Method for preparing a supported metallocene alumoxane catalyst

Claim 2

A process for preparing a supported metallocene alumoxane catalyst for polymerization of olefins, comprising the steps of: (a) adding a water-impregnated catalyst support to a stirred solution of an aluminum trialkyl in an amount sufficient to provide a mole ratio of aluminum trialkyl to water of from 10:1 to 1:1 and allowing the mixture to react; and (b) adding a metallocene to the reacted mixture in an amount sufficient to provide a mole ratio of aluminum to transition metal of from 1000:1 to 1:1.

Claim 3

A process according to claim 1, wherein the catalyst support is silica gel.

Claim 4

The process according to claim 1 or claim 2, wherein the metallocene is represented by the general formula: (Cp) m MR n X q wherein Cp is a cyclopentadienyl ring, M is a Group 4b or 5b transition metal, R is a hydrocarbyl group or hydrocarboxy group having from 1 to 20 carbon atoms, X is a halogen, m is a whole number from 1 to 3 and n and q are whole numbers from 0 to 3.

Claim 5

The process according to any of the preceding claims wherein the metallocene is represented by the general formula: (C₅R′ k ) g R˝ s (C₅R′ k )MQ 3-g wherein (C₅R′ k ) is a cyclopentadienyl or substituted cyclopentadienyl, each R′ is the same or different and is hydrogen or a hydrocarbyl radical containing from 1 to 20 carbon atoms, a silicon-containing hydrocarbyl radical, or a hydrocarbyl radical wherein two carbon atoms are joined together to form a C₄-C₆ ring, R˝ is C₁-C₄ alkylene radical, a dialkyl germanium or silicone, or an alkyl phosphine or amine radical bridging two (C₅R′ k ) rings, Q is a hydrocarbyl radical having 1-20 carbon atoms, hydrocarboxy radical having 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, s is 0 or 1, g is 0, 1 or 2, s is 0 when g is 0, k is 4 when s is 1, k is 5 when s is 0, and M is a Group 4b or 5b transition metal.

Claim 6

The process according to any of claims 1 to 4, wherein the metallocene is represented by the general formula: R˝ s (C₅R′ k )₂MQ′ wherein (C₅R′ k ) is a cyclopentadienyl or substituted cyclopentadienyl, each R′ is the same or different and is hydrogen or a hydrocarbyl radical containing from 1 to 20 carbon atoms, a silicon-containing hydrocarbyl radical, or a hydrocarbyl radical wherein two carbon atoms are joined together to form a C₄-C₆ ring, R˝ is C₁-C₄ alkylene radical, a dialkyl germanium or silicone, or an alkyl phosphine or amine radical bridging two (C₅R′ k ) rings, Q is a hydrocarbyl radical having 1-20 carbon atoms, hydrocarboxy radical having 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, s is 0 or 1, k is 4 when s is 1, k is 5 when s is 0, and M is a Group 4b or 5b transition metal.

Claim 7

The process according to any of the preceding claims wherein the metallocene is selected from the group consisting of zirconocenes, titanocenes, hafnocenes and vanadocenes.

Claim 8

The process according to any of the preceding claims wherein the mole ratio of aluminum trialkyl to water is from 5:1 to 1:1; and/or wherein the mole ratio of aluminum to transition metal is from 300:1 to 10:1, preferably from 150:1 to 30:1.

Claim 9

The process according to any of the preceding claims wherein the aluminum trialkyl is selected from the group consisting of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tri-n-butyl aluminum, tri-isobutyl aluminum, tri(2-methylpentyl) aluminum, trihexyl aluminum, tri-n-octyl aluminum, and tri-n-decyl aluminum.

Claim 10

A supported metallocene alumoxane catalyst for polymerization of olefins made by the process comprising the steps of: (a) adding a water-impregnated catalyst support, preferably silica gels to a stirred solution of an aluminum trialkyl in an amount sufficient to provide a mole ratio of aluminum trialkyl to water of from 10:1 to 1:1 and allowing the mixture to react; and (b) adding a metallocene to the reacted mixture in an amount sufficient to provide a mole ratio of aluminum to transition metal of from 1000:1 to 1:1.

Claim 11

A supported metallocene alumoxane catalyst for polymerization of olefins made by the process comprising the steps of: (a) adding a water-impregnated catalyst support, preferably silica gels to a stirred solution of an aluminum trialkyl in an amount sufficient to provide a mole ratio of aluminum trialkyl to water of from 10:1 to 1:1 and allowing the mixture to react; and (b) adding a metallocene to the reacted mixture in an amount sufficient to provide a mole ratio of aluminum to transition metal of from 1000:1 to 1:1.

Claim 12

The product according to claim 9 wherein the metallocene is represented by the general formula: (Cp) m MR n X q wherein Cp is a cyclopentadienyl ring, M is a Group 4b or 5b transition metal, R is a hydrocarbyl group or hydrocarboxy group having from 1 to 20 carbon atoms, X is a halogen, m is a whole number from 1 to 3 and n and q are whole numbers from 0 to 3; or wherein the metallocene is represented by the general formula: (C₅R′ k ) g R˝ s (C₅R′ k )MQ 3-g wherein (C₅R′ k ) is a cyclopentadienyl or substituted cyclopentadienyl, each R′ is the same or different and is hydrogen or a hydrocarbyl radical containing from 1 to 20 carbon atoms, a silicon-containing hydrocarbyl radical, or a hydrocarbyl radical wherein two carbon atoms are joined together to form a C₄-C₆ ring, R˝ is C₁-C₄ alkylene radical, a dialkyl germanium or silicone, or an alkyl phosphine or amine radical bridging two (C₅R′ k ) rings, Q is a hydrocarbyl radical having 1-20 carbon atoms, hydrocarboxy radical having 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, s is 0 or 1, g is 0, 1 or 2, s is 0 when g is 0, k is 4 when s is 1, k is 5 when s is 0, and M is a Group 4b or 5b transition metal wherein the metallocene is represented by the general formula: R˝ s (C₅R′ k )₂MQ′ wherein (C₅R′ k ) is a cyclopentadienyl or substituted cyclopentadienyl each R′ is the same or different and is hydrogen or a hydrocarbyl radical containing from 1 to 20 carbon atoms, a silicon-containing hydrocarbyl radical, or a hydrocarbyl radical wherein two carbon atoms are joined together to form a C₄-C₆ ring, R˝ is C₁-C₄ alkylene radical, a dialkyl germanium or silicone, or an alkyl phosphine or amine radical bridging two (C₅R′ k ) rings, Q is a hydrocarbyl radical having 1-20 carbon atoms, hydrocarboxy radical having 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, s is 0 or 1, k is 4 when s is 1, k is 5 when s is 0, and M is a Group 4b or 5b transition metal.

Claim 13

The product according to claim 9 or claim 10, wherein the metallocene is selected from the group consisting of zirconocenes, titanocenes, hafnocenes and vanadocenes.

Claim 14

The product according to any of claims 9 to 11, wherein the mole ratio of aluminum trialkyl to water is from 5:1 to 1:1; and/or the mole ratio of aluminum to transition metal is from 300:1 to 10:1, preferably from 150:1 to 30:1; and/or wherein the aluminum trialkyl is selected from the group consisting of trimethyl aluminum, triethyl aluminum, tripropyl aluminum, tri-n-butyl aluminum, tri-isobutyl aluminum, tri(2-methylpentyl) aluminum, trihexyl aluminum, tri-n-octyl aluminum, and tri-n-decyl aluminum.

Claim 15

Process for preparing metallocene/alumoxane olefin polymerization catalyst by reacting aluminum trialkyl and water in the presence of a water adsorbent, inert solid material at a mole ratio of aluminum trialkyl to water of from 10:1 to 1:1, and adding a transition metal metallocene to the reacted mixture characterized in that: (a) the water is adsorbed by the solid material prior to the reaction; (b) the water containing solid material is added to aluminum trialkyl diluted in a solvent; and (c) the mole ratio of aluminum to metallocene transition metal is from 1000:1 to 1:1.

Claim 16

Process for preparing metallocene/alumoxane olefin polymerization catalyst by reacting aluminum trialkyl and water in the presence of a water adsorbent, inert solid material at a mole ratio of aluminum trialkyl to water of from 10:1 to 1:1, and adding a transition metal metallocene to the reacted mixture characterized in that: (a) the water is adsorbed by the solid material prior to the reaction; (b) the water containing solid material is added to aluminum trialkyl diluted in a solvent; and (c) the mole ratio of aluminum to metallocene transition metal is from 1000:1 to 1:1.

Claim 17

Process according to claim 13 further characterized in that: (a) the water is adsorbed in an amount of 10 to 50%, optionally less than 33%; (b) the aluminum trialkyl solution is stirred during contacting with the water containing solid material and has a concentration of 0.1 to 5M, optionally the water containing solid being added, free of diluent, in powder form; and/or (c) the metallocene is a substituted cyclopentadiene derivative.

Claim 18

Process for polymerizing one or more olefins which comprises conducting the polymerization in the presence of a catalyst prepared in accordance with claims 1 to 8.

Claim 19

Process for polymerizing one or more olefins which comprises conducting the polymerization in the presence of a catalyst prepared in accordance with claims 13 and 14.

Claim 20

Process in accordance with claims 16 wherein the polymerization is performed in accordance with a gas phase polymerization process.