EP0347128A1 — Process for production of a high molecular weight…

Claim 1

Independent Claim 196 words

A process for producing an EPC elastomer in slurry polymerization, comprising: adding an α-olefin monomer in which an EPC 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: adding ethylene to said α-olefin monomer polymerization diluent in an amount sufficient to maintain a desired ethylene/α-olefin ratio in the liquid phase of the reaction vessel and; adding to the mixture of monomers a metallocene/alumoxane catalyst system wherein the metallocene component of the catalyst is of the formula: where M is zirconium, titanium, or hafnium; each R¹ independently is a C₁ to C₂₀ linear or branched alkyl or cyclic alkylene group, R² is a C₁ to C₆ linear, branched or cyclic alkylene, an alkyl substituted silanylene or an alkyl substituted silaalkylene group, each X independently is a halide, hydride, the oxygen of an oxygen bridged zirconocene dimer, or a hydrocarbyl radical, "b" is 0 or 1, and "y" is an integer of 2, 3 or 4; reacting the mixture of olefin monomers for a time sufficient to permit copolymerization of said ethylene and α-olefin monomers to an EPC elastomer.

Claim 2

Dependent Claim 196 words

A process for producing an EPC elastomer in slurry polymerization, comprising: adding an α-olefin monomer in which an EPC 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: adding ethylene to said α-olefin monomer polymerization diluent in an amount sufficient to maintain a desired ethylene/α-olefin ratio in the liquid phase of the reaction vessel and; adding to the mixture of monomers a metallocene/alumoxane catalyst system wherein the metallocene component of the catalyst is of the formula: where M is zirconium, titanium, or hafnium; each R¹ independently is a C₁ to C₂₀ linear or branched alkyl or cyclic alkylene group, R² is a C₁ to C₆ linear, branched or cyclic alkylene, an alkyl substituted silanylene or an alkyl substituted silaalkylene group, each X independently is a halide, hydride, the oxygen of an oxygen bridged zirconocene dimer, or a hydrocarbyl radical, "b" is 0 or 1, and "y" is an integer of 2, 3 or 4; reacting the mixture of olefin monomers for a time sufficient to permit copolymerization of said ethylene and α-olefin monomers to an EPC elastomer.

Claim 3

Dependent Claim 32 words

The process of claim 1 wherein M is zirconium and said zirconocene/alumoxane catalyst system is present on a catalyst support material, preferably a silica gel and/or preferably with said alumoxane being methylalumoxane.

Claim 4

Dependent Claim 19 words

The process of claim 1 or claim 2, wherein the α-olefin monomer is propylene, 1-butene or a mixture thereof.

Claim 5

Dependent Claim 48 words

The process according to any of the preceding claims wherein "b" is 0 and the R² of the zirconocene component of the catalyst is absent, wherein R² of the zirconocene component of the catalyst is ethylene; and/or wherein R² of the zirconocene component of the catalyst is dimethylsilanylene.

Claim 6

Dependent Claim 29 words

The process according to any of the preceding claims wherein the metallocene component of the catalyst is of the formula and "z" is an integer from 0 to 2.

Claim 7

Dependent Claim 28 words

The process according to any of claims 2 to 5, wherein the catalyst has a mole ratio of aluminum to zirconium in the range of 10 to 5,000.

Claim 8

Dependent Claim 20 words

The process according to any of the preceding claims, wherein the temperature for polymerization is in the range of 0-80°C.

Claim 9

Dependent Claim 231 words

A process for producing an ethylene-α-olefin elastomeric copolymer in slurry polymerization, comprising the steps of: adding an α-olefin monomer to a reaction vessel in an amount and under a pressure sufficient to allow utilization of said α-olefin in a liquified state as a polymerization diluent; adding ethylene to said α-olefin polymerization diluent in an amount sufficient to maintain a desired ethylene/propylene ratio in the liquid phase in the reaction vessel, and; adding to the mixture of monomers a supported metallocene/alumoxane catalyst which has been prepolymerized with ethylene or an α-olefin to a weight increase of at least 50% based on the total weight of the catalyst and support material wherein the catalyst support is an alumoxane treated inorganic oxide and the metallocene component of the catalyst is of the formula: where M is zirconium, titanium, or hafnium; each R¹ independently is a C₁ to C₂₀ linear or branched alkyl or cyclic alkylene group, R² is a C₁ to C₆ linear, branched or cyclic alkylene, an alkyl substituted silanylene or an alkyl substituted silaalkylene group, each X independently is a halide, hydride, the oxygen of an oxygen bridged zirconocene dimer, or a hydrocarbyl radical, "b" is 0 or 1, and "y" is an integer of 2, 3, or 4; reacting the mixture of olefin monomers for a time sufficient to permit copolymerization of said ethylene and α-olefin monomers to an EPC elastomer.

Claim 10

Dependent Claim 231 words

A process for producing an ethylene-α-olefin elastomeric copolymer in slurry polymerization, comprising the steps of: adding an α-olefin monomer to a reaction vessel in an amount and under a pressure sufficient to allow utilization of said α-olefin in a liquified state as a polymerization diluent; adding ethylene to said α-olefin polymerization diluent in an amount sufficient to maintain a desired ethylene/propylene ratio in the liquid phase in the reaction vessel, and; adding to the mixture of monomers a supported metallocene/alumoxane catalyst which has been prepolymerized with ethylene or an α-olefin to a weight increase of at least 50% based on the total weight of the catalyst and support material wherein the catalyst support is an alumoxane treated inorganic oxide and the metallocene component of the catalyst is of the formula: where M is zirconium, titanium, or hafnium; each R¹ independently is a C₁ to C₂₀ linear or branched alkyl or cyclic alkylene group, R² is a C₁ to C₆ linear, branched or cyclic alkylene, an alkyl substituted silanylene or an alkyl substituted silaalkylene group, each X independently is a halide, hydride, the oxygen of an oxygen bridged zirconocene dimer, or a hydrocarbyl radical, "b" is 0 or 1, and "y" is an integer of 2, 3, or 4; reacting the mixture of olefin monomers for a time sufficient to permit copolymerization of said ethylene and α-olefin monomers to an EPC elastomer.

Claim 11

Dependent Claim 56 words

The process of claim 8 wherein M is zirconium and the zirconocene component of the catalyst is of the formula: wherein each R¹ independently is a linear or branched hydrocarbyl radical having from 1 to 20 carbon atoms; "z" is an integer from 0 to 2, and each "X" independently is alkyl, aryl, hydride, or halide.

Claim 12

Dependent Claim 19 words

A process according to claim 5 or 9 and including the features of any of claims 2 to 7.

Claim 13

Dependent Claim 134 words

A prepolymerized catalyst for producing EPC elastomers in liquid olefin slurry polymerization, comprising: an inorganic support which has been dried and treated with an alumoxane followed by addition of zirconocene of structure: wherein each R¹ independently is a C₁-C₂₀ linear, branched or cyclic alkyl group or a C₂-C-₄ cyclic alkylene group which forms a fused ring system group; R² is a C₁-C₆ linear, branched or cyclic alkylene, a Si₁-Si₂ alkyl substituted silanylene group or an alkyl substituted silaalkylene group; each X independently is a halide, hydride, an oxygen bridge of a zirconocene dimer, or a hydrocarbyl radical; "y" is a number 2, 3, or 4, and "b" is either 0 or 1; followed by a prepolymerization treatment with ethylene or an α-olefin to increase the weight of the catalyst by at least 50 wt%.

Claim 14

Dependent Claim 134 words

A prepolymerized catalyst for producing EPC elastomers in liquid olefin slurry polymerization, comprising: an inorganic support which has been dried and treated with an alumoxane followed by addition of zirconocene of structure: wherein each R¹ independently is a C₁-C₂₀ linear, branched or cyclic alkyl group or a C₂-C-₄ cyclic alkylene group which forms a fused ring system group; R² is a C₁-C₆ linear, branched or cyclic alkylene, a Si₁-Si₂ alkyl substituted silanylene group or an alkyl substituted silaalkylene group; each X independently is a halide, hydride, an oxygen bridge of a zirconocene dimer, or a hydrocarbyl radical; "y" is a number 2, 3, or 4, and "b" is either 0 or 1; followed by a prepolymerization treatment with ethylene or an α-olefin to increase the weight of the catalyst by at least 50 wt%.

Claim 15

Dependent Claim 61 words

The prepolymerized catalyst according to claim 11 wherein the inorganic support is a silica gel dried at 100 to 1000°C, wherein the alumoxane is methylalumoxane and the ratio with the silica gel is in the range of 1:1 to 1:10 on a weight basis, and/or wherein the mole ratio of aluminum to zirconium is in the range of 1 to 500.

Claim 16

Dependent Claim 23 words

The prepolymerized catalyst of claim 11 or claim 12, wherein the prepolymerization weight gain is in the range of 50 to 500 wt%.

Claim 17

Dependent Claim 23 words

The prepolymerized catalyst according to any of claims 10 to 13 wherein the zirconocene is bis(tetrahydroindenyl)zirconium dichloride, dimethylsilanylene-bis(tetrahydroindenyl) zirconium dichloride or ethylene-bis(tetrahydroindenyl)zirconium dichloride.

Claim 18

Dependent Claim 21 words

The prepolymerized catalyst according to any of the preceding claims wherein the prepolymerized catalyst is washed with a hydrocarbon following prepolymerization.

Claim 19

Dependent Claim 111 words

A process for producing an EPC elastomer comprising contacting under polymerization conditions ethylene and an α-olefin monomer with a metallocene/alumoxane catalyst system wherein the metallocene component of the catalyst is of the formula: where M is zirconium, titanium, or hafnium; each R¹ independently is a C₁ to C₂₀ linear or branched alkyl or cyclic alkylene group: R₂ is a C₁ to C₆ linear, branched or cyclic alkylene, an alkyl substituted silanylene or an alkyl substituted silaalkylene group; each X independently is a halide, hydride, the oxygen of an oxygen bridged zirconocene dimer, or a hydrocarbyl radical; "b" is 0 or 1; and "y" is an integer of 2, 3, or 4.

Claim 20

Dependent Claim 111 words

A process for producing an EPC elastomer comprising contacting under polymerization conditions ethylene and an α-olefin monomer with a metallocene/alumoxane catalyst system wherein the metallocene component of the catalyst is of the formula: where M is zirconium, titanium, or hafnium; each R¹ independently is a C₁ to C₂₀ linear or branched alkyl or cyclic alkylene group: R₂ is a C₁ to C₆ linear, branched or cyclic alkylene, an alkyl substituted silanylene or an alkyl substituted silaalkylene group; each X independently is a halide, hydride, the oxygen of an oxygen bridged zirconocene dimer, or a hydrocarbyl radical; "b" is 0 or 1; and "y" is an integer of 2, 3, or 4.

Claim 21

Dependent Claim 39 words

The process of claim 16 wherein M is zirconium, said zirconocene/alumoxane catalyst system is present on a catalyst support material preferably silica, and zirconium metal is present in from 0.02 to 5.0 weight percent based on total catalyst weight.

Claim 22

Dependent Claim 25 words

The process according to claim 16 or 17 wherein the catalyst has a mole ratio of aluminum to metal (M) in the range of 1-200.

Claim 23

Dependent Claim 17 words

The process according to any of claims 16 to 18, wherein said process is a continuous process.

Claim 24

Dependent Claim 71 words

The process according to any of claims 16 to 19, wherein said process is a continuous slurry process and a hydrocarbon in which an EPC elastomer is substantially insoluble is employed in an amount and under pressure sufficient to allow utilization of said hydrocarbon in liquified form as a polymerization diluent, preferably said hydrocarbon employed as a polymerization diluent being at least in part or in its entirety the α-olefin monomer.

Process for production of a high molecular weight ethylene a-olefin elastomer with a metallogene alumoxane catalyst

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