Process for production of high molecular weight EPDM elastomers using a metallocene-alumoxane catalyst system

Claim 2

A process for producing an elastomer having either a weight-average molecular weight greater than 110,000 or a Mooney viscosity (ML 1+8 at 127° C.) greater than 10, comprising contacting under slurry or solution polymerization conditions ethylene, a C 3 -C 16 α-olefin monomer and a non-conjugated diene monomer with a metallocene-alumoxane catalyst system wherein the metallocene is represented by the formula: ##STR5## wherein "M" is titanium, zirconium or hafnium; each "R 1 " independently is a C 1 to C 20 linear, branched or cyclic alkyl group or a C 2 to C 4 alkylene which forms a fused ring system; "R 2 " is a C 1 to C 6 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 3

A process for producing an elastomer having either a weight-average molecular weight greater than 110,000, or a Mooney viscosity (ML 1+8 at 127° C.) greater than 10, comprising contacting under slurry or solution polymerization conditions ethylene, a C 3 to C 16 α-olefin monomer and a non-conjugated diene monomer with a metallocene-alumoxane catalyst system wherein the metallocene is represented by the formula: ##STR6## wherein "M" is titanium, zirconium, or hafnium; each "R 1 " independently is a C 1 to C 20 linear, branched, or cyclic alkyl group or a C 2 to C 4 alkylene which forms a fused ring system; "R 2 " is a C 1 to C 6 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, and wherein the catalyst is present on a catalyst support material.

Claim 4

A process for producing an elastomer having either a weight-average molecular weight greater than 110,000, or a Mooney viscosity (ML 1+8 at 127° C.) greater than 10, comprising contacting under slurry or solution polymerization conditions ethylene, a C 3 to C 16 α-olefin monomer and a non-conjugated diene monomer with a metallocene-alumoxane catalyst system wherein the metallocene is represented by the formula: ##STR6## wherein "M" is titanium, zirconium, or hafnium; each "R 1 " independently is a C 1 to C 20 linear, branched, or cyclic alkyl group or a C 2 to C 4 alkylene which forms a fused ring system; "R 2 " is a C 1 to C 6 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, and wherein the catalyst is present on a catalyst support material.

Claim 5

The process of claim 2, wherein said process is a continuous polymerization process.

Claim 6

The process of claim 3, wherein said continuous polymerization process is a slurry process and a hydrocarbon in which said elastomer is substantially insoluble is employed in an amount and under a pressure sufficient to allow utilization of said hydrocarbon in liquified form as a polymerization diluent.

Claim 7

The process of claim 2, wherein said catalyst support material is a silica gel treated with methylalumoxane and zirconium is present in an amount of from about 0.10 to about 1.0 weight percent zirconium metal based on total catalyst weight.

Claim 8

The process of claim 2, wherein said metallocene component of the catalyst is a zirconocene.

Claim 9

The process of claim 6, wherein the α-olefin monomer is one of propylene and 1-butene.

Claim 10

The process of claim 6 wherein zirconium is present in an amount of from about 0.02 to about 5.0 weight percent zirconium metal based on total catalyst weight.

Claim 11

The process of claim 6, wherein there exists in the reactor vessel a mole ratio of aluminum to zirconium in the range of 10 to 5,000.

Claim 12

The process of claim 6, wherein R 2 of the zirconocene component of the catalyst is selected from the group consisting of ethylene and dimethylsilanylene.

Claim 13

The process of claim 6, wherein the diene monomer 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 14

The process of claim 11, wherein the zirconocene component of the catalyst is of the formula: ##STR7## wherein R 3 is a C 1 to C 20 linear, branched or cyclic alkyl group and "z" is an integer of 0, 1, or 2.

Claim 15

A process for producing an elastomer, comprising: adding a C 3 -C 16 α-olefin monomer, in which an 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 non-conjugated 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: ##STR8## wherein "M" is titanium, zirconium or hafnium; each "R 1 " independently is a C 1 to C 20 linear, branched or cyclic alkyl group or a C 2 to C 4 alkylene which forms a fused ring system; "R 2 " is a C 1 to C 6 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-olefin, and diene monomers to an elastomer having either a weight-average molecular weight greater than 110,000 or a Mooney viscosity (ML 1+8 at 127° C.) greater than 10.

Claim 16

A process for producing an elastomer, comprising: adding a C 3 -C 16 α-olefin monomer, in which an 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 non-conjugated 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: ##STR8## wherein "M" is titanium, zirconium or hafnium; each "R 1 " independently is a C 1 to C 20 linear, branched or cyclic alkyl group or a C 2 to C 4 alkylene which forms a fused ring system; "R 2 " is a C 1 to C 6 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-olefin, and diene monomers to an elastomer having either a weight-average molecular weight greater than 110,000 or a Mooney viscosity (ML 1+8 at 127° C.) greater than 10.

Claim 17

The process of claim 1, wherein the metallocene component of the catalyst is of the formula: ##STR9## wherein R 3 is a C 1 to C 20 linear, branched or cyclic alkyl group and "z" is an integer of 0, 1 or 2.

Claim 18

The process of claim 14, wherein R 2 of the zirconocene component of the catalyst is ethylene.

Claim 19

The process of claim 14, wherein R 2 of the zirconocene component of the catalyst is dimethylsilanylene.

Claim 20

A process for producing an elastomer, comprising: adding a C 3 -C 16 α-olefin monomer, in which an 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 non-conjugated 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 which is partially or wholly supported on a catalyst support material, wherein the metallocene component of the catalyst is of the formula: ##STR10## wherein "M" is titanium, zirconium, or hafnium; each "R 1 " independently is a C 1 to C 20 linear, branched, or cyclic alkyl group or a C 2 to C 4 alkylene which forms a fused ring system; "R 2 " is a C 1 to C 6 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-olefin, and diene monomers to an elastomer having either a weight-average molecular weight greater than 110,000 or a Mooney viscosity (ML 1+8 at 127° C.) greater than 10.

Claim 21

A process for producing an elastomer, comprising: adding a C 3 -C 16 α-olefin monomer, in which an 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 non-conjugated 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 which is partially or wholly supported on a catalyst support material, wherein the metallocene component of the catalyst is of the formula: ##STR10## wherein "M" is titanium, zirconium, or hafnium; each "R 1 " independently is a C 1 to C 20 linear, branched, or cyclic alkyl group or a C 2 to C 4 alkylene which forms a fused ring system; "R 2 " is a C 1 to C 6 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-olefin, and diene monomers to an elastomer having either a weight-average molecular weight greater than 110,000 or a Mooney viscosity (ML 1+8 at 127° C.) greater than 10.

Claim 22

A process for producing an elastomer, comprising: adding a C 3 -C 16 α-olefin monomer, in which an 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 non-conjugated 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 zirconocene-alumoxane catalyst system wherein the zirconocene component of the catalyst is of the formula: ##STR11## wherein "R 2 " is a C 1 to C 6 linear, branched or cyclic alkylene group, and alkyl substituted silanylene group, or an alkyl substituted silaalkylene group; and each "X" independently is a halogen, hydride, alkyl, aryl or chelating group; reacting the mixture of monomers for a time sufficient to permit polymerization of said ethylene, α-olefin, and diene monomers to an elastomer having either a weight-average molecular weight greater than 110,000 or a Mooney viscosity (ML 1+8 at 127° C.) greater than 10.

Claim 23

A process for producing an elastomer, comprising: adding a C 3 -C 16 α-olefin monomer, in which an 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 non-conjugated 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 zirconocene-alumoxane catalyst system wherein the zirconocene component of the catalyst is of the formula: ##STR11## wherein "R 2 " is a C 1 to C 6 linear, branched or cyclic alkylene group, and alkyl substituted silanylene group, or an alkyl substituted silaalkylene group; and each "X" independently is a halogen, hydride, alkyl, aryl or chelating group; reacting the mixture of monomers for a time sufficient to permit polymerization of said ethylene, α-olefin, and diene monomers to an elastomer having either a weight-average molecular weight greater than 110,000 or a Mooney viscosity (ML 1+8 at 127° C.) greater than 10.

Claim 24

The process of claim 18, wherein the α-olefin monomer is propylene and the diene monomer 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 25

The process of claim 18, wherein the α-olefin is propylene.

Claim 26

The process of claim 18, wherein the α-olefin is 1-butene.

Claim 27

The process of claim 18, wherein R 2 of the zirconocene component of the catalyst is ethylene.

Claim 28

The process of claim 18, wherein R 2 of the zirconocene component of the catalyst is dimethylsilanylene.

Claim 29

The process of claim 18, wherein R 2 of the zirconocene component of the catalyst is ethylene or dimethylsilanylene and the α-olefin polymerization diluent is maintained at a temperature of from about 20° to about 60° C.

Claim 30

A process for producing an elastomer, comprising: adding a C 3 -C 16 α-olefin monomer, in which an 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 non-conjugated 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 zirconocene-alumoxane catalyst system which is partially or wholly supported on a catalyst support material, wherein the zirconocene component of the catalyst is of the formula: ##STR12## wherein each "R 1 " independently is a C 1 to C 20 linear, branched, or cyclic alkyl group or a C 2 to C 4 alkylene which forms a fused ring system; "R 2 " is a C 1 to C 6 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-olefin, and diene monomers to an elastomer having either a weight-average molecular weight greater than 110,000 or a Mooney viscosity (ML 1+8 at 127° C.) greater than 10.

Claim 31

A process for producing an elastomer, comprising: adding a C 3 -C 16 α-olefin monomer, in which an 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 non-conjugated 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 zirconocene-alumoxane catalyst system which is partially or wholly supported on a catalyst support material, wherein the zirconocene component of the catalyst is of the formula: ##STR12## wherein each "R 1 " independently is a C 1 to C 20 linear, branched, or cyclic alkyl group or a C 2 to C 4 alkylene which forms a fused ring system; "R 2 " is a C 1 to C 6 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-olefin, and diene monomers to an elastomer having either a weight-average molecular weight greater than 110,000 or a Mooney viscosity (ML 1+8 at 127° C.) greater than 10.

Claim 32

The process of claim 25, wherein the α-olefin monomer is one of 1-butene or propylene.

Claim 33

The process of claim 25, 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 34

The process of claim 25, wherein R 2 of the zirconocene component of the catalyst is ethylene.

Claim 35

The process of claim 25, wherein there exists in the reactor vessel a mole ratio of aluminum to zirconium in the range of 10 to 5,000.

Claim 36

The process of claim 25, 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 37

The process of claim 25, wherein the zirconocene component of the catalyst is of the formula: ##STR13## wherein R 2 is a C 1 to C 6 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 R 3 is a C 1 to C 20 linear, branched or cyclic alkyl group and "z" is an integer of 0, 1, or 2.

Claim 38

The process of claim 25, wherein the zirconocene component of the catalyst is of the formula: ##STR14## wherein "R 2 " is a C 1 to C 6 linear, branched, or cyclic alkylene group, an alkyl substituted silanylene group or an alkyl substituted silaalkylene group; and each "X" independently is a halogen, hydride, hydrocarbyl radical or chelating group.

Claim 39

A process for producing an elastomer, comprising the steps of: adding a C 3 -C 16 α-olefin monomer to a reaction vessel in an amount sufficient to serve as a polymerization diluent; supplying non-conjugated 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: ##STR15## wherein "R 3 " is a linear or branched hydrocarbyl radical having from 1 to 20 carbon atoms; "z" is an integer number from 0 to 2; R 2 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 about -10° to about 90° C. for a time sufficient to permit copolymerization of said ethylene, α-olefin and diene monomers to an elastomer having a weight-average molecular weight greater than 110,000 and a Mooney viscosity (ML 1+8 at 127° C.) greater than 10.

Claim 40

A process for producing an elastomer, comprising the steps of: adding a C 3 -C 16 α-olefin monomer to a reaction vessel in an amount sufficient to serve as a polymerization diluent; supplying non-conjugated 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: ##STR15## wherein "R 3 " is a linear or branched hydrocarbyl radical having from 1 to 20 carbon atoms; "z" is an integer number from 0 to 2; R 2 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 about -10° to about 90° C. for a time sufficient to permit copolymerization of said ethylene, α-olefin and diene monomers to an elastomer having a weight-average molecular weight greater than 110,000 and a Mooney viscosity (ML 1+8 at 127° C.) greater than 10.