Supported polymerization catalyst

Claim 2

An olefin polymerization supported catalyst comprising the supported reaction product of at least one metallocene of a metal of Group 4b of the Periodic Table and an alumoxane, the aluminum to transition metal molar ratio being in the range of 100:1 to 1:1, said product being formed in the presence of the support, said support being a porous inorganic metal oxide of Group 2a, 3a, 4a, or 4b metal, and wherein the metallocene is employed in the amount of about 0.001 to about 10 millimoles per gram of support.

Claim 3

The olefin polymerization supported catalyst in accordance with claim 1 wherein the support is silica.

Claim 4

The olefin polymerization supported catalyst in accordance with claim 1 wherein the metallocene is selected from titanium and zirconium metallocenes and mixtures thereof.

Claim 5

The olefin polymerization supported catalyst in accordance with claim 1 wherein the alumoxane is methyl alumoxane.

Claim 6

The olefin polymerization supported catalyst in accordance with claim 1 wherein the molar ratio is in the range of 50:1 to 5:1.

Claim 7

The olefin polymerization supported catalyst in accordance with claim 1 wherein the metallocene is represented by the formulas (I) (Cp) m MR n X q (II) (C 5 R' k ) g R" s (C 5 R' k )MQ 3-g and (III) R" s (C 5 R' k ) 2 MQ' wherein Cp is a cyclopentadienyl ring, M is a Group 4b transition metal, R is a hydrocarby group or hydrocarboxy having from 1 to 20 carbon atoms, X is a halogen, m=1-3, n=0-3, q=0-3 and the sum of m+n+q is equal to the oxidation state of M, (C 5 R' k ) is a cyclopentadienyl or a substituted cyclopentadienyl; each R' is the same or different and is hydrogen or a hydrocarbyl radical selected from alkyl, alkenyl aryl, alkylaryl or arylalkyl radical containing from 1 to 20 carbon atoms, or two 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 silicon or an alkyl phosphine or amine radical bridging two (C 5 R' k ) rings; Q is a hydrocarbyl radical selected from aryl, alkyl, alkenyl, alkylaryl, or arylalkyl radicals having from 1-20 carbon atoms, hydrocarboxy radical having from 1-20 carbon atoms or halogen and can be the same or different from each other; Q' is an alkylidiene 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 and k is 5 when s is 0.

Claim 8

The olefin polymerization supported catalyst in accordance with claim 6 wherein the metallocene is selected from bis(cyclopentadienyl) zirconium dichloride, bis(cyclopentadienyl) zirconium methyl chloride, bis(cyclopentadienyl) zirconium dimethyl, bis(methylcyclopentadienyl) zirconium dichloride, bis(methylcyclopentadienyl) zirconium methyl chloride, bis(methylcyclopentadienyl) zirconium dimethyl, bis(pentamethylcyclopentadienyl) zirconium dichloride, bis(pentamethylcyclopentadienyl) zirconium methyl chloride, bis(pentamethylcyclopentadienyl) zirconium dimethyl, bis(n-butyl-cyclopentadienyl) zirconium dichloride, bis(n-butylcyclopentadienyl) zirconium methyl chloride, bis(n-butyl-cyclopentadienyl) zirconium dimethyl, bis(cyclopentadienyl) titanium diphenyl, bis(cyclopentadienyl) titanium dichloride, bis(cyclopentadienyl) titanium methyl chloride, bis(cyclopentadienyl) titanium dimethyl, bis(methylcyclopentadienyl) titanium diphenyl, bis(methylcyclopentadienyl) titanium dichloride, bis(methylcyclopentadienyl) titanium diphenyl, bis(methylcyclopentadienyl) titanium methyl chloride, bis(methylcyclopentadienyl) titanium dimethyl, bis(pentamethylcyclopentadienyl) titanium dichloride, bis(pentamethylcyclopentadienyl) titanium diphenyl, bis(pentamethylcyclopentadienyl) titanium methyl chloride, bis(pentamethylcyclopentadienyl) titanium dimethyl, bis(n-butyl-cyclopentadienyl) titanium diphenyl, bis(n-butyl-cyclopentadienyl) titanium dichloride and mixtures thereof.

Claim 9

The olefin polymerization supported catalyst in accordance with claim 7 wherein the metallocene is selected from bis(cyclopentadienyl) zirconium dichloride, bis(n-butyl-cyclopentadienyl) zirconium dichloride and mixtures thereof, the alumoxane is methyl alumoxane and the support is silica.

Claim 10

The olefin polymerization supported catalyst in accordance with claim 8 wherein the metallocene is bis(n-butyl-cyclopentadienyl) zirconium dichloride.

Claim 13

The method in accordance with claim 10 wherein the alumoxane is added to the support material prior to the metallocene.

Claim 14

The method in accordance with claim 10 wherein the metallocene is added to the support prior to the alumoxane.

Claim 15

The method in accordance with claim 10 wherein the metallocene and alumoxane are added to the support slurry simultaneously.

Claim 16

The method in accordance with claim 10 wherein the metallocene is selected from bis(cyclopentadienyl) zirconium dichloride, bis(cyclopentadienyl) zirconium methyl chloride, bis(cyclopentadienyl) zirconium dimethyl, bis(methylcyclopentadienyl) zirconium dichloride, bis(methylcyclopentadienyl) zirconium methyl chloride, bis(methylcyclopentadienyl) zirconium dimethyl, bis(pentamethylcyclopentadienyl) zirconium dichloride, bis(pentamethylcyclopentadienyl) zirconium methyl chloride, bis(pentamethylcyclopentadienyl) zirconium dimethyl, bis(n-butyl-cyclopentadienyl) zirconium dichloride, bis(n-butylcyclopentadienyl) zirconium methyl chloride, bis(n-butyl-cyclopentadienyl) zirconium dimethyl, bis(cyclopentadienyl) titanium diphenyl, bis(cyclopentadienyl) titanium dichloride, bis(cyclopentadienyl) titanium methyl chloride, bis(cyclopentadienyl) titanium dimethyl, bis(methylcyclopentadienyl) titanium diphenyl, bis(methylcyclopentadienyl) titanium dichloride, bis(methylcyclopentadienyl) titanium diphenyl, bis(methylcyclopentadienyl) titanium methyl chloride, bis(methylcyclopentadienyl) titanium dimethyl, bis(pentamethylcyclopentadienyl) titanium dichloride, bis(pentamethylcyclopentadienyl) titanium diphenyl, bis(pentamethylcyclopentadienyl) titanium methyl chloride, bis(pentamethylcyclopentadienyl) titanium dimethyl, bis(n-butyl-cyclopentadienyl) titanium diphenyl, bis(n-butyl-cyclopentadienyl) titanium dichloride, the alumoxane is methyl alumoxane and the support is silica.

Claim 17

The method is accordance with claim 14 wherein the metallocene is one of bis(cyclopentadienyl) zirconium dichloride, bis(n-butyl-cyclopentadienyl) zirconium dichloride and mixtures thereof.

Claim 18

The method is accordance with claim 14 wherein the metallocene is bis(n-butyl-cyclopentadienyl) zirconium dichloride.