performance are desirable.High MFR reduces " flash of light " and/or improves the obstruct resistance based on the blend based on the polymer of propylene based on the polymer of propylene and low MFR or higher crystallinity of metallocene, especially to the obstruct resistance of water fluid.
Detailed Description Of The Invention
Supatex fabric of the present invention be by comprise the about 99.9wt% of about 70-first based on the polymer of propylene and approximately the second blend polymer based on the polymer of propylene of the about 30wt% of 0.1-form, gross weight based on described composition, wherein said the first polymer has about 100-about 5, the melt flow rate (MFR) of 000g/10min, described the second polymer have the melt flow rate (MFR) of the about 500g/min of about 1-and than the lower melt flow rate (MFR) of described the first polymer or three higher unit group steric regularities.In one embodiment, described the second polymer has three unit group steric regularities greater than about 0.94.In one or more embodiments, described the first polymer is to use the catalyst system that comprises metalloscene catalyst to prepare.In identical or other embodiment, described the first polymer is reactor grade polymer (reactor grade polymer).
The invention still further relates to the formation method of the supatex fabric that comprises blend polymer described herein.In one or more embodiments, such method may further comprise the steps: form molten polymer composition, use meltblowing method to form the fiber that comprises described polymer composition, and form fabric by described fiber.The use that described molten polymer composition comprises the about 99.9wt% of about 70-comprises the catalyst system preparation of metalloscene catalyst and has about 100-about 5, the first polymer based on propylene of the melt flow rate (MFR) of 000g/10min, with the about 30wt% of about 0.1-have more low melt flow speed and/or more Senior Three unit group steric regularity is (namely, degree of crystallinity) the second polymer based on propylene is based on the gross weight of described composition.In one embodiment, the about melt flow rate (MFR) of the about 500g/10min of 1-and/or greater than about 0.94 three unit group steric regularities.
Term as used herein " copolymer " is intended to comprise to have two or more monomers, randomly also has the polymer of other monomer, and can refer to interpretation, terpolymer etc.Term as used herein " polymer " includes, but not limited to homopolymers, copolymer, terpolymer etc. and their alloy and blend.Term as used herein " polymer " also comprises anti-impact, block, grafting, random and alternate copolymer.Term " polymer " also should comprise all possible geometric configuration, unless specify in addition.Described configuration can comprise isotaxy, syndiotaxy and atactic symmetries.Term as used herein " blend " refers to the mixture of two or more polymer.
Term as used herein " monomer " or " comonomer " can refer to form the monomer of polymer, the unreacted chemical compound that namely is polymerization form before, and can refer to such monomer, i.e. after it has been attached in the polymer (this paper is also referred to as " [monomer]-derive unit ") is because polymerisation has usually than its still less hydrogen atom before polymerisation.This paper has discussed different monomers, comprises propylene monomer, vinyl monomer and diene monomers.
In some embodiments of the present invention, described first and second comprise polypropylene based in the polymer of propylene each.This paper employed " polypropylene " comprises homopolymers and copolymer or their mixture of propylene.Comprise that the product with one or more propylene monomers of one or more additional monomer polymerizations can more generally be called random copolymer (RCP) or impact copolymer (ICP).Impact copolymer also is called heterophasic copolymer in the art.This paper employed " based on propylene " is intended to comprise the unit that only comprises propylene derived or comprises any polymer with the unit of the propylene derived of one or more comonomer incorporation, wherein the unit of propylene derived is key component (that is, greater than the 50wt% propylene).
The first polymer based on propylene
The blend polymer that is used to form supatex fabric of the present invention comprises the first polymer based on propylene.In one or more embodiments, the described first polymer based on propylene is the reactor grade propylene polymer that uses the catalyst system preparation that comprises Metallocenic compound.So-called " reactor grade " refers to after polymerization not through chemistry or mechanical treatment so that changes the polymer of mean molecule quantity, molecular weight distribution or the viscosity of polymer.From those polymer that are described as the reactor grade especially get rid of be peroxide apply those.
The described first polymer based on propylene can be the homopolymers of unit of propylene derived or unit and one or more comonomers (for example, C of propylene derived
2And/or C
4-C
16Alpha-olefin derived unit) copolymer.When the first polymer is copolymer, co-monomer content can be the about 25wt% of about 0.01-, or the about about 20wt% of 0.1-, or the about about 15wt% of 1-, or the about about 10wt% of 1-, based on the weight of described the first polymer.In a preferred embodiment, the first polymer is Noblen (that is, polypropylene homopolymer).
In one embodiment, the first polymer mainly is crystallization, refers to that it has greater than about 110 ℃, or greater than about 115 ℃, or greater than about 130 ℃ melt temperature.Term as used herein " crystallization " refer to have by differential scanning calorimetry (DSC) with 10 ℃/minute the rate of heat addition measure greater than about 60J/g, or greater than about 70J/g, or greater than about those polymer of the melting heat of 80J/g.
Can following measurement crystallization temperature (Tc), melt temperature (Tm) and melting heat (Hf).For example, polymer or the plasticized polymer sheet material with about 6-10mg takes out in about 150 ℃-200 ℃ lower compactings and with punch die.Described sample placed differential scanning calorimetry (DSC) (Perkin Elmer 7Series Thermal Analysis System) and be heated to 200 ℃ and kept 10 minutes.With 10 ℃/min sample is cooled off to reach 25 ℃ final temperature.Record thermal output and by with the flex point in the electronics mode differentiation thermal output data determination thermal output data change of thermal capacity (indication).Maximum in the differential thermal output data is corresponding to the crystallization temperature of sample.Described sample is remained on 25 ℃ times lasting 10 minutes and is heated to 200 ℃ with 10 ℃/min.Record heat is inputted and is passed through with the flex point (indicating the change of thermal capacity) in the electronics mode differential heat-transmission input data determination heat input data.Maximum in the differential heat input data is corresponding to the melt temperature of sample.Measure the area below the sample melted peak (usually being present between about 0 ℃ and about 200 ℃) and be the measuring of Hf of polymer with joule.
In one or more embodiments, it is about 5 that the described first polymer based on propylene has the about 100-that measures by ASTM D-1238, the melt flow rate (MFR) of 000g/10min, or " MFR " (2.16kg, 230 ℃).In other embodiments, it is about 4 that described the first polymer can have about 350-, 000g/10min, or approximately 500-is about 3, and 000g/10min, or approximately 750-is about 2,500g/10min, or about 1,000-is about 2, the MFR of 000g/10min.
In various embodiments, the described first polymer based on propylene has less than about 0.96, or less than about 0.95, or less than about 0.94 three unit group steric regularities.
In one or more embodiments, it is about 40 that the first polymer based on propylene can have, the weight average molecular weight (Mw) of 000-about 125,000.In identical or other embodiment, it is about 10 that the first polymer can have, the number-average molecular weight (Mn) of 000-about 60,000.It is about 4.0 that the first polymer can also have about 1.0-, or approximately 1.5-is about 3.5, or the about molecular weight distribution (Mw/Mn, or " MWD ") of 2.0-about 3.0.The technology of determining molecular weight (Mn and Mw) and molecular weight distribution (MWD) is referring to U.S. Patent number 4,540,753 (they are incorporated herein for the U.S. and put into practice the purpose reference) and the list of references of wherein quoting, and Macromolecules, 1988, the 21st volume, 3360 pages (they are incorporated herein for the U.S. and put into practice the purpose reference) and the list of references of wherein quoting.
The first polymer based on propylene is to use the catalyst system that comprises metalloscene catalyst to prepare.In one or more embodiments, catalyst system comprises at least a metallocene, preferably uses porous prilled material load, and at least a activator.Described catalyst system can also comprise one or more co-catalysts.
This paper employed " metallocene " typically refers to by formula Cp
mMR
nX
qThe compound of expression, wherein Cp is can substituted cyclopentadienyl rings, or it can substituted derivative, M is the 4th, 5 or 6 group 4 transition metals, for example titanium (Ti), zirconium (Zr), hafnium (Hf), vanadium (V), niobium (Nb), tantalum (Ta), chromium (Cr), molybdenum (Mo) or tungsten (W), R is alkyl or the hydrocarboxyl group that contains 1-20 carbon atom, X is halogen or hydrogen, m=1-3, n=0-3, q=0-3, and the m+n+q sum equals the oxidation state of described transition metal.
The preparation and application of metallocene is disclosed in for example U.S. Patent number 4,530,914; 4,542,199; 4,769,910; 4,808,561; 4,871,705; 4,933,403; 4,937,299; 5,017,714; 5,026,798; 5,057,475; 5,120,867; 5,278,119; 5,304,614; 5,324,800; 5,350,723; In 6,143,686 and 5,391,790.
Selecting the metallocene components for catalyst system of the present invention is such metallocene, namely when using separately, prepare isotaxy, crystalline propene polymer, and when being combined with other metallocene, prepare the polymer that has for the desirable attribute of application-specific of considering.Be suitable for preparing the first metallocene catalyst components based on the polymer of propylene and comprise U.S. Patent number 6,143,686; 5,145,819; 5,243,001; 5,239,022; 5,329,033; 5,296,434; 5,276,208 and 5,374,752; With describe in EP 549 900 and 576 970 those.
Metallocene generally is combined with in order to produce active catalyst system with the activator of certain form.It is can improve one or more metallocenes olefinic polymerization is become any compound or the component of polyolefinic ability or the combination of compound or component that term " activator " is defined as at this paper.
In one embodiment, the ionization activator is used for metallocene is activated.These activators can be " nonionic " or " ion " (being also referred to as non-coordination anion activator or NCA activator).Described ion activation agent is for example four (pentafluorophenyl group) boron three (normal-butyl) ammonium of compound, and it makes the ionization of neutral metal cyclopentadinyl compound.This type of ionization compound can contain active proton, or some other and the residual ion of described ionization compound associate but not coordination or the CATION of loose association only.Can also use the combination of activator, for example, the aikyiaiurnirsoxan beta of combination and ionization activator, those that for example describe among the WO 94/07928.The nonionic activator precursor that can serve as the NCA activator is the strong lewis acid with non-hydrolysable part, at least one is electrophilic in the described part, for example knownly extract those lewis acids of anionic moiety, for example three (perfluorophenyl) boron, three (perfluor naphthyl) boron or three (perfluorinated biphenyl) boron and other highly fluorinated triarylboron from dimethyl zirconocene (the dimethyl bicyclic pentadiene closes zirconium).
Term " non-coordination anion " describe be not coordinated in cationic metal luxuriant or only a little less than be coordinated in described CATION, thereby keep being enough to the anion of the labile state of being replaced by neutral Lewis base." compatible " non-coordination anion is not to be degraded to neutral those when the initial complex compound that forms decomposes.In addition, described anion is not transferred to CATION with anion substituent or fragment, makes it form neutral four-coordination Metallocenic compound and from the neutral accessory substance of described anion.Non-coordination anion that can be used according to the invention is those such anion, they are compatible and with its charge balancing ion luxuriant CATION of stable metal on the meaning under+1 state, still keep enough unstability to allow in polymerization process by olefinic or the displacement of acetylene series unsaturated monomer.
The catalyst system that is used for preparing polymer described herein preferably uses porous prilled material load, for example for example polyolefin or other polymerizable compound of talcum, inorganic oxide, butter and resin material.Especially, catalyst system is normally by allowing at least metallocene components, activator component and carrier component contact the composition of gained.
Desirable carrier material is the porous inorganic oxide material, and they comprise those of the oxide that is selected from the periodic table of elements the 2nd, 3,4,5,13 or 14 family's metals.Silica, aluminium oxide, silica-alumina and their mixture especially are fit to.Other inorganic oxide that can use individually or be combined with silica, aluminium oxide or silica-alumina is magnesia, titanium dioxide, zirconia etc.
Be suitable for Metallocenic compound of the present invention, and the more detailed description of activator, carrier material and overall catalyst system is referring to U.S. Patent number 7,081,299, described document is incorporated herein by reference in full.In some embodiments of the present invention, being used for preparing the first metallocene based on the polymer of propylene is silicon dioxide carried bridging 2, the 4-phenyl indenyl metallocene of the dibasic indenyl metallocenes of 4-or bridging.
The load type catalyst system of describing in the document of this paper and reference can be used for any suitable polymerization technique.The method and apparatus that carries out these polymerisations is known.Described loaded catalyst activator can and use under condition of similarity by the amount similar to known olefinic polymerization catalyst.
Term as used herein " polymerization " comprises copolymerization and ternary polymerization, term " alkene " and " olefinic type monomers " comprise alpha-olefin, alkadienes, distortion cyclic olefin (strained cyclicolefin), styrene monomer, acetylene series unsaturated monomer, cyclic olefin, use in combination individually or with other unsaturated monomer.The metallocene supported catalyst compositions can be used for usually known can be under the coordination polymerization condition coordination polymerization of the unsaturated monomer of polymerization.The monomer that is suitable for polymer of the present invention comprises propylene and C
2And/or C
4-C
10Alpha-olefin.Polymerizing condition also be know and comprise polymerisation in solution, slurry polymerization and low-pressure vapor phase polymerization.Thereby carried type metallocene catalyst composition described herein especially can be by the known operation pattern using of fixed bed, moving bed, fluid bed or the slurry process of carrying out in single, serial or parallel connection reactor.
The polymerization technique that is used for olefinic polymerization can comprise polymerisation in solution, slurry polymerization or gas-phase polymerization technology.The method and apparatus of implementing these polymerisations be know and for example be described in, 12ENCYCLOPEDIA OF POLYMER SCIENCE AND ENGINEERING 504 541 (JohnWiley and Sons, 1988) and among the 2 METALLOCENE-BASED POLYOLEFINS 366378 (John Wiley and Sons, 2000).
Polymer of the present invention can prepare in intermittence, semicontinuous or continuous propylene polymerization system with described catalyst.Desirable polymerization system is continuation method, comprises diluent slurry, bulk slurry (endless tube and stirred tank) and gas phase (stirring and fluid bed).Continuous polymerization can in the single reactor of any the above-mentioned type, in two or more reactors of serial operation, or be carried out in two or more reactors of parallel operation.When operating two or more reactors by continuation method, described a plurality of reactors can all have same type or they can be any combinations of described type.
Hydrogen is generally used for olefinic polymerization to control polyolefinic final performance, and is for example such described in the POLYPROPYLENE HANDBOOK 76 78 (Hanser Publishers, 1996).Use this paper catalyst system, well-known, the hydrogen of higher concentration (dividing potential drop) improves the polyolefin, particularly polyacrylic melt flow rate (MFR) (MFR) that produces.Therefore MFR can be affected by density of hydrogen, and this affects again best fiber fabrication process temperature.Usually, polyacrylic MFR is higher, then can obtain thinner fiber and more uniform coverage in fabric.In addition, the resin of higher MFR can be processed under lower temperature.Affected by density of hydrogen between polymerization period or the final MFR of polymer by the final mass of the fabric of the fiber manufacturing that comprises polymer described herein.
Polyacrylic polymer by above-mentioned catalyst system and method manufacturing has improved performance.Described polypropylene is isotactic by the height that the meso running length (a meso run length) of polypropylene chains is measured often, keeps than Narrow Molecular Weight Distribution simultaneously.Isotactic polypropylene is those polymer of side alkyl space ordering on the same side of main polymer chain or plane of wherein polymer chain.Use isotactic polypropylene as an example, isotactic structure is described as having pending methyl group usually, described pending methyl group be connected at ternary (ternary) carbon atom through the continuous monomeric unit on the same side on the supposition plane of polymer carbon backbone chain, as shown below:
The degree of isotacticity can be passed through the NMR commercial measurement, and the typical nomenclature of isotaxy five unit groups is " mmmm ", wherein " meso " the two unit groups on the same side or continuous methyl in each described plane of " m " expression.Oppositely the single insertion of configuration produces rr three unit groups as follows:
As be known in the art, any skew of the regularity of polymer architecture or upset reduce the isotacticity degree and therefore reduce the degree of crystallinity that described polymer can have.Ideally, described mmmm stroke or meso running length are longer, then polypropylene isotaxy more highly.When wishing isotachyte, defective and counter-rotating for example 1, it is undesirable that 3-or 2,1-insert.
In some embodiments, the of the present invention first polymer based on propylene can have less than 50 three-dimensional defectives (stereo defect)/1000 unit, or less than a unit, 25 three-dimensional defective/1000, or less than a unit, 100 three-dimensional defective/10,000, or less than 80 three-dimensional defective/10,000 unit, and greater than 50, or greater than 75, or in another embodiment, greater than 100 by
13The meso running length (MRL) of C NMR indication.
Be suitable for comprising Achieve as the first exemplary commercial polymer based on the polymer of propylene
TMAcrylic polymers can obtain from ExxonMobil Chemical Company, and Metocene
TMAnd Moplen
TMAcrylic polymers can obtain from LyondellBasell.
The second polymer based on propylene
The blend polymer that is used to form supatex fabric of the present invention comprises the second polymer based on propylene.The described second polymer based on propylene can be homopolymers or propylene and one or more C of propylene
2And/or C
4-C
10The copolymer of alpha-olefin.
The described second polymer main difference based on propylene is that in the described first polymer based on propylene it has than top lower MFR to described the first polymer description or higher degree of crystallinity.In one or more embodiments of this paper, the described second polymer based on propylene has the (2.16kg by ASTM D-1238,230 ℃) the about 500g/10min of about 0.1-that measures, or about about 250g/10min of 1-, or about about 150g/10min of 5-, or about about 100g/10min of 10-, or the MFR of about about 75g/10min of 10-.
In other embodiment of this paper, the described second polymer based on propylene can have similar based on the polymer of propylene to described first, or even higher MFR, but have than described first based on the higher degree of crystallinity of the polymer of propylene.Degree of crystallinity reflects in the isotacticity level of polymer, and in these embodiments, and three unit group steric regularities of described the second polymer are greater than about 0.94, or greater than about 0.95, or greater than about 0.96." the three unit group steric regularities " of the employed polymer of this paper is the relative steric regularity of two adjacent propylene units sequences (by the chain that bonding end to end forms, being expressed as the binary combination of m and r sequence).It is typically expressed as in the unit number of specific steric regularity and the copolymer all ratios of propylene three unit groups.Three unit group steric regularities (mmmm mark) of propylene copolymer can be passed through propylene copolymer
13C-NMR spectrum and following formula are measured:
Mm mark=PPP (mm)/(PPP (mm)+PPP (mr)+PPP (rr))
The peak area of being derived by the methyl of second unit in three propylene units chains that wherein formed by head-to-tail bond below PPP (mm), PPP (mr) and PPP (rr) expression:
Propylene copolymer
13C NMR spectrum is measured described in 172 like that such as U.S. Patent number 5,504.The frequency spectrum relevant with methyl carbon zone (1,000,000/19-23 part (ppm)) can be divided into first area (21.2-21.9ppm), second area (20.3-21.0ppm) and the 3rd zone (19.5-20.3ppm).Each peak in described spectrum is with reference to periodical Polymer, the 30th volume (1989), and the article in the 1350th page belongs to.In the first area, in three propylene units chains by the methyl resonance of second unit of PPP (mm) representative.In second area, by the methyl resonance of second unit of PPP (mr) representative, and adjacent cells is near methyl (PPE-methyl) resonance (20.7ppm) of the propylene units of propylene units and ethylene unit in three propylene units chains.In the 3rd zone, by the methyl resonance of second unit of PPP (rr) representative, and adjacent cells is near methyl (EPE-methyl) resonance (19.8ppm) of the propylene units of ethylene unit in three propylene units chains.The computational methods of three unit group steric regularities are summarised in U.S. Patent number 5,504, in the technology shown in 172.The deduction propylene inserts (2 from the total peak area in second area and the 3rd zone, 1-and 1,3-inserts two kinds) the error peak area, then obtain the peak area take 3 propylene units that formed by head-to-tail bond-chain (PPP (mr) and PPP (rr)) as benchmark.Therefore, the peak area of PPP (mm), PPP (mr) and PPP (rr) can be estimated, three unit group steric regularities of the propylene units chain that is formed by head-to-tail bond can be measured thus.
In one or more embodiments here, the second polymer can comprise a small amount of comonomer, so that the second polymer can be polyacrylic random copolymer (RCP) or impact copolymer (ICP).Exemplary RCP comprises the about 8wt% comonomer of about 1-usually, or about about 5wt% comonomer of 2-.In one or more embodiments, the RCP comonomer is ethene.
In some embodiments of the present invention, the second polymer is the copolymer of one or more comonomers of propylene and about about 25wt% of 0.1-.Comonomer can be straight or branched.In one or more embodiments, the straight chain comonomer can comprise ethene and/or C
4-C
10Alpha-olefin includes but not limited to butylene, hexene and octene.The side chain comonomer can comprise 4-methyl-1-pentene, 3-Methyl-1-pentene and 3,5,5-trimethyl-1-hexene.In one or more embodiments, comonomer can comprise styrene.
In some embodiments, the second polymer is the copolymer (and also can comprise other comonomer) of propylene and ethene.For example, described the second polymer can comprise the unit of the about 99wt% derived from propylene of about 75-and the unit of about about 25wt% derived from ethylene of 1-.In some embodiments, described the second polymer can comprise the unit of the about 25wt% ethylene derivative of about 2-, or the unit of about about 18wt% ethylene derivative of 3-, or the unit of about about 10wt% ethylene derivative of 5-.
Randomly, the second polymer can also comprise one or more diene.Term " diene " is defined as the hydrocarbon compound with two unsaturated sites,, has the compound of two two keys that connect carbon atom that is.Depend on context, term " diene " refers to the diene monomers before polymerization widely, for example, forms the part of polymerisation medium, or the diene monomers after polymerization begins (being also referred to as the unit that diene monomers unit or diene are derived).Being suitable for exemplary diene of the present invention comprises, but be not limited to, butadiene, pentadiene, hexadiene (for example 1, the 4-hexadiene), heptadiene (for example 1, the 6-heptadiene), octadiene (for example 1, the 7-octadiene), nonadiene (for example 1, the 8-nonadiene), decadinene (for example 1, the 9-decadinene), 11 carbon diene (for example 1,10-11 carbon diene), 12 carbon diene (for example 1,11-12 carbon diene), oleatridecadiene (for example 1, the 12-oleatridecadiene), 14 carbon diene (for example 1,13-14 carbon diene), 15 carbon diene, 16 carbon diene, 17 carbon diene, 18 carbon diene, 19 carbon diene, 20 carbon diene, 21 carbon diene, 22 carbon diene, two oleatridecadienes, the tetracosa carbon diene, 25 carbon diene, 26 carbon diene, heptacosadiene, 28 carbon diene, 29 carbon diene, 30 carbon diene and the polybutadiene with the molecular weight (Mw) less than 1000g/mol.The example of straight chain acyclic dienes includes, but are not limited to Isosorbide-5-Nitrae-hexadiene and 1,6-octadiene.The example of side chain acyclic dienes includes, but are not limited to the 5-methyl isophthalic acid, 4-hexadiene, 3,7-dimethyl-1,6-octadiene and 3,7-dimethyl-1,7-octadiene.The example of the alicyclic diene of monocycle includes, but are not limited to Isosorbide-5-Nitrae-cyclohexadiene, 1, and 5-cyclo-octadiene and 1,7-encircle 12 carbon diene.The example that many rings are alicyclic to be condensed with the bridging cyclic diolefine includes, but are not limited to tetrahydroindene; Norbornadiene; The methyl tetrahydroindene; Dicyclopentadiene; Dicyclo (2.2.1) heptan-2, the 5-diene; And thiazolinyl-, alkylidene radical, cycloalkenyl group and ring alkylidene radical ENB [comprising, for example 5-methylene-2-ENB, 5-ethidine-2-ENB, 5-propenyl-2-ENB, 5-isopropylidene-2-ENB, 5-(4-cyclopentenyl)-2-ENB, 5-cyclohexylidene base-2-ENB and 5-vinyl-2-ENB].The example of the alkene that cycloalkenyl group replaces includes, but are not limited to vinyl cyclohexene, allyl cyclohexene, vinyl cyclo-octene, 4 vinyl cyclohexene, allyl cyclodecene, vinyl cyclododecene and Fourth Ring 12 carbon diene.In some embodiments of the present invention, diene is selected from 5-ethidine-2-ENB (ENB); Isosorbide-5-Nitrae-hexadiene; 5-methylene-2-ENB (MNB); 1,6-octadiene; The 5-methyl isophthalic acid, the 4-hexadiene; 3,7-dimethyl-1, the 6-octadiene; 1,3-cyclopentadiene; Isosorbide-5-Nitrae-cyclohexadiene; Vinyl norbornene (VNB); Bicyclopentadiene (DCPD) and their combination.In one or more embodiments, diene is ENB.
When having one or more diene, the second polymer can comprise the unit that the about 6wt% diene of 0.05-is derived.In other embodiments, the second polymer comprises the unit that the about 5.0wt% diene of about 0.1-is derived, or the about about 3.0wt% diene of the 0.1-unit of deriving, or the about about 1.0wt% diene of the 0.1-unit of deriving.
In one or more embodiments, described the second polymer can have according to above-mentioned DSC program determination more than or equal to about 0.5 joule/gram (J/g), and be less than or equal to about 80J/g, or be less than or equal to about 75J/g, or be less than or equal to about 70J/g, or be less than or equal to about 60J/g or be less than or equal to the melting heat (Hf) of about 50J/g.In other embodiment of this paper, the second polymer can have greater than about 80J/g, or greater than about 90J/g, or greater than the melting heat of 100J/g.
The first and second polymer can have identical or different fusing point.In some embodiments, the fusing point of described the second polymer can be less than the fusing point of described the first polymer, for example less than 100 ℃, or less than 90 ℃, or be less than or equal to 80, or be less than or equal to 75 ℃.In other embodiments, described the second polymer has than the higher fusing point of described the first polymer, for example greater than 110 ℃, or greater than 120 ℃, or greater than 130 ℃.In some embodiment of this paper, described the first and second polymer all have greater than about 110 ℃ fusing point, and the fusing point of described the second polymer than the fusing point of described the first polymer about greatly at least 5 ℃.
Described the second polymer can further have 75% or larger, 80% or larger, and 82% or larger, 85% or larger or 90% or larger passing through
13Three unit group steric regularities of three propylene units that C NMR measures.In some embodiments, three unit group steric regularities of described the second polymer are that about 50-is about 99%, or approximately 60-is about 99%, or approximately 75-is about 99%, or approximately 80-is about 99%, or about 60-about 97%.Three unit group steric regularities are measured by the method for describing in the U.S. Patent Application Publication 2004/0236042, and described document is incorporated herein for reference.
In various embodiments, the described second polymer based on propylene has than described first based on the higher melt temperature of the polymer of propylene (Tm).For example, in one embodiment, the described first polymer based on propylene has about 153-155 ℃ melt temperature and described the second polymer and has Tm 〉=156 ℃.The described second polymer based on propylene can use metallocene catalyst system such as toply prepare as described in the first polymer.Perhaps, described the second polymer can use and be known in the art any other catalyst that produces the polymer with characteristic described herein, preparations such as other single-site catalysts, Ziegler-Natta catalyst.In some embodiment of this paper, use Ziegler-Natta catalyst to prepare the second polymer.
Be suitable as the second exemplary commercial polymer based on the polymer of propylene and comprise the Achieve that can obtain from ExxonMobil Chemical Company
TMAnd ExxonMobil
TMAcrylic polymers is (such as but not limited to PP3155E1, PP3155E3, PP3885, PP3864F5, PP3325E1, PP3374E3 and Achieve
TM3854) and Vistamaxx
TMElastomer can be from the Versify of Dow Chemical Company acquisition
TMPolymer, with Moplen HP561R, Moplen HP566R, the Moplen HP462R that can obtain from LyondellBasell, can be from PPH9099 and the PPH9020 of Totalfina acquisition, can be from the HG455FB of Borealis acquisition, can be from the HG3600 of Arco acquisition, the DR7052.01 that can obtain from Dow, the 201-CA25 that can obtain from Ineos and the PP512P that can obtain from Sabic.
Supatex fabric
Supatex fabric of the present invention is to be formed by the described herein first and second blends based on the polymer of propylene.In certain embodiments of the invention, described fabric can comprise the about 99.9wt% of about 70wt%-, or about about 99wt% of 75wt%-, or about about 98wt% of 80wt%-, or described the first polymer of about about 95wt% of 85wt%-and about about 30wt% of 0.1wt%-, or about about 25wt% of 1wt%-, or about about 20wt% of 2wt%-, or described the second polymer of about about 15wt% of 5wt%-.
In one embodiment, the polymer composition that is used to form described supatex fabric is comprised of the described first polymer and the described second polymer based on propylene based on propylene basically.This paper employed " basically being comprised of the described first polymer and the described second polymer based on propylene based on propylene " refers to that described supatex fabric comprises other component that is less than 2wt%, based on the gross weight of described polymer composition.
The present invention not only relates to supatex fabric, and relates to the method that forms the supatex fabric that comprises blend polymer described herein.In one or more embodiments, these methods may further comprise the steps: form and to comprise described first based on the polymer of propylene and the described second molten polymer composition based on the polymer of propylene, form and comprise the fiber of described polymer composition and form fabric by described fiber.
Method is with described the first and second polyblends behind any reactor of dense mixture that can be by guaranteeing each component.The blend of polymer and homogenizing are well known in the art and comprise list and twin-screw mixing extruder, the static mixer that mixes low viscous melt polymerization material stream, hit the stream blender, and design is used for disperseing in the close contact mode other machine and the method for described the first and second polymer.For example, can be by melt blended or dry blend with continuous or discontinuous method polymer blend component and other accessory constituent.These methods are commonly known in the art and comprise single screw rod and twin screw compounding extruder and design are used for other machine and the method for closely melting and homogenising polymer component.Melt blended or compounding extrusion machine usually is equipped with granulating head and changes into pellet form with the polymer with homogenizing.Then described homogenizing pellet can be supplied with fiber extruder or nonwovens process equipment with preparation fiber or fabric.Perhaps, can be with the extruder of the dry blend of described the first and second polymer and supply nonwovens process equipment.
The blend that also can prepare by current known any reactor blending method in the art described the first and second polymer.Reactor blend is because the high degree of dispersion of the polymer of the sequential polymerization of one or more monomers and original position preparation and the blend that can not machinery separates, and wherein a kind of polymer forms in the presence of other polymer.Polymer can prepare in any above-mentioned polymerization.Reactor blend can prepare in single reactor or in two or more reactors of arranged in series.Can be further by reactor blending blend behind reactor being combined to prepare the blend of described the first and second polymer.
Fluoropolymer resin through blend can be used to prepare the supatex fabric product.This paper employed " supatex fabric " refers to the textile material by the preparation of the method except weaving.In supatex fabric, by allowing middle one dimension yarn conditions pass fiber directly is processed into the planar sheet fabric construction, then obtain the fabric that links up with chemistry, hot mode bonding or mechanical interlocking (or this dual mode).
Supatex fabric of the present invention can form by any method that is known in the art.Preferably, by melting and spraying or spunbond method prepares supatex fabric.
In typical spunbond method, polymer is supplied with the extruder of heating so that described polymer melting and homogenizing.Extruder is supplied with spinning head with molten polymer, and wherein polymer is passed in the described spinning head fibration with the tiny opening of a row or multi-row arrangement, forms filament curtain.Usually with air at low temperatures with described long filament quenching, stretch common pneumatic stretching, and it is upper and form supatex fabric to be deposited on mobile mat, belt or " forming wire ".Referring to, for example, U.S. Patent number 4,340,563; 3,692,618; 3,802,817; 3,338,992; 3,341,394; 3,502,763; With U.S. Patent number 3,542,615.
Usually in the about 50 microns diameter range of about 10-, this depends on process conditions and treats the thus required final use of fabric of fibrid preparation the fiber for preparing in the spunbond method.For example, improve the fiber that polymer molecular weight or reduction processing temperature cause larger diameter.The change of quench air temperature and pneumatic tensile pressures also has impact to fibre diameter.
This paper employed " meltblown fibers " and " meltblown fabric " refer to the fiber of following formation: molten thermoplastic extruded as melting clue or long filament under certain processing temperature via the die capillaries of many tiny, common circles and enter the high speed that converges, usually in the air-flow of heat, described air-flow attenuates the long filament of molten thermoplastic and reduces their diameter, and this can be to be reduced to the microfiber diameter.After this, by the described meltblown fibers of high velocity air carrying and be deposited on and collect the upper net width of cloth or the supatex fabric that has the meltblown fibers of random dispersion with formation in surface.This kind method general description is for example, and U.S. Patent number 3,849 is in 241 and 6,268,203.Meltblown fibers is continuous or discrete and is generally less than about 10 microns, preferably less than about 5 microns microfiber.Term as used herein melts and sprays and is intended to contain the melt spray method.
Commercial meltblowing method uses has high yield (throughput), surpasses 0.3 gram/hole/minute (" ghm "), or surpasses 0.4ghm, or surpasses 0.5ghm, or surpasses 0.6ghm, or surpasses the extruder of 0.7ghm.Fabric of the present invention can use commercial meltblowing method, or prepares in test or pilot-scale method.In one or more embodiments of the invention, use has the about 3.0ghm of about 0.1-, or about about 2.0ghm of 0.2-, or approximately the extruder of the rate of extrusion (throughput rate) of the about 1.0ghm of 0.3-forms the fiber that is used for forming supatex fabric.
Fabric described herein can be individual layer, maybe can be multilayer laminated body.A kind of application is by meltblown fabric (" M ") and nonwoven fabric (" S ") prepared layer laminate (or " composite "), and this is with the strength advantage of nonwoven fabric and the larger barrier property combination of meltblown fabric.Typical layered product or composite have three or more layers, namely are clipped in the meltblown layer (one or more) between two or more spunbond layers, or have " SMS " Fabric composites.The example of other combination is SSMMSS, SMMS and SMMSS composite.Composite also can be by meltblown fabric of the present invention and other synthetic or natural material make, to be prepared with the goods of usefulness.
A kind of parameter that is commonly used to describe supatex fabric is their basic weight, or the fabric weight of per unit area.Fabric of the present invention can have about 500 g/ms of about 0.1-(" gsm "), or about about 450gsm of 1-, or about about 400gsm of 10-, or the basic weight of about about 350gsm of 25-.
Various additives can be attached to make in the polymer of fiber as herein described and fabric, this depends on the purpose of expection.These additives can comprise, but be not limited to stabilizing agent, antioxidant, filler, colouring agent, nucleator, dispersant, releasing agent, slipping agent, fire retardant, plasticizer, pigment, sulfuration or curing agent, sulfuration or curing agent promoter, cure retarder, processing aid, tackifying resin etc.Other additive can comprise filler and/or reinforcing material, such as carbon black, clay, talcum, calcium carbonate, mica, silica, silicate, their combination etc.The secondary antioxidants of advocating peace comprises, for example, and sterically hindered phenol, bulky amine and phosphate.Nucleator comprises, for example, and Sodium Benzoate and talcum.In addition, in order to improve crystalline rate, can also use other nucleator, such as Z-N olefin product or other highly crystalline polymer.Other additive such as dispersant, for example Acrowax C is also includable.Slipping agent comprises, for example, and oleamide and mustard acid amides.Also usually use catalyst passivating agent, for example calcium stearate, hydrotalcite and calcium oxide, and/or other acid neutralizing agent known in the prior art.
Above-mentioned nonwoven products can be used for for example health product of many goods, includes but not limited to diaper, feminine care product and adult incontinence products.Described nonwoven products can also be used for medical product for example sterile package, isolation robe, operating room robe, operation robe, surgical drage, first aid dressing and other disposable product.
Fabric of the present invention also can be used as air or liquid filter.The example of filter application comprises for example pool filter comprising of automobile and vehicle passenger cabin filter, family's ventilation filter, clean room filter, industrial ash content and particulate filter, operation and nuisance dust mask, beverage filter, medicine filter, medical filter device, water purification filter and recuperation filter.Described filter can be sheet or the box-like formula is used, and can be multilayer or multi-density.
Fabric of the present invention also can be used as g. absorbent products, for example oil absorber, chemical substance absorbent or water absorbent goods.Some other specific nonwoven articles include, but not limited to swimsuit, coat, scrub pad, cloth lining, automotive interior spare, face shield and mouth mask, vacuum bag, Wiping material and other product.
Embodiment
Among the embodiment, the first polymer based on propylene (being labeled as " component A ") and the second polymer based on propylene (being labeled as " B component ") are used for individually or blend is used to form the fluoropolymer resin that forms supatex fabric through melting and spraying below.Can be from Greenville, form fabric on the BIAX pilot production line that the BIAX-Fiberfilm of WI is purchased.Described pilot production line is equipped with 3.5 " extruders and have roughly 25 " (0.635m) wide capillary die heads of 200 hole/inches (0.015 " capillary size) of the output that can reach 300+lb/hr roughly.The maximum rate of extrusion of extruder is 0.57ghm roughly.Described production line also is equipped with 1m diameter single-drum collector.Environment temperature at the trial is roughly 60 °F (15.5 ℃).All fabric embodiment that the below reports have the roughly basic weight of 300gsm.
Component A is the reactor grade propylene homopolymers of metallocene catalyst with MFR of about 1550g/10min.
B component 1 is the Noblen of ziegler-natta catalyzed with MFR of about 36g/10min.
B component 2 is the Noblens of ziegler-natta catalyzed with MFR of about 65g/10min.
B component 3 is to have the ethylene comonomer content of 13wt% and the elastomer based on propylene of the metallocene catalyst of the MFR of about 290g/10min.
B component 4 is the Noblens with ziegler-natta catalyzed that the peroxide of the MFR of about 1200g/10min applies.
Embodiment
Employed one inch of this paper equals 2.54 centimetres.Degrees Fahrenheit (°F) can followingly change into degree centigrade (℃): ℃=(°F-32) x 5/9.
Embodiment 1: in comparative example 1, use 100wt% component A to prepare fabric under different rates of extrusion, air themperature, die pressure and water quenching speed.The fabric that vision and sense of touch observation post get, and in table 1, report the result.
Table 1 (Achieve 6936G1)
Embodiment 2: in embodiment 2, use 95wt% component A to prepare fabric with 5wt% B component 1 under different rates of extrusion, air themperature, die pressure and water quenching speed.The fabric that vision and sense of touch observation post get, and in table 2, report the result.
Table 2 (5%PP3155)
Embodiment 3: in embodiment 3, use 90wt% component A to prepare fabric with 10wt% B component 1 under different rates of extrusion, air themperature, die pressure and water quenching speed.The fabric that vision and sense of touch observation post get, and in table 3, report the result.
Table 3 (10%PP3155)
Embodiment 4: in embodiment 4, use 90wt% component A to prepare fabric with 10wt% B component 2 under different rates of extrusion, air themperature, die pressure and water quenching speed.
The fabric that vision and sense of touch observation post get, and in table 4, report the result.
Table 4 (10%PP3885)
Embodiment 5: in embodiment 5, use 90wt% component A to prepare fabric with 10wt% B component 3 under different rates of extrusion, air themperature, die pressure and water quenching speed.The fabric that vision and sense of touch observation post get, and in table 5, report the result.
Table 5 (10%VM2330)
Embodiment 6: in comparative example 6, use 100wt% B component 4 to prepare fabric under different rates of extrusion, air themperature, die pressure and water quenching speed.The fabric that vision and sense of touch observation post get, and in table 6, report the result.
Table 6 (PP3546G)
As reflecting among top embodiment and the Biao, add a small amount of low MFR polymer or have greater than the polymer (B component) of about 0.94 or 0.95 or 0.96 three unit group steric regularities help to improve bulkiness in the reactor grade homo-polypropylene (component A) of high MFR metallocene catalyst and the melt-blown non-woven fabric that reduces to be made by described blend polymer in binding (that is, poor long filament separation).The interpolation of the second polymer it is believed that the solidification rate of following improvement the first polymer: improve to allow higher processing temperature and therefore higher water quenching speed so that faster cooling and do not stay the elongation viscosity of high residue moisture or by making the nucleated raising crystalline rate of metallocene polymers.Faster curing or crystallization tends to produce more high loft in fabric.
Table 7 (blend that the polypropylene melt-blown of metallocene catalyst and Z-N melt and spray).The B component of the component A of blend 1=10wt% (polypropylene of ziegler-natta catalyzed with MFR of 400gr/min) and 90wt% (polypropylene of metallocene catalyst with MFR of 1400gr/min) and the component A of blend 2=20wt% and the B component of 80wt%, described wt% is based on the gross weight of blend:
Table 7
* from the contrast of the reference fabric with different flash of light levels
Table 7 (sequence 2.9-2.18) has shown polymer with metallocene catalyst (process conditions and the performance of the～meltblown fabric 1400MFR) made.Polymer (blend 1 with the 400MFR reactor grade) blend of the low MFR that will make with the Z-N catalyst allow in the lower even fabric that have low flash of light level in the lower preparation of quite low processing temperature (480 °F) of contour rate of extrusion (0.6ghm).Under high rate of extrusion (0.75ghm) and/or high processing temperature (510 °F), the flash of light level that blend 2 allows preparation to have significantly to reduce and the fabric of improved barrier property (higher hydrostatic pressing (hydrohead) or " HH ").
The present invention can further describe as follows:
1. the supatex fabric of being made by polymer composition, described polymer composition comprises:
A. approximately the about 99.9wt% of 70-to have about 100-about 5, the first polymer based on propylene of the melt flow rate (MFR) of 000g/10min is based on the gross weight of described composition; With
B. about the second polymer based on propylene of the melt flow rate (MFR) with the about 500g/10min of about 1-of the about 30wt% of 0.1-,
The wherein said second polymer based on propylene has following at least one: (i) than described first based on the lower melt flow rate (MFR) of the polymer of propylene; Or (ii) than described first based on the higher degree of crystallinity of the polymer of propylene;
The wherein said first polymer based on propylene is to use the catalyst system that comprises metalloscene catalyst to prepare.
2.1 fabric, wherein said polymer composition comprises the described second polymer based on propylene of the about 15wt% of about 5-.
3.1 fabric, the wherein said second polymer based on propylene is to use the catalyst system preparation comprise Ziegler-Natta catalyst.
4.1 fabric, wherein said fabric is meltblown fabric.
5.1 fabric, the wherein said first polymer based on propylene is Noblen.
6.5 fabric, the wherein said first polymer based on propylene is reactor grade propylene homopolymers.
7.1 fabric, the wherein said second polymer based on propylene is Noblen.
8.1 fabric, the wherein said second polymer based on propylene also comprises one or more that account for described the second polymer 0.01-25wt% and is selected from C
2And/or C
4-C
10The comonomer of alpha-olefin.
9.1 fabric, the wherein said first polymer based on propylene has the melt flow rate (MFR) of the about 3000g/10min of about 500-.
10.1 fabric, the wherein said second polymer based on propylene has the melt flow rate (MFR) of the about 250g/10min of about 1-.
11.1 fabric, the wherein said second polymer based on propylene has the melt flow rate (MFR) of the about 50g/10min of about 1-.
12.1 fabric, wherein said the first polymer has three unit group steric regularities greater than about 0.94.
13.1 fabric, the wherein said second polymer based on propylene has than described first based on three higher unit group steric regularities of the polymer of propylene.
14.1 fabric, the wherein said first polymer based on propylene have by
13C NMR measure greater than about 75 meso running length.
15. comprise the goods of 1 fabric.
16.15 goods, wherein said goods are selected from one or more in health product, medical product, filter medium, oil suction product, suction product or the chemical substance absorbing products.
17. the preparation method of supatex fabric comprises:
A. form molten polymer composition, described molten polymer composition comprises: (i) approximately the use of the about 99.9wt% of 70-comprises the catalyst system preparation of metalloscene catalyst and has about 100-about 5, the first polymer based on propylene of the melt flow rate (MFR) of 000g/10min is based on the gross weight of described composition; (ii) about the second polymer based on propylene of the melt flow rate (MFR) with the about 500g/10min of about 1-of the about 30wt% of 0.1-, the wherein said second polymer based on propylene has following at least one: (i) than described first based on the lower melt flow rate (MFR) of the polymer of propylene; Or (ii) than described first based on the higher degree of crystallinity of the polymer of propylene;
B. use meltblowing method to form the fiber that comprises described polymer composition; With
C. form fabric by described fiber.
18.17 method, the wherein said second polymer based on propylene has than described first based on three higher unit group steric regularities of the polymer of propylene.
19.17 method, the wherein said second polymer based on propylene is to use the catalyst system preparation comprise Ziegler-Natta catalyst.
20.17 method, the wherein said first polymer based on propylene is Noblen.
21.20 method, the wherein said first polymer based on propylene is reactor grade propylene homopolymers.
22.17 method, the wherein said second polymer based on propylene is Noblen.
23.17 method, the wherein said second polymer based on propylene also comprises one or more that account for described the second polymer 0.01-25wt% and is selected from C
2And/or C
4-C
10The comonomer of alpha-olefin.
24.17 method, the wherein said first polymer based on propylene has the melt flow rate (MFR) of the about 3000g/10min of about 500-.
25.17 method, the wherein said first polymer based on propylene has the MWD of about 1.0-about 4.0.
26.17 method, the wherein said first polymer based on propylene have by
13C NMR measure greater than about 75 meso running length.
27.17 method, wherein said fiber is to use the extruder of the rate of extrusion with the about 3ghm of about 0.1-to form.
28.27 method, wherein said rate of extrusion is the about 1.0ghm of about 0.3-.
29.27 method, the melt temperature of wherein said extruder is about 175 ℃-about 290 ℃.
30.17 method, the air themperature of wherein said meltblowing method is about 175 ℃-about 290 ℃.
31.17 method, wherein the air pressure at the die head place of described meltblowing method is the about 215kPa of about 10kPa-.
32.17 method, wherein said fabric has the about 500g/m of about 0.1-
2Basic weight.
Used one group of numerical upper limits and one group of numerical lower limits to describe some embodiment and feature.Self-evident is that the scope from any lower limit to any upper limit should be considered, except as otherwise noted.Some lower limit, the upper limit and scope appear in following one or more claim.All numerical value are " approximately " or " roughly " described indicated value, and consider that those skilled in the art are with experimental error and the deviation estimated.
The above has defined various terms.If the term that uses in the claim limits in the above, then should give the widest definition for it, because having known described term, the association area personnel are reflected in the patent of the publication of at least one piece of printing or announcement.In addition, all patents of quoting among the application, test procedure and other document are consistent with the present invention and for reference for fully introducing on the degree of all authorities that allow this introducing in this publication.
Although foregoing relates to embodiment of the present invention, can in the situation that does not break away from base region of the present invention, design other and other embodiments of the present invention, and scope of the present invention is determined by claim subsequently.
Claims (32)
1. the supatex fabric of being made by polymer composition, described polymer composition comprises:
A. approximately the about 99.9wt% of 70-to have about 100-about 5, the first polymer based on propylene of the melt flow rate (MFR) of 000g/10min is based on the gross weight of described composition; With
B. about the second polymer based on propylene of the melt flow rate (MFR) with the about 500g/10min of about 1-of the about 30wt% of 0.1-, the wherein said second polymer based on propylene has following at least one: (i) than described first based on the lower melt flow rate (MFR) of the polymer of propylene; Or (ii) than described first based on the higher degree of crystallinity of the polymer of propylene;
The wherein said first polymer based on propylene is to use the catalyst system that comprises metalloscene catalyst to prepare.
2. the fabric of claim 1, wherein said polymer composition comprises the described second polymer based on propylene of the about 15wt% of about 5-.
3. claim 1 or 2 fabric, the wherein said second polymer based on propylene are to use the catalyst system preparation that comprises Ziegler-Natta catalyst.
4. each fabric among the claim 1-3, wherein said supatex fabric is the melt-blown non-woven fabric.
5. each fabric among the claim 1-4, the wherein said first polymer based on propylene is Noblen.
6. the fabric of claim 5, the wherein said first polymer based on propylene is reactor grade propylene homopolymers.
7. each fabric among the claim 1-6, the wherein said second polymer based on propylene is Noblen.
8. each fabric among the claim 1-7, the wherein said second polymer based on propylene also comprise and account for described second and be selected from C based on one or more of the polymer 0.01-25wt% of propylene
2And/or C
4-C
10The comonomer of alpha-olefin.
9. each fabric among the claim 1-8, the wherein said first polymer based on propylene has the melt flow rate (MFR) of the about 3000g/10min of about 500-.
10. each fabric among the claim 1-9, the wherein said second polymer based on propylene has the melt flow rate (MFR) of the about 250g/10min of about 1-.
11. each fabric among the claim 1-10, the wherein said second polymer based on propylene has the melt flow rate (MFR) of the about 50g/10min of about 1-.
12. each fabric among the claim 1-11, the wherein said first polymer based on propylene have three unit group steric regularities greater than about 0.94.
13. each fabric among the claim 1-12, the wherein said second polymer based on propylene have than described first based on three higher unit group steric regularities of the polymer of propylene.
14. each fabric among the claim 1-13, the wherein said first polymer based on propylene have by
13C NMR measure greater than about 75 meso running length.
15. comprise the goods of each fabric among the claim 1-14.
16. the goods of claim 15, wherein said goods are selected from health product, medical product, filter medium, oil suction product, suction product or the chemical substance absorbing products one or more.
17. the preparation method of supatex fabric comprises:
A. form polymer composition, described polymer composition comprises: (i) approximately the use of the about 99.9wt% of 70-comprises the catalyst system preparation of metalloscene catalyst and has about 100-about 5, the first polymer based on propylene of the melt flow rate (MFR) of 000g/10min is based on the gross weight of described composition; (ii) about the second polymer based on propylene of the melt flow rate (MFR) with the about 500g/10min of about 1-of the about 30wt% of 0.1-, the wherein said second polymer based on propylene has following at least one: (i) than described first based on the lower melt flow rate (MFR) of the polymer of propylene; Or (ii) than described first based on the higher degree of crystallinity of the polymer of propylene;
B. use meltblowing method to form the fiber that comprises described polymer composition; With
C. form fabric by described fiber.
18. the method for claim 17, the wherein said second polymer based on propylene have than described first based on three higher unit group steric regularities of the polymer of propylene.
19. the method for claim 16 or 17, the wherein said second polymer based on propylene are to use the catalyst system that comprises Ziegler-Natta catalyst to prepare.
20. each method among the claim 17-19, the wherein said first polymer based on propylene is Noblen.
21. the method for claim 20, the wherein said first polymer based on propylene are reactor grade propylene homopolymers.
22. each method among the claim 17-21, the wherein said second polymer based on propylene is Noblen.
23. also comprising one or more that account for described the second polymer 0.01-25wt%, each method among the claim 17-22, the wherein said second polymer based on propylene be selected from C
2And/or C
4-C
10The comonomer of alpha-olefin.
24. each method among the claim 17-23, the wherein said first polymer based on propylene has the melt flow rate (MFR) of the about 3000g/10min of about 500-.
25. each method among the claim 17-24, the wherein said first polymer based on propylene has the MWD of about 1.0-about 4.0.
26. each method among the claim 17-25, the wherein said first polymer based on propylene have by
13C NMR measure greater than about 75 meso running length.
27. each method among the claim 17-26, wherein said fiber are to use the extruder of the rate of extrusion with the about 3ghm of about 0.1-to form.
28. the method for claim 27, wherein said rate of extrusion are the about 1.0ghm of about 0.3-.
29. the method for claim 27 or 28, the melt temperature of wherein said extruder are about 175 ℃-about 290 ℃.
30. each method among the claim 17-29, the air themperature of wherein said meltblowing method are about 175 ℃-about 290 ℃.
31. each method among the claim 17-30, wherein the air pressure at the die head place of described meltblowing method is the about 215kPa of about 10kPa-.
32. each method among the claim 17-31, wherein said fabric have the about 500g/m of about 0.1-
2Basic weight.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US35488210P | 2010-06-15 | 2010-06-15 | |
| US61/354,882 | 2010-06-15 | ||
| PCT/US2011/034967 WO2011159400A1 (en) | 2010-06-15 | 2011-05-03 | Nonwoven fabrics made from polymer blends and methods for making same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102971454A true CN102971454A (en) | 2013-03-13 |
| CN102971454B CN102971454B (en) | 2015-05-27 |
Family
ID=44263170
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201180029041.8A Expired - Fee Related CN102971454B (en) | 2010-06-15 | 2011-05-03 | Nonwoven fabrics made from polymer blends and methods for making same |
Country Status (3)
| Country | Link |
|---|---|
| US (1) | US20130137331A1 (en) |
| CN (1) | CN102971454B (en) |
| WO (1) | WO2011159400A1 (en) |
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|---|---|---|---|---|
| CN109477266A (en) * | 2016-07-22 | 2019-03-15 | 埃克森美孚化学专利公司 | Polypropylene nonwoven fiber, fabric and its manufacturing method |
| TWI829029B (en) * | 2020-10-30 | 2024-01-11 | 荷蘭商耐克創新有限合夥公司 | Recyclable, asymmetrical-faced composite nonwoven textile having silicone-coated fibers and method of manufacturing a composite nonwoven textile |
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| EP3296355B1 (en) * | 2014-09-05 | 2019-06-19 | ExxonMobil Chemical Patents Inc. | Fibers comprising polymer compositions and nonwoven materials prepared therefrom |
| US9879364B2 (en) * | 2015-10-30 | 2018-01-30 | Exxonmobil Chemical Patents Inc. | Polymer compositions for staple and multifilament fibers |
| CN110760130A (en) * | 2018-07-27 | 2020-02-07 | 合肥杰事杰新材料股份有限公司 | Low-odor polypropylene material and preparation method thereof |
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| TWI829029B (en) * | 2020-10-30 | 2024-01-11 | 荷蘭商耐克創新有限合夥公司 | Recyclable, asymmetrical-faced composite nonwoven textile having silicone-coated fibers and method of manufacturing a composite nonwoven textile |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102971454B (en) | 2015-05-27 |
| WO2011159400A1 (en) | 2011-12-22 |
| US20130137331A1 (en) | 2013-05-30 |
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