WO1999035171A1 - Elastomeres copolymeres polyolefiniques a point de fusion eleve, catalyseurs et procedes de synthese - Google Patents

Elastomeres copolymeres polyolefiniques a point de fusion eleve, catalyseurs et procedes de synthese Download PDF

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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
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bis
indene
methyl
copolymer
polymerization process
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PCT/US1999/000540
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English (en)
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Robert M. Waymouth
Raisa L. Kravchenko
Jennifer Maciejewski Petoff
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The Board Of Trustees Of The Leland Stanford Jr. University
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Priority to AU21115/99A priority Critical patent/AU2111599A/en
Priority to PCT/US1999/000540 priority patent/WO1999035171A1/fr
Publication of WO1999035171A1 publication Critical patent/WO1999035171A1/fr

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    • 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.

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Abstract

L'invention concerne des copolymères polyoléfiniques à point de fusion élevé, convenant en tant qu'élastomères thermoplastiques, des catalyseurs et leurs procédés de synthèse. Ces copolymères oléfiniques élastomères se caractérisent par: une fraction en mole de composant cristallisable Xc comprise entre 30 et environ 99 %; des températures de transition vitreuses basses, inférieures à -20 °C, et généralement inférieures à -50 °C; des points de fusion supérieurs à environ 90 °C; des poids moléculaires élevés; une répartition des poids moléculaires MW/Mn≤10; et une répartition serrée de la composition entre les chaînes ≤ 15 %. Les nouveaux copolymères de l'invention trouvent des applications étendues, des mélanges pour réacteur aux copolymères blocs pouvant être fractionnés séquentiellement, de sorte que des fractions de différentes cristallinité soient produites, lesdites fractions présentant des compositions de comonomères différant de moins de 15 % du polymère parent (produit du réacteur). L'invention porte également sur un procédé de production desdits copolymères au moyen d'un catalyseur métallocène cyclopentadiénylique non ponté, substitué ou non, qui est capable de passer dans plusieurs états à caractéristiques de copolymérisation différentes, cette interconversion étant commandée par la sélection de substituants de ligands de cyclopendiényle, de sorte que la vitesse d'interconversion des deux états se trouve dans plusieurs ordres de grandeur de vitesse de formation d'une chaîne polymère unique. Lorsque ri⊃rf, le polymère peut être caractérisé comme étant multibloc; si ri∫rf, le résultat est un mélange polymère et lorsque ri/rf est proche de 1, le polymère résultant est un mélange d'alliage et de multibloc. Les catalyseurs métallocènes de l'invention sont capables de s'interconvertir entre plus de deux états, un mode de réalisation à quatre états étant représenté dans la Figure 2.
PCT/US1999/000540 1998-01-09 1999-01-08 Elastomeres copolymeres polyolefiniques a point de fusion eleve, catalyseurs et procedes de synthese WO1999035171A1 (fr)

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Cited By (41)

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WO2000040625A1 (fr) * 1999-01-08 2000-07-13 The Board Of Trustees Of The Leland Stanford Junior University Copolymeres d'ethylene a repartition etroite de la composition et a temperatures de fusion elevees, et procedes de production desdits copolymeres
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
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
US7622529B2 (en) 2004-03-17 2009-11-24 Dow Global Technologies Inc. Polymer blends from interpolymers of ethylene/alpha-olefin with improved compatibility
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 (ja) * 2016-10-24 2018-05-10 三井化学株式会社 遷移金属化合物、オレフィン重合用触媒およびオレフィン重合体の製造方法

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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 (fr) * 1999-01-08 2000-07-13 The Board Of Trustees Of The Leland Stanford Junior University Copolymeres d'ethylene a repartition etroite de la composition et a temperatures de fusion elevees, et procedes de production desdits copolymeres
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
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
US7622529B2 (en) 2004-03-17 2009-11-24 Dow Global Technologies Inc. Polymer blends from interpolymers of ethylene/alpha-olefin with improved compatibility
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 (ja) * 2016-10-24 2018-05-10 三井化学株式会社 遷移金属化合物、オレフィン重合用触媒およびオレフィン重合体の製造方法

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