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EP0347129A1
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Process for production of high molecular weight EPDM elastomers using a metallocene-alumoxane catalyst system
Assignee: ExxonMobil Chemical Patents Inc
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Filing: 1989-06-09
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Granted: —
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Expires: 2009-06-09
Abstract
Abstract A process for producing a high molecular weight EPDM elastomer having low crystallinity using a bridged bis-metallocene-alumoxane catalyst wherein the metallocene component of the catalyst has the formula: wherein "M" is titanium, zirconium or hafnium; each "R¹" independently is a C₁ to C₂₀ linear, branched or cyclic alkyl group or a C₂ to C₄ alkylene which forms a fused ring system; "R²" is a C₁ to C₆ linear, branched or cyclic alkylene group, an alkyl substituted silanylene group or an alkyl substituted silaalkylene group; each "X" independently is a halogen, hydride, alkyl, aryl or chelating group, and "y" is an integer of 2 to 4.
Inventors
- 👤 Sigmund Floyd
- 👤 Elvin Lynn Hoel
Bibliographic Details
Application Number
—
Jurisdiction
EP
Data Source
google_patents
Last Synchronized
2026-10-30 19:52
CPC Classifications
C; C08; C08F; C08F210/00; C08F210/16; C08F210/18; C08F4/00; C08F4/42; C08F4/44; C08F4/60; C08F4/62; C08F4/64; C08F4/659; C08F4/65912; C08F4/65916; C08F4/6592; C08F4/65922; C08F4/65927
Claims Analysis
Total Claims: 17
Claim 1
Independent Claim
213 words
A process for producing an EPDM elastomer, comprising: adding an α-olefin monomer in which an EPDM elastomer is substantially insoluble to a reaction vessel in an amount and under pressure sufficient to allow utilization of said α-olefin in liquified form as a polymerization diluent; supplying diene monomer to said diluent; adding ethylene to said diluent in an amount sufficient to maintain a desired ethylene/α-olefin ratio in the liquid phase of the reaction vessel; and, adding to said diluent a metallocene-alumoxane catalyst system wherein the metallocene component of the catalyst is of the formula: wherein "M" is titanium, zirconium or hafnium; each "R¹" independently is a C₁ to C₂₀ linear, branched or cyclic alkyl group or a C₂ to C₄ alkylene which forms a fused ring system; "R²" is a C₁ to C₆ linear, branched or cyclic alkylene group, an alkyl substituted silanylene group or an alkyl substituted silaalkylene group; each "X" Independently is a halogen, hydride, hydrocarbyl radical or chelating group, and "y" is an integer of 2, 3 or 4; reacting the mixture of monomers for a time sufficient to permit polymerization of said ethylene, α-olefln, and diene monomers to an EPDM elastomer having either a weight-average molecular weight greater than 110,000 or a Mooney viscosity (ML₁₊₈ at 127°C) greater than 10.
Claim 2
Dependent Claim
213 words
A process for producing an EPDM elastomer, comprising: adding an α-olefin monomer in which an EPDM elastomer is substantially insoluble to a reaction vessel in an amount and under pressure sufficient to allow utilization of said α-olefin in liquified form as a polymerization diluent; supplying diene monomer to said diluent; adding ethylene to said diluent in an amount sufficient to maintain a desired ethylene/α-olefin ratio in the liquid phase of the reaction vessel; and, adding to said diluent a metallocene-alumoxane catalyst system wherein the metallocene component of the catalyst is of the formula: wherein "M" is titanium, zirconium or hafnium; each "R¹" independently is a C₁ to C₂₀ linear, branched or cyclic alkyl group or a C₂ to C₄ alkylene which forms a fused ring system; "R²" is a C₁ to C₆ linear, branched or cyclic alkylene group, an alkyl substituted silanylene group or an alkyl substituted silaalkylene group; each "X" Independently is a halogen, hydride, hydrocarbyl radical or chelating group, and "y" is an integer of 2, 3 or 4; reacting the mixture of monomers for a time sufficient to permit polymerization of said ethylene, α-olefln, and diene monomers to an EPDM elastomer having either a weight-average molecular weight greater than 110,000 or a Mooney viscosity (ML₁₊₈ at 127°C) greater than 10.
Claim 3
Dependent Claim
41 words
The process according to claim 1, wherein said metallocene component of the catalyst is a zirconocene, the α-olefin monomer is propylene and/or 1-butene, and/or wherein the diene is one or more of the following 1,4 hexadiene; 5-ethylidene-2-norbornene; 5-methylene-2-norbornene; 5-vinylidene-2-norbornene; or dicyclopentadiene.
Claim 4
Dependent Claim
31 words
The process according to claim 1 or claim 2, wherein said zirconocene-alumoxane catalyst system is partially or wholly present on a catalyst support material, preferably a silica gel treated with methylalumoxane.
Claim 5
Dependent Claim
22 words
The process according to any of the preceding claims, wherein R² of the zirconocene component of the catalyst is ethylene and/or dimethylsilanylene.
Claim 6
Dependent Claim
43 words
The process according to any of the preceding claims, wherein the metallocene component of the catalyst is of the formula: wherein R³ is a C₁ to C₂₀ linear, branched or cyclic alkyl group and "z" is an integer of 0, 1 or 2.
Claim 7
Dependent Claim
73 words
The process according to any of claims 2 to 5, wherein there exists in the reactor vessel a mole ratio of aluminum to zirconium in the range of 10 to 5,000 and/or wherein the polymerization diluent is subjected to an amount of ethylene to maintain a total pressure in the reaction vessel in the range of 10 to 1,000 psi in excess of the combined vapor pressure of the α-olefin and diene monomers.
Claim 8
Dependent Claim
12 words
A process according to claim 5 or 6 wherein "z" is 0.
Claim 9
Dependent Claim
24 words
The process according to any of the preceding claims wherein the propylene polymerization diluent is maintained at a temperature of from 20 to 60°C.
Claim 10
Dependent Claim
207 words
A process for producing an EPDM elastomer, comprising the steps of: adding an α-olefin monomer to a reaction vessel in an amount sufficient to serve as a polymerization diluent; supplying diene monomer to said α-olefin monomer polymerization diluent; suspending in said α-olefin monomer polymerization diluent a supported zirconocene-alumoxane catalyst system wherein the zirconocene component of the catalyst is of the formula: wherein "R³" is a linear or branched hydrocarbyl radical having from 1 to 20 carbon atoms; "z" is an integer number from 0 to 2; R² bridging group is a linear, branched or cyclic alkylene radical having from one to six carbon atoms or an alkyl substituted silanylene group having from one to two silicon atoms; and each "X" independently is alkyl, aryl, hydride, or halogen; subjecting said α-olefin polymerization diluent to ethylene in an amount to maintain total pressure in the reaction vessel in excess of the vapor pressure of the α-olefin and diene monomers, and; maintaining the α-olefin polymerization diluent at a temperature of from -10 to 90°C for a time sufficient to permit copolymerization of said ethylene, α-olefin and diene monomers to an EPDM elastomer having a weight-average molecular weight greater than 110,000 and a Mooney viscosity (ML₁₊₈ at 127°C) greater than 10.
Claim 11
Dependent Claim
207 words
A process for producing an EPDM elastomer, comprising the steps of: adding an α-olefin monomer to a reaction vessel in an amount sufficient to serve as a polymerization diluent; supplying diene monomer to said α-olefin monomer polymerization diluent; suspending in said α-olefin monomer polymerization diluent a supported zirconocene-alumoxane catalyst system wherein the zirconocene component of the catalyst is of the formula: wherein "R³" is a linear or branched hydrocarbyl radical having from 1 to 20 carbon atoms; "z" is an integer number from 0 to 2; R² bridging group is a linear, branched or cyclic alkylene radical having from one to six carbon atoms or an alkyl substituted silanylene group having from one to two silicon atoms; and each "X" independently is alkyl, aryl, hydride, or halogen; subjecting said α-olefin polymerization diluent to ethylene in an amount to maintain total pressure in the reaction vessel in excess of the vapor pressure of the α-olefin and diene monomers, and; maintaining the α-olefin polymerization diluent at a temperature of from -10 to 90°C for a time sufficient to permit copolymerization of said ethylene, α-olefin and diene monomers to an EPDM elastomer having a weight-average molecular weight greater than 110,000 and a Mooney viscosity (ML₁₊₈ at 127°C) greater than 10.
Claim 12
Dependent Claim
130 words
A process for producing an EPDM elastomer having either a weight-average molecular weight greater than 110,000 or a Mooney viscosity (ML₁₊₈ at 127°C) greater than 10, comprising contacting under polymerization conditions ethylene, an α-olefin monomer and a diene monomer with a metallocene-alumoxane catalyst system wherein the metallocene is represented by the formula: wherein "M" is titanium, zirconlum or hafnium; each "R¹" independently is a C₁ to C₂₀ linear, branched or cyclic alkyl group or a C₂ to C₄ alkylene which forms a fused ring system; "R²" is a C₁ to C₆ linear, branched or cyclic alkylene group, an alkyl substituted silanylene group or an alkyl substituted silaalkylene group; each "X" independently is a halogen, hydride, alkyl, aryl or chelating group, and "y" is an integer of 2, 3, or 4.
Claim 13
Dependent Claim
130 words
A process for producing an EPDM elastomer having either a weight-average molecular weight greater than 110,000 or a Mooney viscosity (ML₁₊₈ at 127°C) greater than 10, comprising contacting under polymerization conditions ethylene, an α-olefin monomer and a diene monomer with a metallocene-alumoxane catalyst system wherein the metallocene is represented by the formula: wherein "M" is titanium, zirconlum or hafnium; each "R¹" independently is a C₁ to C₂₀ linear, branched or cyclic alkyl group or a C₂ to C₄ alkylene which forms a fused ring system; "R²" is a C₁ to C₆ linear, branched or cyclic alkylene group, an alkyl substituted silanylene group or an alkyl substituted silaalkylene group; each "X" independently is a halogen, hydride, alkyl, aryl or chelating group, and "y" is an integer of 2, 3, or 4.
Claim 14
Dependent Claim
49 words
The process of claim 10, wherein said process is a continuous polymerization process, preferably a slurry process employing a hydrocarbon in which an EPDM elastomer is substantially insoluble in an amount and under a pressure sufficient to allow utilization of said hydrocarbon in liquified form as a polymerization diluent.
Claim 15
Dependent Claim
78 words
The process of claim 10 or claim 11, wherein M is zirconium and the zirconocene-alumoxane catalyst is present on a catalyst support material, the zirconium being present in an amount of from 0.02 to 5.0 weight percent zirconium metal based on total catalyst weight, preferably with the catalyst support material being a silica gel treated with methylalumoxane and/or zirconium being present in an amount of from 0.10 to 1.0 weight percent zirconium metal based on total catalyst weight.
Claim 16
Dependent Claim
48 words
The process according to any of claims 10 to 12, wherein M is zirconium and the zirconocene component of the catalyst is of the formula: wherein R³ is a C₁ to C₂₀ linear, branched or cyclic alkyl group and "z" is an integer of 0, 1, or 2.
Claim 17
Dependent Claim
32 words
The process according to any of claims 10 to 13, wherein there exists in the reactor vessel a mole ratio of aluminum to metal M in the range of 10 to 5,000.
References Cited (Backward Citations)
EP0260999A1
Cited
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