New 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 IVB, VB, or VIB of the Periodic Table (66th Edition of Handbook of Chemistry and Physics, CRC Press, [1985-86], CAS Version), at least one non-metallocene compound of a transition metal of Group IVB, VB, or VIB and an alumoxane, said reaction product formed in the presence of the support.

Claim 3

A catalyst in accordance with claim 1 wherein the support is a porous inorganic oxide of a Group IIA, IIIA, IVA, or IVB element.

Claim 4

A catalyst in accordance with claim 2 wherein the support is silica.

Claim 5

A catalyst in accordance with any of the preceding claims wherein the metallocene is selected from titanium, zirconium, hafnium, and vanadium metallocenes and mixtures of any two or more thereof.

Claim 6

A catalyst in accordance with any of the preceding claims wherein the non-metallocene transition metal compound is selected from titanium tetrachloride, vanadium tetrachloride, and vanadium oxytrichloride and mixtures of any two or more thereof.

Claim 7

A catalyst in accordance with any of the preceding claims wherein the alumoxane is methylalumoxane.

Claim 8

A catalyst in accordance with any of the preceding claims wherein the aluminum to transition metal molar ratio in the supported product is from 1:1 to 300:1.

Claim 9

A catalyst in accordance with claim 7 wherein the molar ratio is from 50:1 to 5:1.

Claim 10

A catalyst in accordance with any of the preceding claims wherein the metallocene is represented by the formulas (I) (Cp) m MR n X q (II) (C₅Rʹ k ) g Rʺ s (C₅Rʹ k )MQ 3-g and (III) Rʺ s (C₅Rʹ k )₂MQʹ wherein Cp is a cyclopentadienyl ring, M is a Group 4b, 5b, or 6b transition metal, R is a hydrocarbyl 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, (C₅Rʹk) is a cyclopentadienyl or a substituted cyclopentadienyl; each Rʹ is the same or different and is hdyrogen or a hydrocarbyl radical selected from alkyl, alkenyl, aryl, alkylaryl or arylalkyl radicals containing from 1 to 20 carbon atoms, or two carbon atoms are joined together to form a C₄-C₆ ring, Rʺ is a C₁-C₄ alkylene radical, a dialkyl germanium or silicon or an alkyl phosphine or amine radical bridging two (C₅Rʹ 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; Qʹ is an alkylidene radical having from 1 to 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 and wherein the non-metallocene transition metal compound is represented by TrXʹ 4-q (OR¹) q , TrXʹ 4-q R, VOXʹ₃, and VO(ORʹ)₃, wherein Tr is a Group IVB, VB, or VIB metal, 0 ≦ q ≦ 4, Xʹ is a halogen and R¹ is an alkyl, aryl, or cycloalkyl group having from 1-20 carbon atoms, and R² is an alkyl, aryl, aralkyl, or substituted aralkyl group having from 1-20 carbon atoms.

Claim 11

A catalyst in accordance with claim 9 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 and the non-metallocene compound is selected from titanium tetrachloride, vanadium tetrachloride, and vanadium oxytrichloride.

Claim 13

The method in accordance with claim 11 wherein the molar ratio of the alumoxane to metallocene based on the aluminum and metal is from 300:1 to 1:1 and the molar ratio of the metallocene compound to the non-metallocene transition metal compound is from 100 to 0.01 moles metallocene per mole of non-metallocene transition metal compound.

Claim 14

A catalyst system for olefin polymerization which comprises a supported catalyst according to any one of claims 1 to 10, and an organometallic co-catalyst.

Claim 15

A catalyst system according to claim 13 wherein the co-catalyst comprises an aluminumalkyl compound.

Claim 16

A process for producing polymers of ethylene, or copolymers of ethylene and alpha-olefins or diolefins, which process comprises polymerizing the monomers in the presence of a supported catalyst according to any one of claims 1 to 10, a supported catalyst prepared by the method according to claim 11 or 12, or a catalyst system according to claim 13 or 14.