WO1999035171A1 - High-melting polyolefin copolymer elastomers, catalysts and methods of synthesis - Google Patents

High-melting polyolefin copolymer elastomers, catalysts and methods of synthesis Download PDF

Info

Publication number
WO1999035171A1
WO1999035171A1 PCT/US1999/000540 US9900540W WO9935171A1 WO 1999035171 A1 WO1999035171 A1 WO 1999035171A1 US 9900540 W US9900540 W US 9900540W WO 9935171 A1 WO9935171 A1 WO 9935171A1
Authority
WO
WIPO (PCT)
Prior art keywords
bis
indene
methyl
copolymer
polymerization process
Prior art date
Application number
PCT/US1999/000540
Other languages
French (fr)
Inventor
Robert M. Waymouth
Raisa L. Kravchenko
Jennifer Maciejewski Petoff
Original Assignee
The Board Of Trustees Of The Leland Stanford Jr. University
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 The Board Of Trustees Of The Leland Stanford Jr. University filed Critical The Board Of Trustees Of The Leland Stanford Jr. University
Priority to PCT/US1999/000540 priority Critical patent/WO1999035171A1/en
Priority to AU21115/99A priority patent/AU2111599A/en
Publication of WO1999035171A1 publication Critical patent/WO1999035171A1/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/02—Ethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F110/00—Homopolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F110/04—Monomers containing three or four carbon atoms
    • C08F110/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F4/00—Polymerisation catalysts
    • C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
    • C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
    • C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
    • C08F4/62—Refractory metals or compounds thereof
    • C08F4/639—Component covered by group C08F4/62 containing a transition metal-carbon bond
    • C08F4/63912—Component covered by group C08F4/62 containing a transition metal-carbon bond in combination with an organoaluminium compound

Definitions

  • Copolymers filed January 9, 1998 by Waymouth and Kravchenko, the benefit of the filing date of which is hereby claimed under 35 U.S. Code ⁇ 112, 119(e) and 120, and under appropriate provisions of the PCT rules.
  • This invention relates to high melting polyolefin copolymers suitable as thermoplastic elastomers and catalysts and methods for their synthesis. These olefin copolymers are characterized by low glass transition temperatures, melting points above about 90°C, high molecular weights, and a narrow composition distribution between chains.
  • the copolymers of the invention are novel reactor blends that can be sequentially fractionated into fractions of differing crystallinities, said fractions nevertheless show compositions of comonomers which differ by less than 15 % from the parent reactor blend.
  • the invention also relates to a process for producing such copolymers by utilizing an unbridged metallocene catalyst that is capable of interconverting between states with different copolymerization characteristics.
  • Ethylene alpha-olefin copolymers are important commercial products. These copolymers find a particularly broad range of application as elastomers. There are generally three family of elastomers made from such copolymers. One class is typified by ethylene-propylene copolymers (EPR) which are saturated compounds, optimally of low crystallinity, requiring vulcanization with free-radical generators to achieve excellent elastic properties. Another type of elastomer is typified by ethylene-propylene terpolymers (EPDM), again optimally of low crystallinity, which contain a small amount of a non- conjugated diene such as ethylidene norbornene.
  • EPR ethylene-propylene copolymers
  • EPDM ethylene-propylene terpolymers
  • These novel polymers are useful as elastomeric and/or thermoplastic materials as well as compatibilizers for other polyolefin blends.
  • Multiblock polymer or copolymer means a polymer comprised of multiple block sequences of monomer units where the structure or composition of a given sequence differs from that of its neighbor. Furthermore a multiblock copolymer as defined herein will contain a given sequence at least twice in every polymer chain. b.
  • crystallizable component we mean a monomer component whose homopolymer is a crystalline polymer. The melting point is taken as a maximum in a melting endotherm, as determined by differential scanning calorimetry.
  • copolymers of the present invention in one embodiment can be characterized as reactor blends in that they can be fractionated into fractions of differing degrees of crystallinity and differing melting points. Nevertheless, the comonomer composition of the various fractions of the copolymers are within 15% of the composition of the resultant polymer product produced in the reactor.
  • the melting points of the copolymers of the present invention are high, typically above 90 °C and the melting point indices, T m / X c are also high, typically above 80 °C and preferably above 115°C.
  • the fractions can also exhibit high melting point indices. For example, it is possible to isolate a hexanes soluble fraction from the copolymers of the present invention that exhibits a melting point as high as 115 °C and a melting point index as high as 160 °C.
  • the glass transition temperatures of the copolymers are low, typically less than -20 °C and preferably below -50 °C.
  • the copolymers of the present invention exhibit useful elastomeric properties. They can be used in a variety of applications typical of amorphous or partially crystalline elastomers and as compatibilizers for copolymer blends.
  • One embodiment of the invention includes metallocene catalysts which are able to interconvert between states whose coordination geometries are different.
  • the invention includes selecting the substituents of the metallocene cyclopentadienyl ligands so that the rate of interconversion of the two states is within several orders of magnitude of the rate of formation of a single polymer chain. That is, if the rate of interconversion between states of the catalyst, ⁇ , is greater than the rate of formation of an individual polymer chain, rf , on average, the polymer resulting from use of the inventive process and catalysts can be characterized as multiblock (as defined above). If the rate of interconversion is less than the rate of formation, the result is a polymer blend. Where the rates are substantially balanced, the polymer can be characterized as a mixture of blend and multiblock. There may be a wide range of variations and intermediate cases amongst these three exemplars.
  • the nature of the substituents on the cyclopentadienyl ligands is critical; the substitution pattern of the cyclopentadienyl ligands should be such that the coordination geometries are different in order to provide for different reactivities toward ethylene and other alpha olefins while in the two states (see Figure 1) and that the rate of interconversion of the states of the catalyst are within several orders of magnitude of the rate of formation of a single chain.
  • a further embodiment includes metallocene catalysts which are able to interconvert between more than two states whose coordination geometries are different. This is provided for by metallocenes with cyclopentadienyl-type ligands substituted in such a way that more than two stable states of the catalyst have coordination geometries that are different, for example, a catalyst with four geometries is illustrated in one embodiment in Figure 2.
  • the properties of the copolymers can be controlled by changing the nature of the cyclopentadienyl units on the catalysts, by changing the nature of the metal atom in the catalyst, by changing the nature of the comonomers and the comonomer feed ratio, and by changing the temperature.
  • the molecular weights of the polymers produced with the catalysts of the invention are very high.
  • the molecular weight of the polymer product can be controlled, optionally, by controlling the temperature or by adding any number of chain transfer agents such as hydrogen or metal alkyls, as is well known in the art.
  • the catalyst system of the present invention consists of the transition metal component metallocene in the presence of an appropriate cocatalyst.
  • the transition metal compounds have the formula:
  • M is a Group 3, 4 or 5 Transition metal, a Lanthanide or an Actinide
  • X and X' are the same or different uninegative ligands, such as but not limited to hydride, halogen, hydrocarbyl, halohydrocarbyl, amine, amide, or borohydride substituents (preferably halogen, alkoxide.
  • Ri, R2, R3, R9, and Rio may be the same or different hydrogen, alkyl, alkylsilyl, aryl, alkoxyalkyl, alkoxyaryl, alkoxysilyl, aminoalkyl, aminoaryl or substituted alkyl, alkylsilyl or aryl substituents of 1 to about 30 carbon atoms.
  • R2-R10 have the same definition as Ri , R2, R3, R9, and Rio above.
  • Alternately preferred L and L' of Formula 1 include ligands of Formula 2 wherein
  • Rl is an aryl group, such as a substituted phenyl, biphenyl, or naphthyl group, and R2 and R3 are connected as part of a ring of three or more carbon atoms.
  • L or L' of Formulas 1- 3 for producing the copolymers of this invention are substituted indenyl ligands, more particularly 2-arylindene of formula:
  • 2-aryl indenes include at present as preferred best mode compounds: 2-phenylindene; l-methyl-2-phenyl indene; 2-(3,5-dimethylphenyl) indene; 2-
  • Preferred metallocenes according to the present invention include: bis(2-phenylindenyl) zirconium dichloride; bis(2-phenylindenyl) zirconium dimethyl; bis(l-methyl-2-phenylindenyl) zirconium dichloride; bis(l-methyl-2-phenylindenyl) zirconium dimethyl; bis[2-(3,5-dimethylphenyl)indenyl] zirconium dichloride; bis[2-(3,5-bis-trifluoromethylphenyl)indenyl] zirconium dichloride; bis[2-(3,5-bis-tertbutylphenyl)indenyl] zirconium dichloride; bis[2-(3,5-bis-trimethylsilylphenyl)indenyl] zirconium dichloride; bis[2-(4,-fluorophenyl)indenyl] zirconium dichloride; bis[2-(2,3,4,5,-tetrafloropheny
  • metallocene catalyst components of the catalyst system according to the present invention include: bis(3,4-dimethyl-l-phenylcyclopentadienyl) zirconium dichloride; bis(3,4-dimethyl-l-p-tolylcyclopentadienyl) zirconium dichloride; bis(3,4-dimethyl-l-(3,5 bis(trifluoromethyl)phenyl)cyclopentadienyl)zirconium dichloride; bis(3,4-dimethyl-l-(4-tert-butylphenyl)cyclopentadienyl) zirconium dichloride;
  • hafnium compounds such as: bis(3,4-dimethyl-l-phenylcyclopentadienyl) hafnium dichloride; bis(3,4-dimethyl-l-p-tolylcyclopentadienyl) hafnium dichloride; bis(3,4-dimethyl-l-(3,5 bis(trifluoromethyl)phenyl)cyclopentadienyl)hafnium dichloride; bis(3,4-dimethyl-l-(4-tert-butylphenyl)cyclopentadienyl) hafnium dichloride;
  • the catalysts of the present invention comprise un-bridged, non-rigid, fluxional metallocenes which can change their geometry with a rate that is within several orders of magnitude of the rate of formation of a single polymer chain, on average.
  • the relative rates of interconversion and of formation can be controlled by selecting the substituents (or absence thereof) of the cyclopentadienyl ligands so that they can alternate in structure between states of different coordination geometries which have different selectivity toward a particular comonomer.
  • these catalyst systems can be placed on a suitable support such as silica, alumina, or other metal oxides, MgCl2 or other supports.
  • catalysts can be used in the solution phase, in slurry phase, in the gas phase, or in bulk monomer. Both batch and continuous polymerizations can be carried out.
  • Appropriate solvents for solution polymerization include liquified monomer, and aliphatic or aromatic solvents such as toluene, benzene, hexane, heptane, diethyl ether, as well as halogenated aliphatic or aromatic solvents such as CH2CI2, chloro benzene, fluorobenzene, hexaflourobenzene or other suitable solvents.
  • Various agents can be added to control the molecular weight, including hydrogen, silanes and metal alkyls such as diethylzinc
  • metallocenes of the present invention in the presence of appropriate cocatalysts, are useful for the homo-polymerization and co-polymerization of alpha-olefins, such as propylene, 1-butene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-octene, and combinations thereof, and of copolymerization with ethylene.
  • alpha-olefins such as propylene, 1-butene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-octene, and combinations thereof, and of copolymerization with ethylene.
  • the polymerization of olefins is carried out by contacting the olefin(s) with the catalyst systems comprising the transition metal component and in the presence of an appropriate cocatalyst, such as an aluminoxane, a Lewis acid such as B(C6F5)3, or a protic acid in the presence of a non- coordinating counterion such as B(C6F5)4 " .
  • an appropriate cocatalyst such as an aluminoxane, a Lewis acid such as B(C6F5)3, or a protic acid in the presence of a non- coordinating counterion such as B(C6F5)4 " .
  • the metallocene catalyst systems of the present invention are particularly useful for the polymerization of ethylene and alpha-olefin comonomers as well as alpha-olefin monomer mixtures to produce co-polymers with novel elastomeric properties.
  • the properties of elastomers are characterized by several variables.
  • the tensile set (TS) is the elongation remaining in a polymer sample after it is stretched to an arbitary elongation (e.g. 100% or 300%) and allowed to recover. Lower set indicates higher elongational recovery.
  • Stress relaxation is measured as the decrease in stress (or force) during a time period (e.g. 30 sec. or 5 min.) that the specimen is held at extension.
  • retained force is measured as the ratio of stress at 50% elongation during the second cycle recovery to the initial stress at 100% elongation during the same cycle. Higher values of retained force and lower values of stress relaxation indicate stronger recovery force. Better general elastomeric recovery properties are indicated by low set, high retained force and low stress relaxation.
  • Bis(2-phenylindenyl)zirconium dichloride (Metallocene 2). This complex was prepared as described in Bruce, M. D. ; Coates, G. W. ; Hauptman, E. ; Waymouth, R. M. ; Ziller, J. W. J. Am. Chem. Soc. 1997, 119, 11174-11182.
  • Example 4 l-Methyl-2-(bis-3 * ,5 * -trifluoromethylphenyl)indene and 3-methyl-2-(bis- 3 * ,5 ' -trifluoromethylphenyl)indene.
  • a solution of 2-bis-3' ,5'-trifluoromethylphenyl)indene (1.819 g, 5.54 mmol) in tetrahydrofuran (30 mL) was cooled to -78 °C and BuLi (2.5 M in hexanes, 2.33 mL, 5.82 mmol) was added dropwise. The resulting orange-brown solution was allowed to warm to room temperature and stirred for an additional 30 min.
  • Butyllithium (2.5 M in hexane, 0.43 mL, 1.08 mmol) was added via syringe to the solution of l-methyl-2-phenylindenyl (212 mg, 1.029 mmol) in diethyl ether (25 mL) at -78 °C. The resulting light yellow solution was allowed to warm to room temperature and stirred for additional 30 min. The ether was removed in vacuo to yield a white powdery solid, which was combined with solid (2-phenylindenyl)zirconium trichloride (400 mg, 1.029 mmol) and toluene (50 mL). The resulting suspension was stirred for 24 h at room temperature.
  • Example 7 Synthesis of (2-phenylindenyl)(l-methyl-2-(bis-3', 5 * -trifluoro- methylpheuyl)indenyl) zirconium dichloride, Metallocene 7. Butyllithium (2.5 M in hexanes, 0.43 mL, 1.08 mmol) was added to the pale yellow solution of l-methyl-2-(bis-3' ,5'-trifiuoromethylphenyl)indene (352 mg, 1.029 mmol) in diethyl ether (20 mL) at -78 °C via syringe. The resulting yellow solution was allowed to warm to room temperature and stirred for additional 30 min.
  • Ether was removed in vacuo to yield a pale yellow solid which was washed with pentane (20 mL) and combined with solid (2-phenylindenyl)zirconium trichloride (400 mg, 1.029 mmol) and toluene (50 mL). The resulting suspension was stirred for 24 h at room temperature. Gradually the solids dissolved to give a yellow turbid solution. This solution was filtered through a glass frit packed with Celite and then evaporated to dryness. The yellow solid 7 was recrystallized from CH2CI2 (10 mL) layered with pentane (20 mL) at -50 °C: (245 mg, 34 %).
  • Example 8 Synthesis of (2-(bis-3 ⁇ 5 * -trifluoromethylphenyl)indenyl) zirconium trichloride.
  • Solid Zr(NMe2)4 1 -260 g, 4.713 mmol
  • l-methyl-2-(bis-3' ,5'- trifluoromethylphenyl)indene 1.505 g, 4.58 mmol
  • Butyllithium (2.5 M in hexanes, 0.55 mL, 1.38 mmol) was added to the solution of l-methyl-2-phenylindene (277 mg, 1.31 mmol) in diethyl ether (25 mL) at -78 °C via syringe.
  • Butyllithium (2.5 M in hexanes, 0.40 mL, 1.00 mmol) was added to the solution of 2-(bis-3,5-trifluoromethylphenyl)indene (328 mg, 0.958 mmol) in diethyl ether (30 mL) at -78 °C via syringe. The resulting light yellow solution was allowed to warm to room temperature, stirred for additional 2.5 h and the ether was removed in vacuo to yield a gray powdery solid, which was washed with pentane, filtered, and dried in vacuo.
  • a 300-mL stainless steel Parr reactor was charged with liquid propylene (100 mL). Propylene was cooled to the reaction temperature and pressurized with ethylene. The monomer mixture was equilibrated at the reaction temperature under constant ethylene pressure for at least 20 min. Immediately prior to the catalyst injection the ethylene line was disconnected and the reactor was cooled to 2-3 °C below the reaction temperature to compensate for the anticipated exothermic effect of catalyst injection. In a nitrogen filled drybox a 50-mL pressure tube was charged with zirconocene/MAO solution in toluene (20 mL), removed from the box and pressurized with argon (250 psig).
  • METHOD B Copolymerization of Ethylene and Propylene ( > 60 mole % E).
  • a 300-mL Parr autoclave was charged with 60 mL of liquid propylene and cooled to the reaction temperature.
  • MAO dissolved in 10 mL of toluene, was injected under ethylene pressure and the reactor was allowed to equilibrate for 10-15 min.
  • Polymerization was initiated by injecting the corresponding zirconocene dichloride solution in 10 mL of toluene under ethylene pressure set to 30-40 psi above the head pressure of preequlibrated ethylene/propylene mixture in the reactor. Polymerization was conducted for 25 min and quenched by injecting 10 mL of methanol under Ar pressure. The reactor was slowly vented and opened. The copolymer was precipitated in acidified methanol (5% HC1), filtered, washed with methanol and dried in a vacuum oven at 40 °C to constant weight.
  • the metallocene was dissolved in 25 mL of toluene in the N2 dry box.
  • Methylaluminoxane (MAO) was dissolved in 35 mL of 1-hexene.
  • the MAO solution was loaded into a 150 mL 2-ended injection tube. Meanwhile, a 300 mL stainless steel Parr reactor was evacuated to 100 mtorr and refilled with Ar. The reactor was flushed three times with 50 psig Ar and then 129 psig ethylene.
  • the MAO solution was introduced to the reactor and was allowed to equilibrate with under the desired head pressure of ethylene for 30 min.
  • Ethylene-Propylene Copolymer Characterization Copolymer composition and monomer sequence distribution were determined using c NMR spectroscopy. Copolymer samples (180-300 mg) were dissolved in 2.5 mL of o-dichlorobenzene/10 vol. % benzene- ⁇ in 10 mm tubes. The spectra were measured at 140 °C using pulse repetition intervals of 13 s and gated proton decoupling. The isotacticity of propylene triads (%mm) was determined from the ratio of integrals of the first triplet in the methyl region (all pmp m P centered triads) over T ⁇ peak (all PPP triads).
  • the glass transition, melting points and heats of fusion were determined by differential scanning calorimetry using Perkin- Elmer DSC-7.
  • the DSC scans were obtained by first heating copolymer samples to 160 °C for 20 min, cooling them to 20 °C over 2 h, ageing them at room temperature for 24 h and then reheating from -100 °C to 200 °C at 20 °C/min. All DSC values in the tables are reheat values.
  • Copolymer composition and monomer sequence distribution were determined using 3c NMR spectroscopy.
  • Copolymer samples (180-300 mg) were dissolved in 2.5 mL of o-dichlorobenzene/10 vol. % benzene-d ⁇ in 10 mm tubes.
  • Approximately 5 mg of chromium acetylacetonate was added to samples to decrease spin relaxation times.
  • the spectra were measured at 100 °C using pulse repetition intervals of 5 s and gated proton decoupling.
  • the glass transition, melting points and heats of fusion were determined by differential scanning calorimetry using a Perkin-Elmer DSC-7.
  • the DSC scans were obtained by first heating copolymer samples to 200 °C for 10 min, cooling them to 20 °C at 20 °C per minute, aging them at room temperature for 24 h and then reheating from 0 °C to 200 °C at 20 °C/min. All DSC values in the tables are reheat values. Scans to determine the glass transition temperature were obtained by cooling the sample to -150 °C and then heating to 0 °C at 40 °C/min. Mechanical tests were performed at 23 °C with ASTM D-1708 dumbell specimens
  • Tensile tests were run according to ASTM D638-96. Tensile modulus of elasticity was determined as the tangent slope at lowest strain. Elongation after break (percent elongation following break) was measured from benchmarks as immediate set of the center 10mm section of the specimen. The three cycle recovery test was performed by extension of the specimen three times to 100% elongation with a 30 second hold at each extension and a 60 second hold at each recovery. Cumulative set after the first two cycles was measured from the strain at which stress exceeds the baseline on the third cycle. A stress relaxation test was also conducted by extension to 50% elongation and measuring the decay of the stress.
  • Ethylene/Propylene Copolymerizations were carried out according to Method A; results are reported in Tables 3 and 4. Table 3. First Order Markov Copolymerization Parameters for 1, 2, 4, 6-9 /MAO.
  • polymers prepared with metallocene 1 containing 42% ethylene are amorphous, whereas polymers of similar composition (48 %E) derived from metallocene 9 (Example 75) are crystalline and exhibit a melting range of 21-123 °C with a heat of fusion of 7.5 J/g.
  • compositional heterogeneity of the copolymer sample of Example 78 was investigated by extraction in boiling heptane.
  • the microstructures of the heptane soluble (50 wt%) and insoluble (50 wt%) fractions of Example 78 were analyzed by Solution 13c NMR spectroscopy (Table 5).
  • the ethylene contents (%E) of the fractions differ by 3% or less and the reactivity ratios calculated from the dyad distribution differ by less than 0.16 from the average of the whole polymer sample, clearly indicating the compositional homogeneity of these copolymers.
  • Comparative Example 105 is a commercial Ethylene/Octene Elastomer obtained from Dow (Engage 8200on)
  • Comparative Example 106 is an Ethylene/Butene Elastomer obtained from Exxon (Exact 4033tm)
  • comparative Example 107 is a polypropylene elastomer as described in Waymouth et al. US 5,594,080.
  • T m range (°C) 23-130 16-1 16 11-117 20 - 70 20 - 70 40-160
  • compositional hetereogeneity of these copolymers was investigated by extracting the copolymers in boiling ether and hexanes. The results of these fractionation experiments on the copolymer samples of Example 90 and 91 are reported in Table 8.
  • polymers of the present invention and the polymerization catalysts and processes by which the polymers are produced will have wide applicability in industry, inter alia, as elastomers having higher melting points than currently available elastomers, as thermoplastic materials, and as components for blending with other polyolefins for predetermined selected properties, such as raising the melting point of the blend.
  • typical polymers of this invention while they have degrees of crystallinity similar to that of Dow's Engage 8200tm and EXXON's 4033tm, they have a broader melting point range that extends to higher temperatures, e.g. , to 130°C, and above.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)

Abstract

This invention relates to high melting polyolefin copolymers suitable as thermoplastic elastomers and catalysts and methods for their synthesis. These elastomeric olefin copolymers are characterized by a mole fraction of crystallizable component XC from about 30 to about 99 %; low glass transition temperatures, below -20 °C, and typically below -50 °C; melting points above about 90 °C; high molecular weights; a molecular weight distribution MW/Mn∫/=10; and a narrow composition distribution between chains of ∫/=15 %. The novel copolymers of the invention range from reactor blends to multiblock copolymers that can be sequentially fractionated into fractions of differing crystallinities, which fractions nevertheless show compositions of comonomers which differ by less than 15 % from the parent polymer (reactor product). The invention also relates to a process for producing such copolymers by utilizing an unbridged, substituted or unsubstituted cyclopentadienyl metallocene catalyst that is capable of interconverting between states with different copolymerization characteristics, which interconversion is controlled by selecting the substituents of the cyclopentadienyl ligands so that the rate of interconversion of the two states is within several orders of magnitude of the rate of formation of a single polymer chain. Where ri > rf the polymer can be characterized as multiblock; where ri < rf, the result is a polymer blend and where ri/rf is close to 1, the resulting polymer is a mixture of blend and multiblock. The metallocene catalysts of the invention are able to interconvert between more than two states, with embodiments of four states being shown in Figure 2.

Description

TITLE: HIGH-MELTING POLYOLEFIN COPOLYMER ELASTOMERS, CATALYSTS AND METHODS OF SYNTHESIS
DESCRD7TION
CROSS REFERENCE TO RELATED APPLICATIONS:
This application is the regular application of an earlier filed Provisional application
Serial Number 60/071,050, entitled Catalyst and Process for Synthesis of Olefin Block
Copolymers, filed January 9, 1998 by Waymouth and Kravchenko, the benefit of the filing date of which is hereby claimed under 35 U.S. Code §§ 112, 119(e) and 120, and under appropriate provisions of the PCT rules.
TECHNICAL FIELD:
This invention relates to high melting polyolefin copolymers suitable as thermoplastic elastomers and catalysts and methods for their synthesis. These olefin copolymers are characterized by low glass transition temperatures, melting points above about 90°C, high molecular weights, and a narrow composition distribution between chains. The copolymers of the invention are novel reactor blends that can be sequentially fractionated into fractions of differing crystallinities, said fractions nevertheless show compositions of comonomers which differ by less than 15 % from the parent reactor blend. The invention also relates to a process for producing such copolymers by utilizing an unbridged metallocene catalyst that is capable of interconverting between states with different copolymerization characteristics.
BACKGROUND:
Ethylene alpha-olefin copolymers are important commercial products. These copolymers find a particularly broad range of application as elastomers. There are generally three family of elastomers made from such copolymers. One class is typified by ethylene-propylene copolymers (EPR) which are saturated compounds, optimally of low crystallinity, requiring vulcanization with free-radical generators to achieve excellent elastic properties. Another type of elastomer is typified by ethylene-propylene terpolymers (EPDM), again optimally of low crystallinity, which contain a small amount of a non- conjugated diene such as ethylidene norbornene. The residual unsaturation provided by the diene termonomomer allows for vulcanization with sulfur, which then yields excellent elastomeric properties. Yet another class is typified by ethylene-alpha olefin copolymers of narrow composition distribution which possess excellent elastomeric properties even in the absence of vulcanization. For example US Patent 5,278,272, to Dow describes a class of substantially linear polyolefin copolymer elastomers with narrow composition distribution and excellent processing characteristics. (These latter class of elastomers are typified for example by the EXACT™, and ENGAGEm brand products sold commercially by Exxon and Dow, respectively.) One of the limitations of the latter class of elastomers is the low melting temperature of these materials which limits their high temperature performance. Hence it would be extremely advantageous to industry to produce copolymers of ethylene and alpha olefins which would show both elastomeric properties in the unvulcanized state and high melting points.
THE INVENTION SUMMARY, OBJECTS AND ADVANTAGES:
It is among the objects of this invention to provide methods of production of a class of novel polyolefin copolymers with a combination of interesting and useful physical characteristics, including a molecular weight distribution, M /Mn < /= 10, a narrow composition distribution, < /= 15%, high melting point index, melting points greater than about 90°C and elastomeric properties. It is a further object of this invention to produce a novel family of crystallizable, high-melting polyolefin copolymers having a narrow composition distribution where the melting point of the polymer is greater than about 90°C. It is a further object of this invention to produce a class of high-melting, multiblock, blend, and multiblock/blend polyolefin copolymer elastomers. These novel polymers are useful as elastomeric and/or thermoplastic materials as well as compatibilizers for other polyolefin blends.
We have unexpectedly found that it is possible to prepare high melting polyolefin elastomers of narrow composition distribution using novel unbridged metallocenes as olefin polymerization catalysts. For convenience, certain terms used throughout the specification are defined below (with " < / = " or " > / = " meaning less than or equal to, or greater than or equal to): a. "Multiblock" polymer or copolymer means a polymer comprised of multiple block sequences of monomer units where the structure or composition of a given sequence differs from that of its neighbor. Furthermore a multiblock copolymer as defined herein will contain a given sequence at least twice in every polymer chain. b. The term "composition distribution" refers to the variation in comonomer composition between different polymer chains and can be described as a difference, in mole percent, of a given weight percent of a sample from the mean mole percent composition. The distribution need not be symmetrical around the mean; when expressed as a number, for example 15% , this shall mean the larger of the distributions from the mean. c. As used herein, the term "elastomeric" refers to a material which tends to regain its shape upon extension, such as one which exhibits a positive power of recovery at 100, 200 and 300% elongation. d. The term "melting point index", also referred-to as MPI = Tm / Xc, means the ratio of the melting point of the copolymer, Tm, to the mole fraction of the crystal lizable component, Xc. By crystallizable component, we mean a monomer component whose homopolymer is a crystalline polymer. The melting point is taken as a maximum in a melting endotherm, as determined by differential scanning calorimetry.
The copolymers of the present invention have the following characteristics:
(a) a mole fraction of crystallizable component Xc from 30 - 99%;
(b) a molecular weight distribution Mw/ Mn </= 10; and
(c) melting points above about 90°C; which copolymers comprise from 0-70% by weight of an ether soluble fraction, and from 0-95% of a hexanes soluble fraction which can exhibit a melting range up to about 125°C, and from 0-95% of a hexanes insoluble fraction which can exhibit a melting range up to about 142°C.
The copolymers of the present invention in one embodiment can be characterized as reactor blends in that they can be fractionated into fractions of differing degrees of crystallinity and differing melting points. Nevertheless, the comonomer composition of the various fractions of the copolymers are within 15% of the composition of the resultant polymer product produced in the reactor.
The melting points of the copolymers of the present invention are high, typically above 90 °C and the melting point indices, Tm/ Xc are also high, typically above 80 °C and preferably above 115°C. The fractions can also exhibit high melting point indices. For example, it is possible to isolate a hexanes soluble fraction from the copolymers of the present invention that exhibits a melting point as high as 115 °C and a melting point index as high as 160 °C. The glass transition temperatures of the copolymers are low, typically less than -20 °C and preferably below -50 °C.
The molecular weights of the polymers of the present invention can be quite high, with weight average molecular weights in excess of Mw = 1,000,000 readily obtained and molecular weights as high as 2,000,000 observed. The molecular weight distributions of the copolymers are typically Mw/Mn < /= 10, preferably Mw/Mn < /= 8 and most preferably < /= 6. In one embodiment, the copolymers of the present invention exhibit useful elastomeric properties. They can be used in a variety of applications typical of amorphous or partially crystalline elastomers and as compatibilizers for copolymer blends.
While not wishing to be bound by theory, it is believed that in the process of the invention, different active species of the catalyst are in equilibrium during the construction of the copolymer chains. This is provided for in the present invention by a class of unbridged metallocenes that are capable of isomerizing between states that have different copolymerization characteristics during the polymerization process. This process can thus lead to multiblock copolymers or copolymer blends where the blocks or components of the blends have different compositions of comonomers.
One embodiment of the invention includes metallocene catalysts which are able to interconvert between states whose coordination geometries are different. Thus, the invention includes selecting the substituents of the metallocene cyclopentadienyl ligands so that the rate of interconversion of the two states is within several orders of magnitude of the rate of formation of a single polymer chain. That is, if the rate of interconversion between states of the catalyst, η , is greater than the rate of formation of an individual polymer chain, rf , on average, the polymer resulting from use of the inventive process and catalysts can be characterized as multiblock (as defined above). If the rate of interconversion is less than the rate of formation, the result is a polymer blend. Where the rates are substantially balanced, the polymer can be characterized as a mixture of blend and multiblock. There may be a wide range of variations and intermediate cases amongst these three exemplars.
The nature of the substituents on the cyclopentadienyl ligands is critical; the substitution pattern of the cyclopentadienyl ligands should be such that the coordination geometries are different in order to provide for different reactivities toward ethylene and other alpha olefins while in the two states (see Figure 1) and that the rate of interconversion of the states of the catalyst are within several orders of magnitude of the rate of formation of a single chain.
A further embodiment includes metallocene catalysts which are able to interconvert between more than two states whose coordination geometries are different. This is provided for by metallocenes with cyclopentadienyl-type ligands substituted in such a way that more than two stable states of the catalyst have coordination geometries that are different, for example, a catalyst with four geometries is illustrated in one embodiment in Figure 2.
According to the process of this invention, the properties of the copolymers can be controlled by changing the nature of the cyclopentadienyl units on the catalysts, by changing the nature of the metal atom in the catalyst, by changing the nature of the comonomers and the comonomer feed ratio, and by changing the temperature. The molecular weights of the polymers produced with the catalysts of the invention are very high. The molecular weight of the polymer product can be controlled, optionally, by controlling the temperature or by adding any number of chain transfer agents such as hydrogen or metal alkyls, as is well known in the art.
The catalyst system of the present invention consists of the transition metal component metallocene in the presence of an appropriate cocatalyst. In broad aspect, the transition metal compounds have the formula:
L' " X' Formula 1
in which M is a Group 3, 4 or 5 Transition metal, a Lanthanide or an Actinide, X and X' are the same or different uninegative ligands, such as but not limited to hydride, halogen, hydrocarbyl, halohydrocarbyl, amine, amide, or borohydride substituents (preferably halogen, alkoxide. or to C7 hydrocarbyl), and L and L' are the same or different polynuclear hydrocarbyl, silahydrocarbyl, phosphahydrocarbyl, azahydrocarbyl, arseni- hydrocarbyl or borahydrocarbyl rings, typically a substituted cyclo-pentadienyl ring or heterocyclopentadienyl ring, in combination with an appropriate cocatalyst. Exemplary preferred Transition Metals include Titanium, Hafnium, Vanadium, and, most preferably, Zirconium. An exemplary Group 3 metal is Yttrium, a Lanthanide is Samarium, and an Actinide is Thorium.
Preferably L and L' have the formula:
Figure imgf000007_0001
Formula 2
where Ri, R2, R3, R9, and Rio may be the same or different hydrogen, alkyl, alkylsilyl, aryl, alkoxyalkyl, alkoxyaryl, alkoxysilyl, aminoalkyl, aminoaryl or substituted alkyl, alkylsilyl or aryl substituents of 1 to about 30 carbon atoms.
Ligands of this general structure include substituted cyclopentadienes. Other ligands L and L' of Formula 2 for the production of propylene-ethylene copolymers include substituted cyclopentadienes of the general formula:
Figure imgf000008_0001
Formula 3
where R2-R10 have the same definition as Ri , R2, R3, R9, and Rio above. Preferred cyclopentadienes of Formula 3 include 3,4-dimethyl-l-phenyl-l,3-cyclopentadiene (R2=R3 =CH3, R6=H); 3,4-dimethyl-l-p-tolyl-l ,3-cyclopentadiene (R2=R3 =CH3, R6=CH3); 3,4,-dimethyl-l-(3,5-bis(trifluoromethyl)phenyl)-l,3-cyclopentadiene (R2= 3 =CH3, R6=CF3); and 3,4-dimethyl-l-(4-tert-butylphenyl)-l ,3-cyclo-pentadiene (R2= R3 =CH3, R6=tBu). Alternately preferred L and L' of Formula 1 include ligands of Formula 2 wherein
Rl is an aryl group, such as a substituted phenyl, biphenyl, or naphthyl group, and R2 and R3 are connected as part of a ring of three or more carbon atoms. Especially preferred for L or L' of Formulas 1- 3 for producing the copolymers of this invention are substituted indenyl ligands, more particularly 2-arylindene of formula:
Figure imgf000008_0002
Formula 4
where R4 - R14 may be the same or different hydrogen, halogen, aryl, hydrocarbyl, silahydrocarbyl, or halohydrocarbyl substituents. That is, Rl of Formula 2 is R4-R8- substituted benzene, and R2, R3 are cyclized in a 6-carbon ring to form the indene moiety.
Particularly preferred 2-aryl indenes include at present as preferred best mode compounds: 2-phenylindene; l-methyl-2-phenyl indene; 2-(3,5-dimethylphenyl) indene; 2-
(3,5- bis-trifluoromethylphenyl) indene; l-methyl-2-(3,5-bis-trifluoromethylphenyl) indene;
2-(3,5-bis-tertbutylphenyl) indene; l-methyl-2-(3,5-bis-tertbutylphenyl) indene; 2-(3,5-bis- trimethyl- silylphenyl)indene; l-methyl-2-(3,5-bis-trimethylsilylphenyl)indene; 2-(4- fluorophenyl) indene; 2-(2, 3, 4, 5-tetrafluorophenyl) indene; 2-(2, 3, 4, 5, 6- pentafluorophenyl) indene; 2-(l -naphthyl) indene; 2-(2-naphthyl) indene; 2-[(4- phenyl)phenyl] indene; and 2-[(3-phenyl) phenyl] indene.
Preferred metallocenes according to the present invention include: bis(2-phenylindenyl) zirconium dichloride; bis(2-phenylindenyl) zirconium dimethyl; bis(l-methyl-2-phenylindenyl) zirconium dichloride; bis(l-methyl-2-phenylindenyl) zirconium dimethyl; bis[2-(3,5-dimethylphenyl)indenyl] zirconium dichloride; bis[2-(3,5-bis-trifluoromethylphenyl)indenyl] zirconium dichloride; bis[2-(3,5-bis-tertbutylphenyl)indenyl] zirconium dichloride; bis[2-(3,5-bis-trimethylsilylphenyl)indenyl] zirconium dichloride; bis[2-(4,-fluorophenyl)indenyl] zirconium dichloride; bis[2-(2,3,4,5,-tetraflorophenyl)indenyl] zirconium dichloride; bis(2-(2,3,4,5,6-pentafluorophenyl)indenyl]) zirconium dichloride; bis[2-(l-naphthyl)indenyl] zirconium dichloride; bis(2-(2-naphthyl)indenyl]) zirconium dichloride; bis(2-[(4-phenyl)phenyl]indenyl]) zirconium dichloride; bis[2-[(3-phenyl)phenyl]indenyl] zirconium dichloride;
(pentamethylcyclopentadienyl)(l-methyl-2-phenylindenyl) zirconium dichloride; (pentamethylcyclopentadienyl)(2-phenylindenyl) zirconium dichloride;
(pentamethylcyclopentadienyl)(l-methyl-2-phenylindenyl) zirconium dimethyl;
(pentamethylcyclopentadienyl)(2-phenylindenyl) zirconium dimethyl;
(cyclopentadienyl)(l-methyl-2-phenylindenyl) zirconium dichloride;
(cyclopentadienyl)(2-phenylindenyl) zirconium dichloride; (cyclopentadienyl)(l-methyl-2-phenylindenyl) zirconium dimethyl;
(cyclopentadienyl)(2-phenylindenyl) zirconium dimethyl;
(l-methyl-2-phenylindenyl)(2-phenylindenyl) zirconium dichloride;
(l-methyl-2-phenylindenyl)[2-(3,5-bis-trifluoromethylphenyl)indenyl] zirconium dichloride;
[l-methyl-2-(3,5-bis-trifluoromethylphenyl)indenyl](2-phenylindenyl) zirconium dichloride; [l-methyl-2-(3,5-bis-trifluoromethylphenyl)indenyl][2-(3,5-bis- trifluoromethylphenyl)indenyl] zirconium dichloride;
(l-methyl-2-phenylindenyl)[2-(3,5-bis-tertbutylphenyl)indenyl] zirconium dichloride; and the corresponding hafnium compounds such as: bis(2-phenylindenyl) hafnium dichloride; bis(2-phenylindenyl) hafnium dimethyl; bis(l-methyl-2-phenylindenyl) hafnium dichloride; bis(l-methyl-2-phenylindenyl) hafnium dimethyl; bis [2-(3,5-dimethylphenyl)indenyl] hafnium dichloride; bis[2-(3,5-bis-trifluoromethyphenyl)indenyl] hafnium dichloride; bis[2-(3,5-bis-tertbutylphenyl)indenyl] hafnium dichloride; bis[2-(3,5-bis-trimethylsilylphenyl) indenyl] hafnium dichloride; bis[2,(4-fluorophenyl)indenyl] hafnium dichloride; bis[2-(2,3,4,5-tetrafluorophenyl)indenyl] hafnium dichloride; bis [2-(2,3,4,5.6-pentafluorophenyl)indenyl] hafnium dichloride; bis[2-(l-naphthyl)indenyl] hafnium dichloride; bis[2-(2-naphthyl)indenyl] hafnium dichloride; bis(2-((4-phenyl)phenyl)indenyl]) hafnium dichloride; bis[2-[(3-phenyl)phenyl]indenyl] hafnium dichloride;
(pentamethylcyclopentadienyl)( 1 -methyl-2-phenylindenyl) hafnium dichloride;
(pentamethylcyclopentadienyl)(2-phenylindenyl) hafnium dichloride;
(pentamethylcyclopentadienyl)(l-methyl-2-phenylindenyl) hafnium dimethyl;
(pentamethylcyclopentadienyl)(2-phenylindenyl) hafnium dimethyl; (cyclopentadienyl)(l-methyl-2-phenylindenyI) hafnium dichloride;
(cyclopentadienyl)(2-phenylindenyl) hafnium dichloride;
(cyclopentadienyl)(l-methyl-2-phenylindenyl) hafnium dimethyl;
(cyclopentadienyl)(2-phenylindenyl) hafnium dimethyl;
(l-methyl-2-phenylindenyl)(2-phenylindenyl) hafnium dichloride; (l-methyl-2-phenylindenyl)[2-(3,5-bis-trifluoromethylphenyl)indenyl] hafnium dichloride;
[l-methyl-2-(3,5-bis-trifluoromethylphenyl)indenyl](2-phenylindenyl) hafnium dichloride;
[l-methyl-2-(3,5-bis-trifluoromethylphenyl)indenyl][2-(3,5-bis- trifluoromethylphenyl)indenyl] hafnium dichloride;
(l-methyl-2-phenylindenyl)[2-(3,5-bis-tertbutylphenyl)indenyl] hafnium dichloride; and the like.
Other metallocene catalyst components of the catalyst system according to the present invention include: bis(3,4-dimethyl-l-phenylcyclopentadienyl) zirconium dichloride; bis(3,4-dimethyl-l-p-tolylcyclopentadienyl) zirconium dichloride; bis(3,4-dimethyl-l-(3,5 bis(trifluoromethyl)phenyl)cyclopentadienyl)zirconium dichloride; bis(3,4-dimethyl-l-(4-tert-butylphenyl)cyclopentadienyl) zirconium dichloride;
(3,4-dimethyl-l-phenyl-l ,3-cyclopentadiene)(3,4-dimethyl-l-p-tolylcyclopentadienyl) zirconium dichloride;
(3,4-dimethyl-l-phenylcyclopentadienyl)(3,4-dimethyl-l-(3,5 bis(trifluoromethyl)phenyl)cyclopentadienyl) zirconium dichloride;
(3,4-dimethyl-l-phenylcyclopentadienyl)(3,4-dimethyl-l-(4-te/ -butylphenyl) cyclopentadienyl) zirconium dichloride; and the corresponding hafnium compounds, such as: bis(3,4-dimethyl-l-phenylcyclopentadienyl) hafnium dichloride; bis(3,4-dimethyl-l-p-tolylcyclopentadienyl) hafnium dichloride; bis(3,4-dimethyl-l-(3,5 bis(trifluoromethyl)phenyl)cyclopentadienyl)hafnium dichloride; bis(3,4-dimethyl-l-(4-tert-butylphenyl)cyclopentadienyl) hafnium dichloride;
(3,4-dimethyl-l-phenylcyclopentadienyl)(3,4-dimethyl-l-p-tolylcyclopentadienyl) hafnium dichloride; (3,4-dimethyl-l-phenylcyclopentadienyl)(3,4-dimethyl-l-(3,5 bis(trifluoromethyl)phenyl)cyclopentadienyl) hafnium dichloride; (3,4-dimethyl-l-phenylcyclopentadienyl)(3,4-dimethyl-l-(4-terr-butylphenyl) cyclopentadienyl) hafnium dichloride; and the like.
It should be understood that other unbridged, rotating, non-rigid, fluxional metallocenes may be employed in the methods of this invention, including those disclosed in our above-identified Provisional application, which is hereby incorporated by reference to extent needed for support.
The Examples disclose a method for preparing the metallocenes in high yield. Generally, the preparation of the metallocenes consists of forming the indenyl ligand followed by metallation with the metal tetrahalide to form the complex.
Appropriate cocatalysts include alkylaluminum compounds, methylaluminoxane, or modified methylaluminoxanes of the type described in the following references: U.S. Patent 4,542, 199 to Kaminsky, et al,; Ewen, J. Am. Chem. Soc , 106 (1984), p. 6355; Ewen, et al. , J. Am. Chem. Soc. 109 (1987) p. 6544; Ewen, et al., J. Am. Chem. Soc. 110 (1988), p. 6255; Kaminsky, et al, Angew. Chem. , Int. Ed. Eng. 24 (1985), p. 507. Other cocatalysts which may be used include Lewis or protic acids, such as B(CόF5)3 or (PhNMe2H) B(C6F5)4", which generate cationic metallocenes with compatible non- coordinating anions in the presence or absence of alkyl-aluminum compounds. Catalyst systems employing a cationic Group 4 metallocene and compatible non-coordinating anions are described in European Patent Applications 277,003 and 277,004 filed on 27.01.88 by Turner, et al. ; European Patent Application 427,697-A2 filed on 09.10-90 by Ewen, et al. ; Marks, et al., J. Am. Chem. Soc , 113 (1991), p. 3623; Chien, et al., J. Am. Chem. Soc, 113 (1991), p. 8570; Boch ann et al., Angew. Chem. Intl., Ed. Engl. 7 (1990), p. 780; and Teuben et al., Organometallics, 11 (1992), p. 362, and references therein.
The catalysts of the present invention comprise un-bridged, non-rigid, fluxional metallocenes which can change their geometry with a rate that is within several orders of magnitude of the rate of formation of a single polymer chain, on average. In accordance with the invention, the relative rates of interconversion and of formation can be controlled by selecting the substituents (or absence thereof) of the cyclopentadienyl ligands so that they can alternate in structure between states of different coordination geometries which have different selectivity toward a particular comonomer. In one of many embodiments, these catalyst systems can be placed on a suitable support such as silica, alumina, or other metal oxides, MgCl2 or other supports. These catalysts can be used in the solution phase, in slurry phase, in the gas phase, or in bulk monomer. Both batch and continuous polymerizations can be carried out. Appropriate solvents for solution polymerization include liquified monomer, and aliphatic or aromatic solvents such as toluene, benzene, hexane, heptane, diethyl ether, as well as halogenated aliphatic or aromatic solvents such as CH2CI2, chloro benzene, fluorobenzene, hexaflourobenzene or other suitable solvents. Various agents can be added to control the molecular weight, including hydrogen, silanes and metal alkyls such as diethylzinc
The metallocenes of the present invention, in the presence of appropriate cocatalysts, are useful for the homo-polymerization and co-polymerization of alpha-olefins, such as propylene, 1-butene, 1-pentene, 4-methyl-l-pentene, 1-hexene, 1-octene, and combinations thereof, and of copolymerization with ethylene. The polymerization of olefins is carried out by contacting the olefin(s) with the catalyst systems comprising the transition metal component and in the presence of an appropriate cocatalyst, such as an aluminoxane, a Lewis acid such as B(C6F5)3, or a protic acid in the presence of a non- coordinating counterion such as B(C6F5)4".
The metallocene catalyst systems of the present invention are particularly useful for the polymerization of ethylene and alpha-olefin comonomers as well as alpha-olefin monomer mixtures to produce co-polymers with novel elastomeric properties. The properties of elastomers are characterized by several variables. The tensile set (TS) is the elongation remaining in a polymer sample after it is stretched to an arbitary elongation (e.g. 100% or 300%) and allowed to recover. Lower set indicates higher elongational recovery. Stress relaxation is measured as the decrease in stress (or force) during a time period (e.g. 30 sec. or 5 min.) that the specimen is held at extension. There are various methods for reporting hysteresis during repeated extensions. In the present application, retained force is measured as the ratio of stress at 50% elongation during the second cycle recovery to the initial stress at 100% elongation during the same cycle. Higher values of retained force and lower values of stress relaxation indicate stronger recovery force. Better general elastomeric recovery properties are indicated by low set, high retained force and low stress relaxation.
Brief Description of the Drawings The invention is described, inter alia, with reference to the drawings, in which:
Fig. 1 is a stereoisomeric representation of unbridged metallocenes of this invention having different substituents in the positions Ri through R Q with the arrows showing the interconversion between states A and B in which the reactivity toward ethylene, rg, and other alpha olefins differs in the two states; and Fig. 2 shows four possible coordination geometries for unbridged metallocenes of this invention, with the circles representing coordination sites for olefin insertion. Detailed Description Including The Best Mode of Carrying Out The Invention
The following detailed description illustrates the invention by way of example, not by way of limitation of the principles of the invention. This description will clearly enable one skilled in the art to make and use the invention, and describes several embodiments, adaptations, variations, alternatives and uses of the invention, including what are presently believed to be the best modes of carrying out the inventions.
In this regard, the invention is illustrated in the several examples, and is of sufficient complexity that the many aspects, interrelationships, and sub-combinations thereof simply cannot be fully illustrated in a single example. For clarity and conciseness, several of the examples show, or report only aspects of a particular feature or principle of the invention, while omitting those that are not essential to or illustrative of that aspect. Thus, the best mode embodiment of one aspect or feature may be shown in one example or test, and the best mode of a different aspect will be called out in one or more other examples, tests, structures, formulas, or discussions. The metallocene catalysts of the present invention are represented in one embodiment in Figure 1 where the ligands L and L' are substituted cyclopentadienyl rings. As shown in the Figure, in state A cyclopentadienyl substituents Ri, R2 and Rό and R7 project over the ligands X = X' whereas in state B, cyclopentadienyl substituents Rj, R2 and Re and R9 project over the ligands X = X'. As provided for in the process of this invention, catalysts derived from these metallocenes where substituents Rό and R7 are different from Rs and R9 will exhibit reactivity ratios for ethylene in state A (ΓEA) different from that in state B (IΈB)-
Another embodiment of the invention is illustrated in Figure 2 where the ligands L and L' are different substituted 2-arylindenyl ligands such that the metallocene interconverts between four states with different coordination geometries. As shown in the Figure, in two states a methyl group projects over the coordination sites for olefin insertion (represented in this figure by circles) and in two states the methyl group projects away from the coordination sites for the olefin. The following examples illustrate the control of the polymer properties via selection of the ligand substitution groups.
EXAMPLES.
All organometallic reactions were conducted using standard Schlenk and drybox techniques. Elemental analyses were conducted by E+R Microanalytical Laboratory. Unless otherwise specified all reagents were purchased from commercial suppliers and used without further purification. 2 -Phenyl indene, l-methyl-2-phenylindene, 2-(bis(3',5'- trifluoromethyl) phenylindene, bis(2-phenylindenyl)zirconium dichloride, rac- and meso- bis(l-methyl-2-phenylindenyl)zirconium dichloride, ethylene-bis(indenyl)zirconium dichloride and bis(2-(bis(3',5'-trifluoromethyl)phenylindenyl)-zirconium dichloride were prepared according to the literature procedures. (Kravchenko, R. ; Waymouth. R. M. Macromolecules 1998, 31, 1-6.) Hexane, pentane and methylene chloride used in organometallic synthesis were distilled from calcium hydride under nitrogen. Tetrahydrofuran was distilled from sodium/benzophenone under nitrogen. Toluene, ethylene and propylene were passed through two purification columns packed with activated alumina and supported copper catalyst. 1-Hexene and chlorofoπτ /3 were distilled from calcium hydride and benzene-tfό was distilled from sodium/benzophenone.
I. Metallocene Synthesis Ethylene-bis(indenyl)zirconium dichloride (Metallocene 1). This complex was prepared as described in Wild, F. R. W. P. ; Wasiucionek, M. ; Huttner, G. ; Brintzinger, H. H. J. Organomet. Chem. 1985, 288, 63-7.
Bis(2-phenylindenyl)zirconium dichloride (Metallocene 2). This complex was prepared as described in Bruce, M. D. ; Coates, G. W. ; Hauptman, E. ; Waymouth, R. M. ; Ziller, J. W. J. Am. Chem. Soc. 1997, 119, 11174-11182.
Bis(2-phenylindenyl) hafnium dichloride (Metallocene 3). This complex was prepared as described in Bruce, M. D. ; Coates, G. W. ; Hauptman, E. ; Waymouth, R. M. ; Ziller, J. W. J. Am. Chem. Soc. 1997, 119, 11174-11182.
Example 1. Preparation of 2-(bis-3,5-trifluoromethylphenyl)indene (Ligand A)
A 3-neck 500 mL round-bottomed flask fitted with a condenser and an addition funnel was charged with 2.62g (0.11 mol) of Mg turnings and 20 mL of anhydrous diethyl ether. Slow addition of a solution of 25.10 g (0.09 mol) of 3,5-bis(trifluoromethyl) bromobenzene in diethyl ether (100 mL), followed by refluxing for 30 min, gave a brown- grey solution of the aryl Grignard reagent. The solution was cooled to room temperature (RT), filtered over a plug of Celite and evacuated to yield a brown oil. Toluene (40 mL) was added and the suspension cooled to 0°C whereupon a solution of 2-indanone (9.22 g, 0.07 mol) in toluene (60 mL) was added dropwise to give a tan-brown slurry. This mixture was warmed to room temperature and stirred for an additional 3 hours. After cooling to 0°C it was quenched with 150 mL of water, hexane (200 mL) added and the reaction mixture neutralized with 5M HC1. The organic layer was separated, and the aqueous layer was extracted with two 50-mL portions of hexane. The combined organic layers were washed with two 50-mL portions of brine and dried over anhydrous magnesium sulfate. After filtration over Celite, the solvent was removed under vacuo yielding 21.5 g (89% based on 2-indanone) of 2-(bis-3,5-trifluoromethylphenyl) indanol as an off-white solid. lU NMR (CDCI3, 23 C, 400 MHz): d 8.05 (s. 2H), 7.80 (s, 1H), 7.5-7.0 (M, 4H). 3.41 (m. 4H), 2.21 (s, 1H, OH). Under argon, this alcohol (21.5 g. 0.06 mol) and p-toluene-sulfonic acid monohydrate (800 mg) were dissolved in toluene (250 mL) and the solution was heated to reflux for 6 hours to afford 14.4 g. (70%) of 2-(bis-3,5- (trifluoromethyl)-phenyl) indene upon recrystallization from diethyl ether/hexane at -18 C. lH NMR (CDCI3, 23°C, 400 MHz): d 8.01 (s, 2H), Arf), 7.75 (s, 1H. Arf), 7.52 (d, J = 7 Hz, 1H), 7.47 (d, J = 7 Hz, 1H), 7.43 (s, 1H), 7.33 (dd, 2J = 7 Hz, 1H), 7.27 (dd, 2J=7 Hz, 1H), 2.83 (s, 2H). 13C NMR (CDCI3 , 23 C, 100 MHz): L144.3 (s), 143.1 (s), 138.0 (s), 132.1 (q, 2JC-F= 33 Hz), 130.1 (d, JC-H= 167 Hz), 127.0 (dd), Jc-H = 160 Hz, 2JC-H = 7 Hz), 126.0 (dd, JC-H = 159 Hz, 2JC-H = 7 Hz)m 125.2 (brd, JC-H = 162 Hz), 123.9 (dd, JC-H = 156 Hz, 2JC-H= Hz), 123.4 (q, JC-F= 273 Hz, CF3), 121.8 (dd, Jc-H = 160 Hz, 2JC-H = 8 Hz), 120.6 (brd. JC-H = 1 7 Hz), 38.9 (td, JC-H = 127 Hz, 2JC-H =7 Hz, CH2). C,H analysis: Anal. Found (Calcd): C. 62.45 (62-20); H 3.01 (3.07).
Example 2. Preparation of Bis(2-(bis-3,5-trifluoromethylphenyl)indenyl) zirconium dichloride, (Metallocene 4)
N-Butyllithium (2.5 M in hexanes, 0.850 mL, 2.13 mmol) was added to a solution of 2-(bis-3,5-trifluoromethylphenyl) indene (648 mg, 1.97 mmol) in toluene (15 mL). The heterogeneous solution was stirred at ambient temperature for 4 hours 30 minutes to give a green-yellow solution which was treated with a suspension of ZrCl4 (240 mg, 1.03 mmol)in toluene (20 mL) via cannula. The yellow suspension was stirred at room temperature for 2.5 hours, heated to ca. 80° C, and filtered over a plug of Celite. After washing the Celite with hot toluene several times (3 x 10 mL), the filtrate was concentrated and cooled to 18 C to give 442 mg (55%) of light yellow crystals of Bis(2-(Bis-3,5- trifluoromethylphenyl)-indenyl)zirconium dichloride. H NMR (CόDό, 23 C, 400 MHz): d 7.67 (s, 2H, Arf), 7.55 (s, 4H, Arf), 7.19 (m, 4H, Ar), 6.89 (m, 4H, Ar), 5.96 (s, 4H, Cp-H). i 3C NMR (CόDό, 23 C, 100 MHz: d 135.6 (s), 133.1 (s), 131.6 (q, 2JC-F= 33 Hz), 127.1 (brd, JC-H= 161 Hz), 126.8 (s), 126.4 (dd, JC-H= 161 Hz, 2JC-H= 8 Hz), 125.4 (dd, Jc-H = 167 Hz), 2JC-H= 5 Hz), 123.8 (q, JC-F= 273 Hz, C-R), 121. 8 (brd, JC-H = 159 Hz), 102. 5 (dd, JC-H = 176 Hz, 2JC-H = 7 Hz, Cp (C-H). C,H analysis: Anal, found (Calcd.): C, 49.99 (50.01); H 2.32 (2.22).
Example 3. Preparation of Bis(2-(bis-3,5-trifluoromethylphenyl)indenyl) hafnium dichloride, (Metallocene 5) N-Butyllithium (1.6M in hexanes, 2 mL. 3.20 mmol) was added dropwise at room temperature to a solution of 2-(bis-3.5-trifluoromethylphenyl)indene (1.03 g. 3.14 mmol) in diethyl ether (10 L). After stirring for 30 min, the solvent was removed in vacuo leaving a green-yellow solid. In a drybox, HfCl4, (510 mg, 1.59 mmol) was added to the lithium salt. The solids were then cooled to -78 °C at which temperature toluene (45 mL) was slowly added. The flask was allowed to reach ambient temperature and the suspension was stirred for 24 hours after which time it was heated for 15 min to ca. 80 °C (heat gun). The solvent was then removed in vacuo. The solid was extracted with CH2CI2 (50 mL) and the solution filtered over a plug of Celite. After washing the Celite with 4 x 15 mL CH2CI2, the solvent was removed in vacuo from the filtrate. The solid was dissolved in 15 mL of CH2CI2, filtered and over filtrate a layer of hexane (40 mL) was slowly added. Crystals of Bis(2-(bis-3,5-trifluoromethylphenyl)indenyl) hafnium dichloride Catalyst E were obtained from this layered solution at -18 C. l NMR (CόDό, 23°C, 200 MHz); d 7.65 (s, 2H, Arf), 7.51 (s, 4H, Arf), 6.7-7.3 (m, 8H Ar), 5.63 (s, 4H, Cp-H). l C NMR (C6Dό 23°C, 100 MHz): d 135.8 (s), 132.9 (s), 131.6 (q, 2JC-F= 34 Hz), 127.2 (brd, JC-H = 160 Hz), 126.3 (dd, JC-H = 161 Hz, 2JC-H = 8 Hz), 126.0 (s), 125.6 (dd, JC-H = 167 Hz, 2JC-H = 5 Hz), 123.8 (q, Jc-F= 273 Hz, CF3), 121.7 (brd, JC-H = 161 Hz), 100.1 (dd, JC-H = 176 Hz, 2JC-H = Hz, Cp C-H). C, H analysis: Anal. Found (Calcd.): C, 45.10 (45-18); H, 1.87 (2.01).
Example 4. l-Methyl-2-(bis-3* ,5*-trifluoromethylphenyl)indene and 3-methyl-2-(bis- 3 * ,5 ' -trifluoromethylphenyl)indene. A solution of 2-bis-3' ,5'-trifluoromethylphenyl)indene (1.819 g, 5.54 mmol) in tetrahydrofuran (30 mL) was cooled to -78 °C and BuLi (2.5 M in hexanes, 2.33 mL, 5.82 mmol) was added dropwise. The resulting orange-brown solution was allowed to warm to room temperature and stirred for an additional 30 min. Then CH3I (1.20 mL, 19 mmol) was added to this solution and the greenish reaction mixture was stirred for 20 h at room temperature. Methanol (20 mL) was added and the solvents removed in vacuo. The resulting brown solid was extracted with toluene (30 mL) and filtered through a glass frit packed with Celite. The brown solution was washed with H2O (2 x 10 mL) and saturated NaCl solution (2 x 10 mL), dried over MgSO4, and then evaporated to dryness. Crystallization from hexanes gave yellow crystals of 5.7 (1.073 g). H NMR (20 °C, CDCI3, 400 MHz): 7.87 (s, 2H), 7.75 (s, 1H), 7.49 (d, 1H, J = 7.3 Hz), 7.42 (d, 1H, J = 7.6 Hz), 7.37 (t, 1H, J = 7.3 Hz), 7.26 (td, 1H, J = 7.3 Hz, J = 1.2 Hz), 3.78 (s, 2H), 2.33 (s, 3H). Anal. Calcd (Found) for C18H12F6: C 63.16 (63.12); H 3.53 (3.62). Repeated crystallization from hexanes gave a mixture of isomers of the ligand (309 mg) in 4 : 1 ratio. ]H NMR: 3.14 (q, 1H, J = 7.0 Hz), 0.87 (d, 3 H, J = 7.1 Hz). Overall yield 1.073 g, 73%.
Example 5. Synthesis of (2-phenylindenyl) zirconium trichloride.
Solid Zr(NMe2)4 (1.280 g, 4.785 mmol) and 2-phenylindene (0.920 g, 4.785 mmol) were combined with toluene (30 mL) in a 100-mL Schlenk tube and the resulting pale yellow solution was stirred for 2.5 h at room temperature under slightly reduced pressure. Then the solution was evaporated to dryness to give a yellow oil which was extracted with pentane (20 L) and filtered through a cannula fitted with a double layer of filter paper. The resulting pentane solution was concentrated to a total volume of 10 mL and placed into a -50 °C freezer overnight. The resulting yellow solid was isolated, dried in vacuo, and redissolved in CH2CI2 (15 mL). The pale yellow solution was cooled to 0 C and chlorotrimethylsilane (2 mL, 15.8 mmol) was added via syringe. The bright yellow solution was allowed to warm to room temperature and stirred for 1 h. Then the solution was evaporated to dryness to yield a yellow/orange foamy solid. Toluene (30 mL) was added and the mixture was stirred for 48 h to yield a lemon yellow powder, which was isolated and dried in vacuo (1.098 g, 59% yield). This material was used without further purification.
Example 6. Synthesis of (2-phenylindenyl)(l-methyl-2-phenylindenyl) zirconium di- chloride, (Metallocene 6).
Butyllithium (2.5 M in hexane, 0.43 mL, 1.08 mmol) was added via syringe to the solution of l-methyl-2-phenylindenyl (212 mg, 1.029 mmol) in diethyl ether (25 mL) at -78 °C. The resulting light yellow solution was allowed to warm to room temperature and stirred for additional 30 min. The ether was removed in vacuo to yield a white powdery solid, which was combined with solid (2-phenylindenyl)zirconium trichloride (400 mg, 1.029 mmol) and toluene (50 mL). The resulting suspension was stirred for 24 h at room temperature. Gradually the solids dissolved to give a yellow turbid solution. The mixture was filtered through a glass frit packed with Celite and then evaporated to dryness. The resulting yellow solid was recrystallized from CH2CI2 (10 mL) layered with pentane (30 mL) at -50 °C to give metallocene 6., 181 mg, 31 % yield. !H NMR (20 °C, CόDό, 400 MHz): d 7.41 (d, 2H, J = 1 1.2 Hz), 7.30 (d, 2H, J = 10.8 Hz), 7.24-6.80 (m, 13H), 6.73 (d, 1H, J = 11.2 Hz), 6.50 (d, 1H, J = 3.2 Hz), 6.26 (d, 1H, J = 3.3 Hz), 5.98 (s, 1H), 2.42 (s, 3H). i C { H} NMR (20 °C, CDCI3, 125 MHz): d 133.75 (C), 133.10 (C), 132.38 (C), 131.41 (C), 129.54 (C), 129.06 (C-H), 128.90 (C-H), 128.70 (C-H), 128.67 (C-H), 128.14 (C-H), 126.95 (C), 126.72 (C-H), 126.58 (C-H), 126.56 (C-H), 126.43 (C-H), 126.26 (C-H), 125.58 (C-H), 125.05 (C), 124.90 (CH), 124.56 (C), 124.35 (C-H), 123.68 (C-H), 121.43 (C), 104.34 (C-H, Cp), 100.70 (C-H, Cp), 99.00 (C-H, Cp), 12.54 (CH3). Anal. Calcd (Found) for C3lH24Cl2Zr: C 66.65 (66.92); H 4.33 (4.36).
Example 7. Synthesis of (2-phenylindenyl)(l-methyl-2-(bis-3', 5*-trifluoro- methylpheuyl)indenyl) zirconium dichloride, Metallocene 7. Butyllithium (2.5 M in hexanes, 0.43 mL, 1.08 mmol) was added to the pale yellow solution of l-methyl-2-(bis-3' ,5'-trifiuoromethylphenyl)indene (352 mg, 1.029 mmol) in diethyl ether (20 mL) at -78 °C via syringe. The resulting yellow solution was allowed to warm to room temperature and stirred for additional 30 min. Ether was removed in vacuo to yield a pale yellow solid which was washed with pentane (20 mL) and combined with solid (2-phenylindenyl)zirconium trichloride (400 mg, 1.029 mmol) and toluene (50 mL). The resulting suspension was stirred for 24 h at room temperature. Gradually the solids dissolved to give a yellow turbid solution. This solution was filtered through a glass frit packed with Celite and then evaporated to dryness. The yellow solid 7 was recrystallized from CH2CI2 (10 mL) layered with pentane (20 mL) at -50 °C: (245 mg, 34 %). 1H NMR (20 °C, CόDό, 400 MHz): 7.67 (s, br, 1H), 7.64 (s, br, 2H), 7.30-6.78 (m, 13H), 6.43 (d, 1H, J = 2.4 Hz), 6.19 (d, 1H, J = 2.4 Hz), 5.59 (s, 1H), 5.32 (s, 1/3 H, CH2CI2), 2.24 (s, 3H). 13C { H} NMR (20 °C, CDCI3, 125 MHz): 135.91 (C-H), 133.59 (C), 132.58 (C), 131.47 (C-CF3, 2JC-F = 33 Hz), 130.76 (C), 130.51 (C), 129.02 (C-H), 128.98 (C-H), 128.80 (C-H), 126.87 (C-H), 126.81 (C-H), 126.77 (C-H), 126.62 (C-H), 126.52 (C-H), 126.25 (C-H), 126.21 (C), 125.34 (C-H), 125.05 (C), 124.09 (C-H), 123.86 (C), 123.23 (CF3, JCF = 273 Hz), 123.17 (C), 121.24 (C-H, br), 119.25 (C), 102.70 (C-H, Cp), 101.76 (C-H, Cp), 99.30 (C-H, Cp), 12.12 (CH3). Anal. Calcd (Found) for C33H22Cl2FόZr x I/6 CH2CI2: C 55.86 (56.20); H 3.37 (3.18). After having been stored for 3-4 weeks in the drybox in a clear vial the yellow compound turned green in color. No changes in H NMR spectrum were detected upon the color change.
Example 8. Synthesis of (2-(bis-3\5*-trifluoromethylphenyl)indenyl) zirconium trichloride. Solid Zr(NMe2)4 ( 1 -260 g, 4.713 mmol) and l-methyl-2-(bis-3' ,5'- trifluoromethylphenyl)indene (1.505 g, 4.58 mmol) were combined with toluene (30 mL) in a 100-mL Schlenk tube and the resulting greenish-brown solution was stirred for 2.5 h at room temperature under slightly reduced pressure. Then the solution was evaporated to dryness to give greenish-brown solid, which was extracted with pentane (30 mL) and filtered through a cannula fitted with a double layer of filter paper. The resulting pentane solution was concentrated to a total volume of 8 mL and placed in a -50 °C freezer overnight. Greenish-brown crystals formed. They were isolated, dried in vacuo and redissolved in CH2CI2 (20 mL). The resulting solution was cooled to 0 °C and chlorotrimethylsilane (2 mL, 15.8 mmol) was added via syringe. The turbid yellow solution was allowed to warm to room temperature, stirred for 1 h, concentrated to a total volume of 1 mL and then diluted with toluene (30 mL). The resulting suspension was stirred for 24 h. The lemon yellow powdery solid was isolated and dried in vacuo (1.390 g, 46 %). iH NMR (20 °C, CDCI3, 400 MHz): 8.19-8.17 (br, 1H), 8.10 (br. 2H), 7.99 (br, 1H). 7.83 (br. 1H), 7.77 (br. 1H), 7.61 (br, 2H). 7.53 (appears as poorly resolved dd, 2H), 7.44-7.38 (br. 1H), 7.30 (br, 2H), 7.20 (m. 1H), 7.03 (br, 2H), 6.95 (s, 1H). 6.83 (br, 1H), 2.45 (br, 6H), 0.41 (s, 9H). Broad peaks in the aromatic region appear to indicate the presence of dimerized or oligomerized forms of (bfmPhIn)ZrCl3. In addition, one NMe2 group (2.45 ppm) and one SiMe3 group (0.41 ppm) per every two 2-bis(3' ,5'- trifluromethyl)-phenylindenyl entities appear to be coordinated to the metal. This material was used without further purification.
Example 9. Synthesis of (2-(bis-3',5*-trifluoromethylphenyl)indenyl)(l-methyl-2- phenylindenyl) zirconium dichloride, (Metallocene 8).
Butyllithium (2.5 M in hexanes, 0.55 mL, 1.38 mmol) was added to the solution of l-methyl-2-phenylindene (277 mg, 1.31 mmol) in diethyl ether (25 mL) at -78 °C via syringe. The resulting light yellow solution was allowed to warm to room temperature, stirred for an additional 15 min, and the ether was removed in vacuo to yield a white powdery solid which was combined with solid (2-(bis-3' ,5'-trifluoromethylphenyl)indenyl) zirconium trichloride- Me3SiNMe2 (695 mg, 1.31 mmol) and toluene (40 mL) at 0 °C. The resulting dark green solution was allowed to warm to room temperature and stirred for 40 h during which time the color of the solution gradually turned lemon-yellow. The turbid solution was filtered through a glass frit packed with Celite and then evaporated to dryness. Orange crystals were obtained from a CH2CI2 (5 mL)/pentane (5 mL) solution stored at -50 °C (200 mg, 28 %). ]H NMR (20 °C, CDCI3, 500 MHz): d 7.84 (s, 2H, br), 7.82 (s, 1H, br), 7.52 (t, 2H, J = 7.5 Hz), 7.43 (m, 3H), 7.36 (m, 2H), 7.29 (m, 2H), 7.20 (t, 1H, J = 6.0 Hz), 7.08 (q, 2H, J = 7.0 Hz), 6.68 (d, 1H, J = 2 Hz), 6.38 (d, 1H, J = 2 Hz), 5.99 (s, 1H), 5.32 (s, 1/3 H, CH2CI2), 2.53 (s, 3H). 13C { 1H} NMR (20 °C, CDCI3, 125 MHz): d 135.48 (C), 133.20 (C), 132.23 (C), 132.20 (C), 131.62 (C-CF3, 2JC.F = 34 Hz), 130.23 (C), 129.03 (CH), 128.61 (CH), 128.44 (C-H), 126.87 (C-H), 126.71 (C-H), 126.70 (C-H), 126.54 (C-H), 126.45 (C-H), 126.24 (C-H), 125.90 (C), 125.17 (C-H), 125.01 (C), 124.43 (C), 124.15 (C-H), 124.13 (C-H), 123.22 (CF3, JC.F = 272 Hz), 121.70 (C-H, br), 102.09 (C-H, Cp), 101.20 (C-H, Cp), 98.51 (C-H, Cp), 12.39 (CH3). Anal. Calcd (Found) for C33H22Cl2FόZr x I/6 CH2CI2: C 56.20 (56.11); H 3.18 (3.09).
Example 10. Synthesis of (2-(bis-3*,5*-trifluoromethylphenyl)indenyl)(l-methyl-2- (bis-3*,5*-trifluorometh3'lphenyl)indenyl) zirconium dichloride, (Metallocene 9).
Butyllithium (2.5 M in hexanes, 0.40 mL, 1.00 mmol) was added to the solution of 2-(bis-3,5-trifluoromethylphenyl)indene (328 mg, 0.958 mmol) in diethyl ether (30 mL) at -78 °C via syringe. The resulting light yellow solution was allowed to warm to room temperature, stirred for additional 2.5 h and the ether was removed in vacuo to yield a gray powdery solid, which was washed with pentane, filtered, and dried in vacuo. The solid was then combined with solid (2-(bis-3',5'-trifluoromethylphenyl)indenyl) zirconium trichloride- Me3SiNMe2 (508 mg, 0.958 mmol) and toluene (50 mL) and the reaction mixture was stirred for 40 h at room temperature. The turbid yellow solution was filtered through a glass frit packed with Celite and then evaporated to dryness. The resulting solid was extracted with CH2CI2 (10 mL). The yellow methylene chloride solution was placed in a -50 °C freezer overnight and a yellow precipitate formed (100 mg, 13 %). 1H NMR (20 °C, CόDό, 500 MHz): d 7.56 (s, 2H, br), 7.48 (s, 2H, br), 7.29 (d, 1H, J = 8.5 Hz), 7.08 (m, 2H), 6.90 (m, 2H), 6.83 (t, 2H, J = 7.0 Hz), 6.66 (t, 1H, J = 7.5 Hz), 6.00 (d, 1H, J = 2.5 Hz), 5.73 (d, 1H, J = 2.5 Hz), 5.48 (s, 1H), 2.14 (s, 3H). 9F NMR (20 °C, CόDό, 282 MHz): 63.65 (s, 3F), 63.57 (s, 3F). 3c { H} NMR (20°C, CDCI3, 125 MHz): d 135.61 (C), 133.85 (C), 132.66 (C), 131.64 (C-CF3, 2JC-F = 33 Hz), 131.44 (C-CF3, 2JC-F = 33 Hz), 130.78 (C), 129.03 (CH), 129.00 (CH), 127.85 (C), 126.79 (CH), 126.63 (CH), 126.57 (CH), 126.35 (CH), 125.91 (CH), 124.95 (CH),
124.74 (C), 124.59 (CH), 124.28 (CH), 123.50 (CF3, JC-F = 273 Hz), 123.15 (CF3, JC-
F = 273 Hz), 122.83 (C), 122.09 (C), 121.89 (CH, br), 121.42 (CH, br), 118.74 (C),
103.28 (CH, Cp), 100.28 (CH, Cp), 99.57 (CH, Cp), 12.17 (CH3). Anal. Calcd (Found) for C35H20Cl2Fl2Zr: C 50.61 (50.90); H 2.43 (2.72).
Example 11. Synthesis of Bis(2-(bis-3,5-te/t-butyl-4-methoxyphenyl) indenyl) zirconium dichloride (Metallocene 10).
A sample of 5.584 g (40 mmol) potassium carbonate and 6.3 mL (100 mmol) iodomethane were reacted with 2.554 g (10 mmol) bis-3,5-terf-butyl-4-hydroxybenzoic acid and heated to 45 °C for 30 h. Flash chromatography of the crude product on silica gel with
7.5% ether in hexanes then recrystallisation from hexanes at -20 °C yielded methyl-bis-3,5- tert-butyl-4-methoxybenzoate. Yield: 2.213 g (7.95 mmol, 80%). ]H NMR (CDCI3): d
1.42 (s, 18H), 3.68 (s, 3H), 3.87 (s, 3H), 7.93 (s, 2H); 13C NMR (CDCI3): d 31.91 , 35.86, 51.93, 64.40, 124.35, 128.24. 144.01 , 163.84, 167.45. The methyl ester (8 mmol) was dissolved in 65 mL of THF in an addition funnel and added to a solution of the di-
Grignard of o-xylylenedichloride solution at -78 °C over approx. 60 minutes, consistently maintaining the temperature below -70 °C during the addition. The reaction mixture was warmed to 0 °C in 1-2 h and 80 mL distilled water was added through the addition funnel in 15-30 minutes. After the reaction mixture was allowed to warm to room temperature the
THF was removed completely from the reaction mixture. The remaining suspension was acidified to pH = l and extracted with methylene chloride. The combined organic layers were dried over magnesium sulfate and stirred with 0.300 g (1.57 mmol) para- toluenesulfonic acid monohydrate for 1 h at room temperature. After extraction with distilled water and drying over magnesium sulfate, the crude product was transferred to silica gel and purified by flash chromatography. Yield 2.346 g (7.01 mmol, 87%). 1H NMR (CD2C12): d 1.47 (s. 18H), 3.71 (s, 3H), 3.79 (s, 2H), 7.14 (s, 1H), 7.15 (td, J = 7.0 Hz, J = 0.8 Hz), 1H), 7.25 (t, J = 7.5 Hz, 1H), 7.37 (d, J = 7.5 Hz, 1H), 7.62 (d, J = 7.5 Hz, 1H), 7.54 (s, 2H); 13C NMR (CD2C12): d 32.18, 36.09, 39.47, 64.65, 120.88, 123.89, 124.41 , 124.68, 125.36, 126.87, 130.67, 143.53, 144.24, 146.05, 147.55, 159.94.
A sample of 1.5 mmol of 2-(bis-3,5-fe/t-butyl-4-methoxyphenyl)indene was dissolved in 50 mL of diethylether. The solution was cooled down to 0 °C and 0.6 mL (1.5 mmol) n- butyllithium (2.5 M in hexanes) was added dropwise via syringe. The cooling bath was removed and the mixture was stirred at ambient temperature for 10 h and evacuated to dryness. Zirconium tetrachloride, 175 mg (0.75 mmol), and 100 mL toluene was added and the reaction mixture stirred virgorously at 25 °C for 3 days. Toluene was removed in vacuo and 50 mL methylene chloride added. The suspension was filtered over celite through a Schlenk-frit under argon and washed with methylene chloride until the filtered liquid remained colorless. The resulting clear solution's volume was reduced to 1/4 to 1/5 and a layer of pentane, hexanes or diethylether was applied carefully. The layered solution was stored at -80 °C for crystallization of the product. Yield: 293 mg (0.353 mmol, 36%), yellow solid. lU NMR (CD2Cl2): d 1.56 (s, 36H), 3.82 (s, 6H), ), 6.64-6.68 (m, 4H), 6.72 (s, 4H), 6.98-7.01 (m, 4H), 7.63 (s, 4H); 13C NMR (CD2C12): d 32.16, 36.13, 64.67, 104.50, 124.32, 125.48, 126.11 , 126.40, 127.03, 129.51 , 144.65, 160.45. Anal. Calcd for C48H58Cl2θ2Zr: C, 69.54; H, 7.05. Found: C, 69.41 ; H, 7.24.
General Polymerization Procedures:
METHOD A. Copolymerization of Ethylene and Propylene ( < 50 mole % E).
A 300-mL stainless steel Parr reactor was charged with liquid propylene (100 mL). Propylene was cooled to the reaction temperature and pressurized with ethylene. The monomer mixture was equilibrated at the reaction temperature under constant ethylene pressure for at least 20 min. Immediately prior to the catalyst injection the ethylene line was disconnected and the reactor was cooled to 2-3 °C below the reaction temperature to compensate for the anticipated exothermic effect of catalyst injection. In a nitrogen filled drybox a 50-mL pressure tube was charged with zirconocene/MAO solution in toluene (20 mL), removed from the box and pressurized with argon (250 psig). In the case of polymerizations at 0-2 °C the catalyst injection tube was cooled in an ice bath prior to being injected. The reaction was started by catalyst injection. After catalyst injection, the ethylene line was reconnected and the reaction was run for 15-60 min at constant total pressure and temperature. The reaction was quenched by injecting MeOH (20 mL). The polymer was precipitated in acidified MeOH (5% HC1). filtered, washed with MeOH and dried in a vacuum oven at 40 °C to constant weight.
METHOD B. Copolymerization of Ethylene and Propylene ( > 60 mole % E). A 300-mL Parr autoclave was charged with 60 mL of liquid propylene and cooled to the reaction temperature. MAO, dissolved in 10 mL of toluene, was injected under ethylene pressure and the reactor was allowed to equilibrate for 10-15 min. Polymerization was initiated by injecting the corresponding zirconocene dichloride solution in 10 mL of toluene under ethylene pressure set to 30-40 psi above the head pressure of preequlibrated ethylene/propylene mixture in the reactor. Polymerization was conducted for 25 min and quenched by injecting 10 mL of methanol under Ar pressure. The reactor was slowly vented and opened. The copolymer was precipitated in acidified methanol (5% HC1), filtered, washed with methanol and dried in a vacuum oven at 40 °C to constant weight.
METHOD C. Ethylene-Hexene Copolymerization.
The metallocene was dissolved in 25 mL of toluene in the N2 dry box. Methylaluminoxane (MAO) was dissolved in 35 mL of 1-hexene. The MAO solution was loaded into a 150 mL 2-ended injection tube. Meanwhile, a 300 mL stainless steel Parr reactor was evacuated to 100 mtorr and refilled with Ar. The reactor was flushed three times with 50 psig Ar and then 129 psig ethylene. The MAO solution was introduced to the reactor and was allowed to equilibrate with under the desired head pressure of ethylene for 30 min. 1-Hexene (3.2 mL) and an aliquot of metallocene stock solution (1.8 mL) was introduced to a 25 mL 2-ended injection tube. The ethylene feed was disconnected from the reactor and the pressure was vented by 10 psig. The metallocene solution was injected under the desired head pressure of ethylene to start the reaction. The ethylene feed was immediately reconnected to the reactor. The temperature was controlled at 18 °C throughout the reaction via an ethylene glycol/water cooling loop. The reaction was quenched with methanol injected under Ar pressure after 1 h. The reactor was vented and the copolymer was collected and stirred with acidified methanol overnight. The copolymer was then rinsed with methanol and dried to constant weight in a vacuum oven at 40 °C.
METHOD D. Ethylene Homopolymerization. The homopolymerization procedure was identical to that employed in copolymerizations. However, hexane was substituted for 1-hexene as the reaction solvent.
Ethylene-Propylene Copolymer Characterization. Copolymer composition and monomer sequence distribution were determined using c NMR spectroscopy. Copolymer samples (180-300 mg) were dissolved in 2.5 mL of o-dichlorobenzene/10 vol. % benzene- ό in 10 mm tubes. The spectra were measured at 140 °C using pulse repetition intervals of 13 s and gated proton decoupling. The isotacticity of propylene triads (%mm) was determined from the ratio of integrals of the first triplet in the methyl region (all pmpmP centered triads) over Tββ peak (all PPP triads). The glass transition, melting points and heats of fusion were determined by differential scanning calorimetry using Perkin- Elmer DSC-7. The DSC scans were obtained by first heating copolymer samples to 160 °C for 20 min, cooling them to 20 °C over 2 h, ageing them at room temperature for 24 h and then reheating from -100 °C to 200 °C at 20 °C/min. All DSC values in the tables are reheat values. Infrared spectra were obtained by transmission on melt-pressed films using a Perkin-Elmer 1600 FTIR spectrometer. The IR ratio = A993/A975, calculated from the absorptivities at 993 and 975 cm'l, was averaged over at least three measurements taken in different regions of the film.
Ethylene-1-Hexene Copolymer Characterization.
Copolymer composition and monomer sequence distribution were determined using 3c NMR spectroscopy. Copolymer samples (180-300 mg) were dissolved in 2.5 mL of o-dichlorobenzene/10 vol. % benzene-dό in 10 mm tubes. Approximately 5 mg of chromium acetylacetonate was added to samples to decrease spin relaxation times. The spectra were measured at 100 °C using pulse repetition intervals of 5 s and gated proton decoupling. The glass transition, melting points and heats of fusion were determined by differential scanning calorimetry using a Perkin-Elmer DSC-7. The DSC scans were obtained by first heating copolymer samples to 200 °C for 10 min, cooling them to 20 °C at 20 °C per minute, aging them at room temperature for 24 h and then reheating from 0 °C to 200 °C at 20 °C/min. All DSC values in the tables are reheat values. Scans to determine the glass transition temperature were obtained by cooling the sample to -150 °C and then heating to 0 °C at 40 °C/min. Mechanical tests were performed at 23 °C with ASTM D-1708 dumbell specimens
(2.2 cm gauge length) which were die cut from compression molded sheets of about 0.05 cm thickness. Crosshead separation rate was 25.4 cm/min for the three cycle 100% elongation test and 51 cm/min for the tensile and stress relaxation tests.
Tensile tests were run according to ASTM D638-96. Tensile modulus of elasticity was determined as the tangent slope at lowest strain. Elongation after break (percent elongation following break) was measured from benchmarks as immediate set of the center 10mm section of the specimen. The three cycle recovery test was performed by extension of the specimen three times to 100% elongation with a 30 second hold at each extension and a 60 second hold at each recovery. Cumulative set after the first two cycles was measured from the strain at which stress exceeds the baseline on the third cycle. A stress relaxation test was also conducted by extension to 50% elongation and measuring the decay of the stress.
Examples 12-17. Propylene Homopolymerization with Metallocenes 2, 4, 6-9.
The homopolymerization of propylene was carried out by Method A; results are reported in Table 1. Table 1. Propylene Polymerization with (2-Arylindenyl) Zirconocenes (2, 4, 6-9 / MAO).a
Ex. Catalyst0 Productivity0 %/n4d Mw MWD e ΔHm f xlO"3 e
12 2/MAO 2 530 32 542 3.48 28
13 4/MAO 1 180 72 580 4.66 81
14 6/MAO 2 800 14 293 3.77 —
15 7/MAO 1 350 31 217 4.44 35
16 8/MAO 1 810 24 262 3.74 26
17 9/MAO 1 030 47 270 6.50 57 a) Reaction conditions: bulk propylene, 20 °C, [Zr] = 50 mM,
[Zr] : [Al] = 1 : 1000, tr n = 30 min. ; b) 2 = (PhInd)2ZrCl2, 4 = (bfmPhIn)2ZrCl2,
6 = (PhInd)(lMePhInd)ZrCl2,
7 = (PhInd)(lMebfmPhIn)ZrCl2,
8 = (bfmPhIn)(lMePhInd)ZrCl2,
9 = (bfmPhln) (lMebfmPhIn)ZrCl2; c) (kg-PP)/(mol-Zr-h); d) determined by i C NMR; e) determined by GPC; f) determined by DSC
Examples 18-26. Ethylene/Propylene Copolymerization with Metallocenes 1 and 4.
The copolymerization of ethylene and propylene was carried out according to
Method B to give copolymers with ethylene contents of 60-75%; the results are reported in Table 2. Examples 18-20 are comparative examples prepared with a stereorigid metallocene 1; Examples 21-26 are carried out with catalysts of the present invention.
Note the melting range for polymers prepared by catalysts of the present invention are broader and the heats of fusion higher than polymers produced by comparative bridged catalyst 1.
Table 2. Ethylene/Propylene Copolymerization with Et(Ind)2ZrCl2 1/MAO and (bfmPhIn)2ZrCl2 4/MAO.a
Ex. Catalyst b Tpol» °C %E C Melting Tm, °C d ΔHm, range, °C d J/ d
18 1/MAO 0 66 110-132 124 0.55
19 1/MAO 0 68 110-134 127 1.9
20 1/MAO 0 75 110-134 125 0.17 e
21 4/MAO *' 2 61 31-130 45, 118 14.5 *' 75-136 123 7.1 8
22 4/MAO f 1 64 31-129 45, 119 16.8 8 40-130 123 13.5 e
23 4/MAO f 0 67 60-136 122 3.4
24 4/MAO f 0 69 28-133 45, 119 17.6 8 40-132 122 15.4 e
25 4/MAO f 0 69 30-131 42, 120 4.8
26 4/MAO f 23 60 27-126 44, 115 5.4 30-127 44, 115 14.1 e a) Conditions: [Zr] = l-2 mM, lMAO]:[Zr] = 10 000, trXn=25 min. 60 mL liq. P. DSC sample preparation: annealed at 160-180 °C for 20 min, cooled to 25 °C over 2 h, aged for 24 - 36 h if not otherwise specified. b) 1 = Et(Ind)2ZrCl2,
4 = (bfmPhIn)2ZrCl2 . c) Mole % ethylene determined by 13c NMR spectroscopy. d) Determined by DSC. e) Baseline curved, error may be present in peak area determination. f) Two shown values correspond to two runs on different DSC samples prepared from the same polymer sample, g) Samples aged for 1 mo.
Examples 27-79. Copolymerization of Ethylene and Propylene with Metallocenes 1, 2, 4, 6-9.
Ethylene/Propylene Copolymerizations were carried out according to Method A; results are reported in Tables 3 and 4. Table 3. First Order Markov Copolymerization Parameters for 1, 2, 4, 6-9 /MAO.
Ex. Cat. a T°C NeXp XeXpin %Ein rerpe ree e fee c polymer^
27 1/MAO l±l 5 0.04-0.18 23-54 0.49±0.03 5.4±0.6 0.09±0.01
28 1/MAO 20±1 1 0.07 42 0.50 7.1 0.07
29 2/MAO l±l 5 0.06-0.22 21-44 0.92±0.08 3.8±0.3 0.25±0.01
30 2/MAO 20±1 5 0.06-0.16 23-45 1.3±0.2 5.4±0.9 0.24±0.04
31 4/MAO l±l 5 0.07-0.25 18-43 1.3±0.1 4.2±0.7 0.31 ±0.03
32 4/MAO 20±1 5 0.05-0.08 14-22 1.9+0.1 6.0±0.2 0.33±0.03
33 6/MAO l±l 1 0.09 30 1.32 6.3 0.21
34 6/MAO 19±1 2 0.08-0.13 34-41 1.14±0.01 6.4±0.6 0.18±0.02
35 7/MAO O±l 4 0.04-0.27 15-62 1.49±0.30 7.0±0.39 0.21±0.03
36 7/MAO 19±1 3 0.04-0.13 20-45 1.34±0.22 8.6±1.3 0.15±0.01
37 8/MAO O±l 1 0.26 34 1.77 2.9 0.62
38 8/MAO 18±1 3 0.08-0.11 33-42 1.66 ±0.04 9.0±0.2 0.19±0.01
39 9/MAO O±l 2 0.03 - 0.08 28-64 1.80±0.26 7.3±0.5 0.25±0.03
40 9/MAO 20±1 5 0.05-0.13 31-48 1.72±0.35 10.8±2.7 0.16±0.02
a) 1 = Et(Ind)2ZrCl2, 2 = (PhInd)2ZrCl2,
4 = (bfmPhIn)2ZrCl2, 6 = (PhInd)(lMePhInd)ZrCl2, 7 = (PhInd)(lMebfmPhIn)ZrCl2,
8 = (bfmPhIn)(lMePhInd)ZrCl2,
9 = (bfmPhIn)(lMebfmPhIn)ZrCl2; b) number of experiments used for determination of the average reactivity ratios; c) the range of the ratios of the mole fractions of ethylene (Xe) and propylene (Xp); d) the range of mole % E in copolymers determined using 13c NMR; e) determined using 13c NMR
Note that the product of the reactivity ratios (re #rp) for metallocenes of the present invention are in the range 1.1 < re#rp < 1.8 whereas those for comparative metallocene 1 are less than 1 (re #rp = 0.5). Table 4. Ethylene-Propylene Copolymers Generated with Catalysts 1,2,4 and 6-9/MAO.a
Ex. Catalystb Tpol» %EC Tg> Melt Tm,°C ΔHm, Mw MWDe
°C oCd range, °C J/g •10-3e
41 1/MAO 0 0 — 20-160 143 125 70.6 2.0
42 1/MAO 2 11 -28 26-122 89 63 89.4 2.3
43 1/MAO 2 23 -39 25-90 58 9.3 78.1 2.1
44 1/MAO 2 42 -52 none none none 75.2 2.0
45 2/MAO 20 0 -8 30-160 140 31 542 3.5
46 2/MAO 20 9 -26 30-110 65 8 1 547 5.5
47 2/MAO 20 24 -26 none none none 1 312 3.6
48 4/MAO 0 0 — 20-160 147 100 756 5.7
49 4/MAO 2 9 -21 31-122 100 23 2 397 5.4
50 4/MAO 1 21 -31 31-142 45 2.2 2 292 4.2
51 4/MAO 1 33 -40 none none none 2 235 2.6
52 4/MAO 0 67 — 60-136 122 3.4
53 6/MAO 20 0 — none none none 293 3.8
54 6/MAO 18 34 -34 none none none 596 5.3
55 6/MAO 19 41 — none none none 633 5.2
56 6/MAO 1 30 -33 none none none 1 225 3.1
57 7MAO 20 0 -3 30-157 140 35 217 4.4
58 7MAO 18 20 -22 28-80 50 3.6 334 6.0
59 7MAO 18 23 -25 26-84 46 5.6
60 7MAO 19 29 -31 29-120 48 3.4 488 5.6
61 7MAO 19 45 — none none none 342 3.7
62 7MAO 1 0 -4 30-159 140 32.2 367 3.3
63 7MAO 0 15 -16 55-109 66 2.6 655 3.4
64 7MAO 1 36 -36 none none none 845 3.1
65 7MAO 1 62 — 27-130 118 8.3 869 3.4
66 8/MAO 20 0 -3 30-158 145 26 262 3.7
67 8/MAO 17 33 — none none none
68 8/MAO 19 42 — none none none 515 4.3
69 8/MAO 0 34 — none none none 907 3.2
70 9MAO 20 0 -2.6 20-163 148 57 270 6.5
71 9MAO 20 31 — 61-125 73, 115 2.4 500 10.2
72 9MAO 20 33 -33 44-128 117 4.2 450 6.2
73 9MAO 20 38 — 52-124 62, 115 2.0 558 6.8
74 9MAO 20 43 — 39-126 116 1.75 495 8.8
75 9MAO 19 48 -43 21-123 47, 115 7.5 385 5.9
76 9MAO 20 70 -52 64-126 117 2.9 611 5.0
77 9MAO 0 28 -27 30-81 51 4.7 781 4.2
78 9MAO 0 64 -48 35-125 115 3.5 673 3.7 a) DSC sample ] preparai [ion: annealed at 160-180 °C for 20 min, cooled to 25 °C over 2 h, aged for 36 h; b) 1 = Et(Ind)2ZrCl2, 2 = (PhInd)2ZrCl2, 4 = (bfmPhIn)2ZrCl2, 6 = (PhInd)(lMePhInd)ZrCl2,
7 = (PhInd)(lMebfmPhIn)ZrCl2,
8 = (bfmPhIn)(lMePhInd) ZrCl2,
9 = (bfmPhIn)(lMebfmPhIn)ZrCl2; c) Mole % E determined by 3c NMR spectroscopy; d) Half Cp extrapolated; e) Determined by high temperature GPC.
Note that polymers prepared with metallocene 1 containing 42% ethylene (Example 44) are amorphous, whereas polymers of similar composition (48 %E) derived from metallocene 9 (Example 75) are crystalline and exhibit a melting range of 21-123 °C with a heat of fusion of 7.5 J/g. Also note that propylene polymers obtained from metallocene 1 containing 23% ethylene exhibit a melting range of 25-90°C and ΔHm = 9.5 J/g (Example 43) whereas propylene polymers containing as much as 33 % E derived from metallocene 9 show higher melting range of 44-128°C with ΔHm = 4.2 J/g (Example 72).
The compositional heterogeneity of the copolymer sample of Example 78 was investigated by extraction in boiling heptane. The microstructures of the heptane soluble (50 wt%) and insoluble (50 wt%) fractions of Example 78 were analyzed by Solution 13c NMR spectroscopy (Table 5). The ethylene contents (%E) of the fractions differ by 3% or less and the reactivity ratios calculated from the dyad distribution differ by less than 0.16 from the average of the whole polymer sample, clearly indicating the compositional homogeneity of these copolymers.
Table 5. Fractionation of Ethylene Propylene Copolymer from Metallocene 9
Example Sample %Wt %Ea rerp
78 Whole 100 64 1.54
HS 50 61 1.46
HI 50 64 1.70 a) determined by solution 13c NMR b) HS = heptanes soluble c) HI = heptanes insoluble
Examples 79-104.
The copolymerization of ethylene and 1-hexene was carried out with metallocenes 1, 2, 4, 5 and 9-10 by Method C. The data and characteristics of the polymers are reported in Table 6. Table 6. Summary of the DSC and Molecular Weight Data for Ethylene-1-Hexene Copolymers Generated with Catalysts 1, 2, 3, 4, 9 and 10/MAO.3
Ex. Cat.b Tpol» %EC melt range, T » m> O Ca ΔHm,
Figure imgf000029_0001
MWDe °C oCa J g3 •10-3e
79 1/MAO 19 54 -72 none none 0 53 2.2
80 1/MAO 18 65 -76 none none 0 52 2.1
81 1/MAO 19 69 — none none 0 61 2.2
82 1/MAO 18 77 -77 37-45 43 0.3 75 2.4
83 1/MAO 18 81 -74 33-43 40 4.7 71 2.2
84 2/MAO 18 54 -68 none none 0 1176 3.2
85 2/MAO 18 59 — none none 0 1353 5.5
86 2/MAO 18 64 -72 none none 0 1474 7.4
87 4/MAO 18 44 none none 0 554 7.4
88 4/MAO 18 55 26-126 116 2.7 691 6.3
89 4/MAO 18 62 28-130 40, 120 8.0 994 7.6
90 4/MAO 18 66 61-81 63, 114 3.5 783 6.7
82-124
91 4/MAO 18 70 29-75 38, 121 4.2 1076
76-126
92 4/MAO 18 73 23-130 37, 119 16 826 6.3
93 4/MAO 80 -70 16-116 25, 86 15.7 1164 6.1
94 4/MAO 89 -59 11-117 20, 105 31 1318 4.6
95 4/MAO 18 100 100-145 133 136 1534 4.7
96 3/MAO 18 49 none none 0 1793 2.8
97 3/MAO 18 62 30-50 40 1.0 1287 4.8
98 9/MAO 18 68 14-63 23, 96 2.7 646 5.1
79-114
99 9/MAO 18 70 40-68 22, 108 5.4 700 4.8
92-120
100 9/MAO 18 76 20-67 23, 107 4.0 901 5.8
78-114
101 9/MAO 18 79 15-43 20, 106 8.4 825 4.7
79-114
102 10/MAO 18 48 — none none 0 1193 4.1
103 10/MAO 18 55 -74 34-127 117 4.0 1335 7.8
104 10/MAO 17 64 -74 29-135 117 5.2 1758 7.9 a) DSC sample preparation: annealed at 200 °C for 10 min, cooled to 25 °C at 20 °C/min, aged 24 h. b) 1 = Et(Ind)2ZrCl2,
2 = (PhInd)2ZrCl2,
4 = (bfmPhIn)2ZrCl2,
3 = (PhInd)2HfCl2,
9 = (bfmPhIn)(lMebfmPhIn)ZrCl2,
10 = (DTBM)2ZrCl2- c) Mole % E determined by 13c NMR spectroscopy. d) Half Cp extrapolated (DSC). e) Determined by high temperature GPC. As indicated in Table 6, Comparative Examples 79-83, carried out with bridged metallocene 1 yields random ethylene/hexene copolymers. Polymers made with this metallocene containing 54 - 69 mol % ethylene are amorphous, exhibiting no melting point by DSC analysis as indicated by "none" under the melt range and Tm columns. In contrast, metallocene 4 of the present invention yields polymers containing 55 - 70% ethylene with melting points ranging from 26 - 130°C.
The properties of the ethylene/hexene copolymers of Example 92 and 93 are compared to representative other comparable polyolefin elastomers and reported in Table 7, Parts I and II. Comparative Example 105 is a commercial Ethylene/Octene Elastomer obtained from Dow (Engage 8200on), Comparative Example 106 is an Ethylene/Butene Elastomer obtained from Exxon (Exact 4033tm), and comparative Example 107 is a polypropylene elastomer as described in Waymouth et al. US 5,594,080.
Table 7, Part I Mechanical Properties of Polyolefin Elastomers.
Polymer Ex. 92 Ex. 93 Ex. 94 Comp. Ex Comp. Ex Comp. Ex 105 106 107
Engage Exact polypropylene
8200 4033 37% mmmm
Comonomer Hexene Hexene Hexene Octene Butene None
Mole % Ethylene 73 80 89 87 89 0
PE Melt Index nd nd nd 5 0 0.8
Mw (x l03) 826 1 164 1318 77 4 nd 386
Tm range (°C) 23-130 16-1 16 11-117 20 - 70 20 - 70 40-160
Tm peak (°C) 119 25, 86 20-105 66 64 148
ΔHm(J/g) 16.2 15 6 31 10 5 13 7
Tg(°C)a — -66 -60 -54 —
Density (g/cc) 0 8682 0 8694 0 8819 0 87 0 88 0 8663
Tensile 3 6 4 2 8 8 9 6 16 9 12.3
Strength (MPa)
Tensile 2 9 4 0 10.3 6 9 12 3 8 9
Modulus (MPa)
Elongation at 565 ± 62 428 360 1 130 750 830
Break (%)
Elongation 90 ± 17 26 57 300 210 34 after Break (%) a) Determined by Dynamic Mechanical Analysis Table 7, Part II Mechanical Properties (cont'd.)
100% Ex. 92 Ex. 93 Ex. 94 Comp. Comp. Ex Comp. Ex 107 Elongation 3 Cycle Test: Ex 105 106
% stress 33 17 17 23 23 39 relaxation, 30 s, 1st cycle
% retained force, 24 41 29 28 20 29 2nd cycle
% set, cumulative 19 13 13 13 11 7
Stress Relaxation Test
50% elongation, 51 33 25 28 28 48 5 min
As evident from Table 7, all polyolefin elastomers have a similar density and comparable elastomeric properties. However, the copolymer elastomers of Example 92 and 93 have a particularly useful combination of properties that includes a low glass transition temperature (Tg = -70°C) and melting ranges that extend to 130° C. Note in particular that while the copolymers of Example 92, and comparative Examples 105 and 106 have similar degrees of crystallinity as manifested by their heats of fusion (ΔHf (J/g) from 10.5 - 16.2), the melting point of the copolymer of Example 92 is 119°C. It is unexpected that this high melting point is acheived at a much lower mol % ethylene (73 mol % versus 87 or 89 mol %).
The compositional hetereogeneity of these copolymers was investigated by extracting the copolymers in boiling ether and hexanes. The results of these fractionation experiments on the copolymer samples of Example 90 and 91 are reported in Table 8.
Table 8. Fractionation of Ethylene/Hexene Copolymers from Metallocene 4
Example Sample %wt Ea τm, °c Melt Range, °C
90 Whole 100 66 63, 114 61 - 81, 82 - 124
ESb 16 59 42 35 - 50
El 84 72 41, 118 29 -126
EI/HxSc 80 69 45 25 - 85
91 Whole 100 70 39, 119 29 - 75, 76 - 126
ESb 23 63 35 30 - 43
EIC 77 73 35, 119 24 - 129
EI/HxSc 64 67 34, 119 27 - 126
Hxle 13 75 35, 59, 117 24 - 128
a) determined by solution 13c NMR. b) ES = diethylether soluble, c) EI/HxS = diethylether insoluble/hexane soluble, d) Hxl = hexane insoluble.
Note that the mole fraction of ethylene in the various fractions of the copolymer are all within 10% of the mean mole percent ethylene of the copolymer sample, indicating that these materials have a narrow composition distribution.
INDUSTRIAL APPLICABILITY:
It is evident that the polymers of the present invention, and the polymerization catalysts and processes by which the polymers are produced will have wide applicability in industry, inter alia, as elastomers having higher melting points than currently available elastomers, as thermoplastic materials, and as components for blending with other polyolefins for predetermined selected properties, such as raising the melting point of the blend. As noted in Table 7 and the accompanying discussion, typical polymers of this invention, while they have degrees of crystallinity similar to that of Dow's Engage 8200tm and EXXON's 4033tm, they have a broader melting point range that extends to higher temperatures, e.g. , to 130°C, and above.
It should be understood that various modifications within the scope of this invention can be made by one of ordinary skill in the art without departing from the spirit thereof. We therefore wish this invention to be defined by the scope of the appended claims as broadlly as the prior art will permit, and in view of the specification if need be.

Claims

We Claim:
1. A method of producing an olefin copolymer from a feedstock including ethylene and at least one alpha olefin monomer comprising in any suitable sequence the steps of: a) contacting said feedstock with an unbridged, rotating, non-rigid fluxional metallocene catalyst component in the presence of a co-catalyst for a time sufficient to produce an elastomeric thermoplastic copolymer; b) said unbridged fluxional metallocene catalyst component is selected from at least one compound of the formula:
Figure imgf000033_0001
in which M is a Group 3, 4 or 5 Transition metal, a Lanthanide or an Actinide; X and X' are the same or different uninegative ligands; and L and L' are ligands selected from the same or different substituted, polynuclear, hydrocarbyl, and hetero-hydrocarbyl rings; c) said L and L' ligands are selected so that the fluxional metallocene component isomerizes between at least two coordinate geometry states that have different reactivities toward at least one of ethylene and said alpha olefin while in the respective coordinate geometry states; and d) recovering an elastomeric copolymer product.
2) A polymerization process as in claim 1 wherein: said substituted rings are selected from cyclopentadienyl, heterocyclopentadienyl and indenyl rings; said uninegative ligands are selected from hydride, halogen, hydrocarbyl, halohydrocarbyl, amine, amide, or borohydride ions; said Transition Metal is selected from Titanium, Hafnium, Vanadium, and Zirconium; said Group 3 metal is Yttrium; said Lanthanide is Samarium; and said Actinide is Thorium.
3) A polymerization process as in claim 2 wherein said cyclopentadienyl and herterocyclopentadienyl rings have the formula:
Figure imgf000034_0001
where Rl , R2, R3, R9, and Rio are selected from the same or different hydrogen, alkyl, alkylsilyl, aryl, alkoxyalkyl, alkoxyaryl, alkoxysilyl, aminoalkyl, aminoaryl or substituted alkyl, alkylsilyl or aryl substituents of 1 to about 30 carbon atoms and where said ring is heterocyclopentadienyl, the hetero atom of said ring is seleted from N, P, As and B.
4) A polymerization process as in claim 3 wherein said ligands L and L' are selected cyclo-pentadienes of the general formula:
Figure imgf000034_0002
where R2 through Rio are the same or different hydrogen, alkyl, alkylsilyl, aryl, alkoxyalkyl, alkoxyaryl, alkoxysilyl, aminoalkyl, aminoaryl or substituted alkyl, alkylsilyl or aryl substituents of 1 to about 30 carbon atoms.
5) A polymerization process as in claim 4 wherein said cyclopentadiene is selected from 3,4-dimethyl-l-phenyl-l ,3-cyclopentadiene (R2=R3=CH3, and R6 = H), 3,4-dimethyl-l- p-tolyl-l,3-cyclopentadiene (R2 = R3 =CH3, and Rό=CH3), 3,4,-dimethyl-l-(3,5-bis(tri- fluoromethyl)phenyl)-l ,3-cyclopentadiene (R2= R3=CH3, and Rό=CF3), and 3,4-di- methyl-l-(4-te/ -butylphenyl)-l ,3-cyclopentadiene (R2= R3=CH3, and Rό=tBu).
6) A polymerization process as in claim 3 wherein Rj is an aryl group and R2 and R3 are connected as part of a ring of 3 or more carbon atoms.
7) A polymerization process as in claim 6 wherein said aryl group is selected from phenyl, biphenyl and naphthyl groups.
8) A polymerization process as in claim 6 wherein said aryl group is a 2-aryl indene of the formula:
Figure imgf000035_0001
where R4 through R14 are selected from the same or different hydrogen, halogen, aryl, hydrocarbyl, silahydrocarbyl and halo-hydrocarbyl substituents.
9) A polymerization process as in claim 8 wherein said 2-aryl indene is selected from 2- phenylindene; l-methyl-2-phenyl indene; 2-(3,5-dimethylphenyl) indene; 2-(3,5-bis-tri- fluoromethylphenyl) indene; l-methyl-2-(3,5-bis-trifluoromethylphenyl) indene; 2-(3,5-bis- tertbutylphenyl) indene; l-methyl-2-(3,5-bis-tertbutylphenyl) indene; 2-(3,5-bis-tri- methylsilylphenyl)indene; l-methyl-2-(3,5-bis-trimethylsilylphenyl)indene; 2-(4-fluoro- phenyl) indene; 2-(2, 3, 4, 5-tetrafluorophenyl) indene; 2-(2, 3, 4, 5, 6-pentafluorophenyl) indene; 2-(l -naphthyl) indene; 2-(2-naphthyl) indene; 2-[(4-phenyl)phenyl] indene; and 2- [(3-phenyl) phenyl] indene.
10) A polymerization process as in claim 1 wherein at least some of the resulting copolymer product is fractionated into at least one fraction selected from an ether soluble, a hexanes soluble, and a hexanes insoluble fraction, and the mole fraction of ethylene in the various fractions of the copolymer are substantially within 15% of the mean mole percent ethylene of the initial resultant copolymer product.
11) A polymerization process as in claim 1 wherein the copolymer produced is selected from thermoplastic polymers having a molecular weight distribution, Mψ/Mn, < /= 10; a composition distribution < /= 15%; a melting point of > /= about 90°C; a melting point index of > /= about 80 °C; a glass transition temperature of < /= about -20 °C; a mole fraction of crystallizable component, Xc, of from about 30% to about 99%; and elastomeric properties.
12) A polymerization process as in claim 10 wherein said copolymer fractions are in the range of about 0% to about 70% by weight of said ether soluble fraction, from about 0% to about 95% of said hexanes soluble fraction and from about 0% to about 95% of said hexanes insoluble fraction. 13) A polymerization process as in claim 12 wherein said hexanes soluble fraction has a melting range of up to about 125┬░C, and said hexanes insoluble fraction has a melting range up to about 142┬░C.
14) A polymerization process as in claim 11 wherein said copolymer has a weight average molecular weight, M yy, in excess of about 1 million.
15) A polymerization process as in claim 11 wherein said copolymer has a molecular weight distribution, M\y/Mn, < /= 8.
16) A thermoplastic olefin copolymer having a molecular weight distribution, M /Mn, < /*= 10; a composition distribution < /= 15%; a melting point of > /= about 90┬░C; a melting point index of > /= about 80 ┬░C; a glass transition temperature of < /= about - 20 ┬░C; a mole fraction of crystallizable component, Xc, of from about 30% to about 99%; and elastomeric properties.
17) A thermoplastic olefin copolymer as in claim 16 which comprises from about 0% to about 70% by weight of an ether soluble fraction, from about 0% to about 95% of a hexane soluble fraction, and from about 0% to about 95% of a hexane insoluble fraction.
18) A thermoplastic ethylene/alpha olefin copolymer as in claim 17 wherein said hexanes soluble fraction has a melting range of up to about 125┬░C, and said hexanes insoluble fraction has a melting range up to about 142┬░C.
19) A thermoplastic olefin copolymer as in claim 16 which has a weight average molecular weight, M ╬│, in excess of about 1 million.
20) A thermoplastic olefin copolymer as in claim 16 which has a molecular weight distribution, M\ /Mn, < /= 8.
21) A thermoplastic olefin copolymer as in claim 20 which has a molecular weight distribution, M /Mn, < /= 6.
22) A thermoplastic olefin copolymer as in claim 16 wherein the comonomers are selected from ethylene and alpha olefins.
23) An unbridged fluxional metallocene catalyst component which exhibits plural coordination geometries for olefin polymerization, having the formula:
Figure imgf000037_0001
wherein M is a Group 3, 4 or 5 Transition metal, a Lanthanide or an Actinide; X and X' are the same or different uninegative ligands, and said ligands L and L' are selected from at least one of : (l-methyl-2-phenylindenyl)-(2-phenylindenyl); (l-methyl-2-phenylindenyl)[2- (3,5-bis-trifluoromethyl-phenyl)indenyl];l-methyl-2-(3,5-bis-trifluoromethylphenyl)-idenyl- ](2-phenylindenyl); [l-methyl-2-(3, 5-bis-trifluoromethylphenyl)indenyl][2-(3, 5-bis-trifluoro- methylphenyl)-indenyl]; and (l-methyl-2-phenylindenyl)[2-(3,5-bis-tertbutylphenyl)inderiyl] groups.
PCT/US1999/000540 1998-01-09 1999-01-08 High-melting polyolefin copolymer elastomers, catalysts and methods of synthesis WO1999035171A1 (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US1999/000540 WO1999035171A1 (en) 1998-01-09 1999-01-08 High-melting polyolefin copolymer elastomers, catalysts and methods of synthesis
AU21115/99A AU2111599A (en) 1998-01-09 1999-01-08 High-melting polyolefin copolymer elastomers, catalysts and methods of synthesis

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US7105098P 1998-01-09 1998-01-09
US60/071,050 1998-01-09
PCT/US1999/000540 WO1999035171A1 (en) 1998-01-09 1999-01-08 High-melting polyolefin copolymer elastomers, catalysts and methods of synthesis

Publications (1)

Publication Number Publication Date
WO1999035171A1 true WO1999035171A1 (en) 1999-07-15

Family

ID=26751774

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1999/000540 WO1999035171A1 (en) 1998-01-09 1999-01-08 High-melting polyolefin copolymer elastomers, catalysts and methods of synthesis

Country Status (1)

Country Link
WO (1) WO1999035171A1 (en)

Cited By (41)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2000040625A1 (en) * 1999-01-08 2000-07-13 The Board Of Trustees Of The Leland Stanford Junior University Ethylene copolymers with narrow composition distribution and high melting temperatures, and methods of production thereof
US6184317B1 (en) 1997-07-14 2001-02-06 The Board Of Trustees Of The Leland Stanford Jr. University Catalysts and processes for the synthesis of alternating ethylene/α-olefin copolymers, and isotactic copolymers thereof
US7355089B2 (en) 2004-03-17 2008-04-08 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates
US7498282B2 (en) 2005-10-26 2009-03-03 Dow Global Technology Inc. Multi-layer, elastic articles
US7504347B2 (en) 2004-03-17 2009-03-17 Dow Global Technologies Inc. Fibers made from copolymers of propylene/α-olefins
US7510817B2 (en) 2003-06-26 2009-03-31 Jsr Corporation Photoresist polymer compositions
US7514517B2 (en) 2004-03-17 2009-04-07 Dow Global Technologies Inc. Anti-blocking compositions comprising interpolymers of ethylene/α-olefins
US7517634B2 (en) 2003-06-26 2009-04-14 Jsr Corporation Photoresist polymers
US7524911B2 (en) 2004-03-17 2009-04-28 Dow Global Technologies Inc. Adhesive and marking compositions made from interpolymers of ethylene/α-olefins
US7557147B2 (en) 2004-03-17 2009-07-07 Dow Global Technologies Inc. Soft foams made from interpolymers of ethylene/alpha-olefins
US7579408B2 (en) 2004-03-17 2009-08-25 Dow Global Technologies Inc. Thermoplastic vulcanizate comprising interpolymers of ethylene/α-olefins
US7582716B2 (en) 2004-03-17 2009-09-01 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for blown films with high hot tack
US7592397B2 (en) 2005-03-17 2009-09-22 Dow Global Technologies Inc. Cap liners, closures, and gaskets from multi-block polymers
US7608668B2 (en) 2004-03-17 2009-10-27 Dow Global Technologies Inc. Ethylene/α-olefins block interpolymers
US7622529B2 (en) 2004-03-17 2009-11-24 Dow Global Technologies Inc. Polymer blends from interpolymers of ethylene/alpha-olefin with improved compatibility
US7622179B2 (en) 2004-03-17 2009-11-24 Dow Global Technologies Inc. Three dimensional random looped structures made from interpolymers of ethylene/α-olefins and uses thereof
US7662881B2 (en) 2004-03-17 2010-02-16 Dow Global Technologies Inc. Viscosity index improver for lubricant compositions
US7666918B2 (en) 2004-03-17 2010-02-23 Dow Global Technologies, Inc. Foams made from interpolymers of ethylene/α-olefins
US7671131B2 (en) 2004-03-17 2010-03-02 Dow Global Technologies Inc. Interpolymers of ethylene/α-olefins blends and profiles and gaskets made therefrom
US7671106B2 (en) 2004-03-17 2010-03-02 Dow Global Technologies Inc. Cap liners, closures and gaskets from multi-block polymers
US7687442B2 (en) 2004-03-17 2010-03-30 Dow Global Technologies Inc. Low molecular weight ethylene/α-olefin interpolymer as base lubricant oils
US7695812B2 (en) 2005-09-16 2010-04-13 Dow Global Technologies, Inc. Fibers made from copolymers of ethylene/α-olefins
US7714071B2 (en) 2004-03-17 2010-05-11 Dow Global Technologies Inc. Polymer blends from interpolymers of ethylene/α-olefins and flexible molded articles made therefrom
US7737215B2 (en) 2005-03-17 2010-06-15 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates
US7737061B2 (en) 2005-03-17 2010-06-15 Dow Global Technologies Inc. Compositions of ethylene/alpha-olefin multi-block interpolymer for elastic films and laminates
US7741397B2 (en) 2004-03-17 2010-06-22 Dow Global Technologies, Inc. Filled polymer compositions made from interpolymers of ethylene/α-olefins and uses thereof
US7786216B2 (en) 2005-03-17 2010-08-31 Dow Global Technologies Inc. Oil based blends of interpolymers of ethylene/α-olefins
US7795321B2 (en) 2004-03-17 2010-09-14 Dow Global Technologies Inc. Rheology modification of interpolymers of ethylene/α-olefins and articles made therefrom
US7803728B2 (en) 2004-03-17 2010-09-28 Dow Global Technologies Inc. Fibers made from copolymers of ethylene/α-olefins
US7863379B2 (en) 2004-03-17 2011-01-04 Dow Global Technologies Inc. Impact modification of thermoplastics with ethylene/alpha-olefin interpolymers
US7897689B2 (en) 2004-03-17 2011-03-01 Dow Global Technologies Inc. Functionalized ethylene/α-olefin interpolymer compositions
US7906587B2 (en) 2005-09-16 2011-03-15 Dow Global Technologies Llc Polymer blends from interpolymer of ethylene/α olefin with improved compatibility
US7910658B2 (en) 2005-03-17 2011-03-22 Dow Global Technologies Llc Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates
US7989543B2 (en) 2005-03-17 2011-08-02 Dow Global Technologies Llc Adhesive and marking compositions made from interpolymers of ethylene/α-olefins
US8153243B2 (en) 2005-12-09 2012-04-10 Dow Global Technologies Llc Interpolymers suitable for multilayer films
US8273838B2 (en) 2004-03-17 2012-09-25 Dow Global Technologies Llc Propylene/α-olefins block interpolymers
US8318864B2 (en) 2004-03-17 2012-11-27 Dow Global Technologies Llc Functionalized ethylene/α-olefin interpolymer compositions
US8362162B2 (en) 2005-12-09 2013-01-29 Dow Global Technologies Llc Processes of controlling molecular weight distribution in ethylene/alpha-olefin compositions
US8816006B2 (en) 2004-03-17 2014-08-26 Dow Global Technologies Llc Compositions of ethylene/α-olefin multi-block interpolymer suitable for films
US9102128B2 (en) 2007-10-22 2015-08-11 Dow Global Technologies Llc Multilayer films
JP2018070455A (en) * 2016-10-24 2018-05-10 三井化学株式会社 Transition metal compound, catalyst for olefin polymerization, and manufacturing method of olefin polymer

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5055535A (en) * 1988-12-14 1991-10-08 Atochem Procedure for gas-phase polymerication of ethylene allowing the fabrication of linear polyethylene with a narrow molecular-weight distribution
US5192732A (en) * 1990-11-27 1993-03-09 Atochem Propylene polymerization cocatalyst containing silane and resultant catalysts
US5594080A (en) * 1994-03-24 1997-01-14 Leland Stanford, Jr. University Thermoplastic elastomeric olefin polymers, method of production and catalysts therefor

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5055535A (en) * 1988-12-14 1991-10-08 Atochem Procedure for gas-phase polymerication of ethylene allowing the fabrication of linear polyethylene with a narrow molecular-weight distribution
US5192732A (en) * 1990-11-27 1993-03-09 Atochem Propylene polymerization cocatalyst containing silane and resultant catalysts
US5594080A (en) * 1994-03-24 1997-01-14 Leland Stanford, Jr. University Thermoplastic elastomeric olefin polymers, method of production and catalysts therefor

Cited By (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6184317B1 (en) 1997-07-14 2001-02-06 The Board Of Trustees Of The Leland Stanford Jr. University Catalysts and processes for the synthesis of alternating ethylene/α-olefin copolymers, and isotactic copolymers thereof
WO2000040625A1 (en) * 1999-01-08 2000-07-13 The Board Of Trustees Of The Leland Stanford Junior University Ethylene copolymers with narrow composition distribution and high melting temperatures, and methods of production thereof
US7510817B2 (en) 2003-06-26 2009-03-31 Jsr Corporation Photoresist polymer compositions
US7517634B2 (en) 2003-06-26 2009-04-14 Jsr Corporation Photoresist polymers
US7671131B2 (en) 2004-03-17 2010-03-02 Dow Global Technologies Inc. Interpolymers of ethylene/α-olefins blends and profiles and gaskets made therefrom
US7671106B2 (en) 2004-03-17 2010-03-02 Dow Global Technologies Inc. Cap liners, closures and gaskets from multi-block polymers
US7514517B2 (en) 2004-03-17 2009-04-07 Dow Global Technologies Inc. Anti-blocking compositions comprising interpolymers of ethylene/α-olefins
US9352537B2 (en) 2004-03-17 2016-05-31 Dow Global Technologies Llc Compositions of ethylene/α-olefin multi-block interpolymer suitable for films
US7524911B2 (en) 2004-03-17 2009-04-28 Dow Global Technologies Inc. Adhesive and marking compositions made from interpolymers of ethylene/α-olefins
US7557147B2 (en) 2004-03-17 2009-07-07 Dow Global Technologies Inc. Soft foams made from interpolymers of ethylene/alpha-olefins
US7579408B2 (en) 2004-03-17 2009-08-25 Dow Global Technologies Inc. Thermoplastic vulcanizate comprising interpolymers of ethylene/α-olefins
US7582716B2 (en) 2004-03-17 2009-09-01 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for blown films with high hot tack
US9243090B2 (en) 2004-03-17 2016-01-26 Dow Global Technologies Llc Catalyst composition comprising shuttling agent for ethylene multi-block copolymer formation
US7608668B2 (en) 2004-03-17 2009-10-27 Dow Global Technologies Inc. Ethylene/α-olefins block interpolymers
US7622529B2 (en) 2004-03-17 2009-11-24 Dow Global Technologies Inc. Polymer blends from interpolymers of ethylene/alpha-olefin with improved compatibility
US7622179B2 (en) 2004-03-17 2009-11-24 Dow Global Technologies Inc. Three dimensional random looped structures made from interpolymers of ethylene/α-olefins and uses thereof
US7662881B2 (en) 2004-03-17 2010-02-16 Dow Global Technologies Inc. Viscosity index improver for lubricant compositions
US7666918B2 (en) 2004-03-17 2010-02-23 Dow Global Technologies, Inc. Foams made from interpolymers of ethylene/α-olefins
US8067319B2 (en) 2004-03-17 2011-11-29 Dow Global Technologies Llc Fibers made from copolymers of ethylene/α-olefins
US7504347B2 (en) 2004-03-17 2009-03-17 Dow Global Technologies Inc. Fibers made from copolymers of propylene/α-olefins
US7687442B2 (en) 2004-03-17 2010-03-30 Dow Global Technologies Inc. Low molecular weight ethylene/α-olefin interpolymer as base lubricant oils
US8816006B2 (en) 2004-03-17 2014-08-26 Dow Global Technologies Llc Compositions of ethylene/α-olefin multi-block interpolymer suitable for films
US7714071B2 (en) 2004-03-17 2010-05-11 Dow Global Technologies Inc. Polymer blends from interpolymers of ethylene/α-olefins and flexible molded articles made therefrom
US7732052B2 (en) 2004-03-17 2010-06-08 Dow Global Technologies Inc. Compositions of ethylene/alpha-olefin multi-block interpolymer for elastic films and laminates
US7355089B2 (en) 2004-03-17 2008-04-08 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates
US8609779B2 (en) 2004-03-17 2013-12-17 Dow Global Technologies Llc Functionalized ethylene/alpha-olefin interpolymer compositions
US7741397B2 (en) 2004-03-17 2010-06-22 Dow Global Technologies, Inc. Filled polymer compositions made from interpolymers of ethylene/α-olefins and uses thereof
US8318864B2 (en) 2004-03-17 2012-11-27 Dow Global Technologies Llc Functionalized ethylene/α-olefin interpolymer compositions
US7795321B2 (en) 2004-03-17 2010-09-14 Dow Global Technologies Inc. Rheology modification of interpolymers of ethylene/α-olefins and articles made therefrom
US7803728B2 (en) 2004-03-17 2010-09-28 Dow Global Technologies Inc. Fibers made from copolymers of ethylene/α-olefins
US7842770B2 (en) 2004-03-17 2010-11-30 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for blown films with high hot tack
US7863379B2 (en) 2004-03-17 2011-01-04 Dow Global Technologies Inc. Impact modification of thermoplastics with ethylene/alpha-olefin interpolymers
US7893166B2 (en) 2004-03-17 2011-02-22 Dow Global Technologies, Inc. Ethylene/alpha-olefins block interpolymers
US7897689B2 (en) 2004-03-17 2011-03-01 Dow Global Technologies Inc. Functionalized ethylene/α-olefin interpolymer compositions
US8273838B2 (en) 2004-03-17 2012-09-25 Dow Global Technologies Llc Propylene/α-olefins block interpolymers
US8211982B2 (en) 2004-03-17 2012-07-03 Dow Global Technologies Llc Functionalized ethylene/α-olefin interpolymer compositions
US7737215B2 (en) 2005-03-17 2010-06-15 Dow Global Technologies Inc. Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates
US7737061B2 (en) 2005-03-17 2010-06-15 Dow Global Technologies Inc. Compositions of ethylene/alpha-olefin multi-block interpolymer for elastic films and laminates
US7592397B2 (en) 2005-03-17 2009-09-22 Dow Global Technologies Inc. Cap liners, closures, and gaskets from multi-block polymers
US7910658B2 (en) 2005-03-17 2011-03-22 Dow Global Technologies Llc Compositions of ethylene/α-olefin multi-block interpolymer for elastic films and laminates
US7989543B2 (en) 2005-03-17 2011-08-02 Dow Global Technologies Llc Adhesive and marking compositions made from interpolymers of ethylene/α-olefins
US7786216B2 (en) 2005-03-17 2010-08-31 Dow Global Technologies Inc. Oil based blends of interpolymers of ethylene/α-olefins
US8912282B2 (en) 2005-03-17 2014-12-16 Dow Global Technologies Llc Oil based blends of interpolymers of ethylene/alpha-olefins
US7906587B2 (en) 2005-09-16 2011-03-15 Dow Global Technologies Llc Polymer blends from interpolymer of ethylene/α olefin with improved compatibility
US7695812B2 (en) 2005-09-16 2010-04-13 Dow Global Technologies, Inc. Fibers made from copolymers of ethylene/α-olefins
US7498282B2 (en) 2005-10-26 2009-03-03 Dow Global Technology Inc. Multi-layer, elastic articles
US8362162B2 (en) 2005-12-09 2013-01-29 Dow Global Technologies Llc Processes of controlling molecular weight distribution in ethylene/alpha-olefin compositions
US8969495B2 (en) 2005-12-09 2015-03-03 Dow Global Technologies Llc Processes of controlling molecular weight distribution in ethylene/α-olefin compositions
US8153243B2 (en) 2005-12-09 2012-04-10 Dow Global Technologies Llc Interpolymers suitable for multilayer films
US9102128B2 (en) 2007-10-22 2015-08-11 Dow Global Technologies Llc Multilayer films
JP2018070455A (en) * 2016-10-24 2018-05-10 三井化学株式会社 Transition metal compound, catalyst for olefin polymerization, and manufacturing method of olefin polymer

Similar Documents

Publication Publication Date Title
US6169151B1 (en) High-melting polyolefin copolymer elastomers, catalysts and methods of synthesis
US6518378B2 (en) High-melting polyolefin copolymer elastomers, catalysts and methods of synthesis
WO1999035171A1 (en) High-melting polyolefin copolymer elastomers, catalysts and methods of synthesis
US6160064A (en) Ethylene enhancement of processes for synthesis of high melting theromoplastic elastomeric α-olefin polymers (PRE/EPE effects)
US6566544B1 (en) Catalysts for thermoplastic elastomeric olefin polymers
US6380341B1 (en) Ethylene copolymers with narrow composition distribution and high melting temperatures, and methods of production thereof
KR100418106B1 (en) Metallocene compounds, process for their preparation, and their use in catalysts for the polymerization of olefins
MXPA00002181A (en) Process for the preparation of substantially amorphous alpha-olefin polymers and compositions containing them and process for the preparation of bridged ligand.
WO2003050131A1 (en) Metallocenes and catalyst compositions derived therefrom
KR100843603B1 (en) Transition metal complexes, catalysts composition containing the same and olefin polymerization theirwith
KR102419481B1 (en) Olefin based polymer
KR20020007419A (en) Thermoplastic compositions of isotactic propylene polymers and flexible propylene polymers having reduced isotacticity and a process for the preparation thereof
US6479685B2 (en) Metallocene catalysts for synthesis of high-melting polyolefin copolymer elastomers
KR101969123B1 (en) Polypropylene having high rigidity and for reducing energy in foaming
JP2002534538A (en) Ethylene copolymer having narrow composition distribution and high melting point and method for producing the same
KR100371909B1 (en) Metallocene Catalysts Having Multi-nuclear Constrained Geometry and Ethylene/Aromatic Vinyl Compound Co-polymers Prepared by Using the Same
EP2046842A2 (en) Isotactic-atactic polypropylene and methods of making same
KR101903892B1 (en) Preparing method of ethylene-propylene random copolymer using polyolefin catalyst
KR102502159B1 (en) Propylene-ethylene random copolymer
JP3144851B2 (en) Olefin polymerization method

Legal Events

Date Code Title Description
AK Designated states

Kind code of ref document: A1

Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GD GE GH GM HR HU ID IL IN IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US UZ VN YU ZW

AL Designated countries for regional patents

Kind code of ref document: A1

Designated state(s): GH GM KE LS MW SD SZ UG ZW AM AZ BY KG KZ MD RU TJ TM AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE BF BJ CF CG CI CM GA GN GW ML MR NE SN TD TG

DFPE Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101)
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: KR

REG Reference to national code

Ref country code: DE

Ref legal event code: 8642

122 Ep: pct application non-entry in european phase