Process for producing polyolefins and polyolefin catalysts

Claim 2

A process for preparing a heterogeneous catalyst support comprising bubbling a wet inert gas through a mixture of hydrocarbon an aliphatic solvent and an amount of an aluminum compound of the formula AlR 3 wherein each R can be the same or different and is selected from alkyl groups having from 1 to 10 carbon atoms, thereby producing an aluminoxane support wherein the temperature and pressure of said mixture is sufficient to maintain said hydrocarbon solvent in liquid phase and produce said aluminoxane support.

Claim 3

The process according to claim 1 wherein said wet inert gas is produced by bubbling the inert gas through water at a temperature and rate to essentially saturate said inert gas with water and wherein said wet inert gas is bubbled through said hydrocarbon solvent at a rate and temperature sufficient to essentially react all of said water with said aluminum compound.

Claim 4

The process according to claim 2 wherein the weight ratio of aluminum compound to hydrocarbon solvent is within the range of about 1:1 to 1:100, and the molar ratio of water to aluminum compound is within the range of about 0.01:1 to 1.4:1 and R is selected from alkyl groups having from 1 to 5 carbon atoms.

Claim 5

The process according to claim 3 wherein said weight ratio of aluminum compound to hydrocarbon is within the range of about 1:2 to 1:50 and the molar ratio of water to aluminum compound is within the range of about 0.5:1 to 1:1.

Claim 6

The process according to claim 4 wherein said inert gas is nitrogen, said aluminum compound is trimethylaluminum, and the weight ratio of trimethylaluminum to said aliphatic hydrocarbon is within the range of about 1:4 to 1:10.

Claim 7

A process for producing a heterogeneous catalyst comprising: bubbling a wet inert gas through a mixture of (a) a hydrocarbon solvent, (b) an amount of an aluminum compound of the formula AlR 3 wherein each R can be the same or different and is selected from alkyl groups having from 1 to 10 carbon atoms, and (c) at least two different metallocenes selected from mono, di, tri-cyclopentadienyls and substituted cyclopentadienyls of transition metal each having different termination rate constants of olefin polymerization in the presence of hydrogen, thereby producing a dual metal on aluminoxane polymerization catalyst wherein the temperature and pressure of said mixture is sufficient to maintain said hydrocarbon solvent in liquid phase and produce said aluminoxane support catalyst.

Claim 8

A process for producing a heterogeneous catalyst comprising: bubbling a wet inert gas through a mixture of (a) a hydrocarbon solvent, (b) an amount of an aluminum compound of the formula AlR 3 wherein each R can be the same or different and is selected from alkyl groups having from 1 to 10 carbon atoms, and (c) at least two different metallocenes selected from mono, di, tri-cyclopentadienyls and substituted cyclopentadienyls of transition metal each having different termination rate constants of olefin polymerization in the presence of hydrogen, thereby producing a dual metal on aluminoxane polymerization catalyst wherein the temperature and pressure of said mixture is sufficient to maintain said hydrocarbon solvent in liquid phase and produce said aluminoxane support catalyst.

Claim 9

The process according to claim 6 wherein said wet inert gas is produced by bubbling the inert gas through water at a temperature and rate to essentially saturate said inert gas with water and wherein said wet inert gas is bubbled through said hydrocarbon solvent at a rate and temperature sufficient to essentially react all of said water with said aluminum compound.

Claim 10

The process according to claim 7 wherein the weight ratio of aluminum compound to hydrocarbon solvent is within the range of about 1:1 to 1:100, and the molar ratio of water to aluminum compound is within the range of about 0.01:1 to 1.4:1 and R is selected from alkyl groups having from 1 to 5 carbon atoms.

Claim 11

The process according to claim 8 wherein said weight ratio of aluminum compound to hydrocarbon is within the range of about 1:2 to 1:50 and the molar ratio of water to aluminum compound is within the range of about 0.5:1 to 1:1.

Claim 12

The process according to claim 9 wherein said inert gas is nitrogen, said aluminum compound is trimethylaluminum, said hydrocarbon solvent is an aliphatic hydrocarbon, and the weight ratio of trimethylaluminum to aliphatic hydrocarbon is within the range of about 1:4 to 1:10.

Claim 13

The process according to claim 6 wherein said transition metals are selected from the group consisting of Group IVB, VB, and VIB transition metals.

Claim 14

The process according to claim 11 wherein said transition metals are titanium and zirconium.

Claim 15

The process according to claim 12 wherein the molar ratio of zirconium to titanium is within the range of about 0.01:1 to 99:1.

Claim 16

The process according to claim 13 wherein the molar ratio of zirconium to titanium is within the range of about 1:1 to 30:1.

Claim 17

The process according to claim 14 wherein the zirconium to titanium molar ratio is about 16:1.

Claim 18

The process according to claim 15 wherein the weight ratio of total metallocenes to said aluminum compound is within the range of about 1:5 to 1:10 8 .

Claim 19

The process according to claim 6 wherein said at least two different metallocenes are bis(cyclopentadienyl)zirconium dimethyl and bis(cyclopentadienyl)titanium dimethyl in a molar ratio between about 1:1 to 30:1 respectively, said aluminum compound is trimethylaluminum.

Claim 20

A process of producing a heterogeneous catalyst comprising: (a) bubbling a wet inert gas through a mixture of hydrocarbon solvent and an amount of aluminum compound of the formula AlR 3 wherein each R can be the same or different and is selected from alkyl groups having from 1 to 10 carbon atoms, thereby producing an aluminoxane, and (b) adding at least two different metallocenes selected from mono, di, and tri-cyclopentadienyls and substituted cyclopentadienyls of transition metals each having different termination rate constants of olefin polymerization in the presence of hydrogen, thereby producing a dual metal polymerization catalyst.

Claim 21

A process of producing a heterogeneous catalyst comprising: (a) bubbling a wet inert gas through a mixture of hydrocarbon solvent and an amount of aluminum compound of the formula AlR 3 wherein each R can be the same or different and is selected from alkyl groups having from 1 to 10 carbon atoms, thereby producing an aluminoxane, and (b) adding at least two different metallocenes selected from mono, di, and tri-cyclopentadienyls and substituted cyclopentadienyls of transition metals each having different termination rate constants of olefin polymerization in the presence of hydrogen, thereby producing a dual metal polymerization catalyst.

Claim 22

The process according to claim 18 wherein said wet inert gas is produced by bubbling the inert gas through water at a temperature and rate to essentially saturate said inert gas with water and wherein said wet inert gas is bubbled through said hydrocarbon solvent at a rate and temperature sufficient to essentially react all of said water with said aluminum compound.

Claim 23

The process according to claim 19 wherein the weight ratio of aluminum compound to hydrocarbon solvent is within the range of about 1:1 to 1:100, and the molar ratio of water to aluminum compound is within the range of about 0.01:1 to 1.4:1 and R is selected from alkyl groups having from 1 to 5 carbon atoms.

Claim 24

The process according to claim 20 wherein said weight ratio of aluminum compound to hydrocarbon is within the range of about 1:2 to 1:50 and the molar ratio of water to aluminum compound is within the range of about 0.5:1 to 1:1.

Claim 25

The process according to claim 21 wherein said inert gas is nitrogen, said aluminum compound is trimethylaluminum, said hydrocarbon solvent is an aliphatic hydrocarbon, and the weight ratio of trimethylaluminum to aliphatic hydrocarbon is within the range of about 1:4 to 1:10.

Claim 26

The process according to claim 18 wherein said transition metals are selected from the group consisting of Group IVB, VB, and VIB transition metals.

Claim 27

The process according to claim 23 wherein said transition metals are titanium and zirconium.

Claim 28

The process according to claim 24 wherein the molar ratio of zirconium to titanium is within the range of about 0.01:1 to about 99:1.

Claim 29

The process according to claim 25 wherein the molar ratio of zirconium to titanium is within the range of about 1:1 to 30:1.

Claim 30

The process according to claim 26 wherein the zirconium to titanium molar ratio is about 16:1.

Claim 31

The process according to claim 25 wherein the ratio of total metallocenes to said aluminoxane is within the range of about 1:5 to 1:10 8 .

Claim 32

The process according to claim 18 wherein said at least two different metallocenes are bis(cyclopentadienyl)zirconium dimethyl and bis(cyclopentadienyl)titanium dimethyl in a molar ratio between about 1:1 to 30:1 respectively, said aluminum compound is trimethylaluminum.

Claim 33

The process according to claim 6 wherein said metallocene is represented by the general formula (C 5 R'm)pR"s(C 5 R'm)MeQ 3 -p and R"s(C 5 R'm) 2 MeQ' wherein (C 5 R'm) is cyclopentadienyl or substituted cyclopentadienyl, each R can be the same or different and is selected from hydrogen or a hydrocarbyl radical selected from alkyl, alkenyl, aryl, alkylaryl, or arylalkyl radicals having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C 4 -C 6 ring, R" is a C 1 -C 4 alkylene radical, a dialkyl germanium or silicone or alkyl phosphine or amine radical bridging two (C 5 R'm) rings, Q is a hydrocarbon radical selected from the group consisting of aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radicals having from 1-20 carbon atoms or halogen and can be the same or different, Q' is an alkylidene radical having from 1 to about 20 carbon atoms, Me is a transition metal from Group IVB, VB, or VIB metals of the Periodic Table of the elements, s is 0 or 1, p is 0, 1 or 2, when p is 0, s is 0; m is 4 when s is 1 and m is 5 when s is 0.

Claim 34

The process according to claim 18 wherein said metallocene is represented by the general formula (C 5 R'm)pR"s(C 5 R'm)MeQ 3 -p and R"s(C 5 R'm) 2 MeQ' wherein (C 5 R'm) is cyclopentadienyl or substituted cyclopentadienyl, each R can be the same or different and is selected from hydrogen or a hydrocarbyl radical selected from alkyl, alkenyl, aryl, alkylaryl, or arylalkyl radicals having from 1 to 20 carbon atoms or two adjacent carbon atoms are joined together to form a C 4 -C 6 ring, R" is a C 1 -C 4 alkylene radical, a dialkyl germanium or silicone or alkyl phosphine or amine radical bridging two (C 5 R'm) rings, Q is a hydrocarbon radical selected from the group consisting of aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radicals having from 1-20 carbon atoms or halogen and can be the same or different, Q is an alkylidene radical having from 1 to 20 carbon atoms, Me is a transition metal from Group IVB, VB, or VIB metals of the Periodic Table of the elements, s is 0 or 1, p is 0, 1 or 2, when p is 0, s is 0; m is 4 when s is 1 and m is 5 when s is 0.