Supported polymerization catalyst

• US 4,808,561 A
• Filed: 03/18/1988
• Issued: 02/28/1989
• Est. Priority Date: 06/21/1985
• Status: Expired due to Term

• Current Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Welborn, Howard C. Jr.
• Primary Examiner(s): Garvin, Patrick P.
• Application Number:
  US07/170,485
• Time in Patent Office: 347 Days
• Field of Search: 502/103, 502/104, 502/117, 502/120, 502/113, 502/118, 502/129, 502/132, 502/133
• US Class Current: 502/104
• CPC Class Codes: C08F 10/00 Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
• CPC Class Codes: C08F 210/02 Ethene
• CPC Class Codes: C08F 210/08 Butenes
• CPC Class Codes: C08F 210/14 Monomers containing five or more carbon atoms
• CPC Class Codes: C08F 210/16 Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
• CPC Class Codes: C08F 210/18 with non-conjugated dienes, e.g. EPT rubbers
• CPC Class Codes: C08F 232/02 having no condensed rings
• CPC Class Codes: C08F 236/00 Copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds C08F232/00 takes precedence
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/09 Long chain branches
• CPC Class Codes: C08F 2500/25 Cycloolefine
• CPC Class Codes: C08F 4/615 with aluminium or compounds thereof
• CPC Class Codes: C08F 4/6392 containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: C08F 4/65912 in combination with an organoaluminium compound
• CPC Class Codes: C08F 4/65916 supported on a carrier, e.g. silica, MgCl2, polymer
• CPC Class Codes: C08F 4/6592 containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
• CPC Class Codes: C08F 4/76 selected from titanium, zirconium, hafnium, vanadium, niobium or tantalum
• CPC Class Codes: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

An olefin polymerization supported catalyst comprising a support and the reaction product of a metallocene of Group 4b, 5b or 6b of the Periodic Table and an alumoxane, said reaction product formed in the presence of a support.

Claims

1. 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.

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

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

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

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

1 to 5;

1.

6. 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) (C₅ R'"'"'_k)_g R"_s (C₅ R'"'"'_k)MQ_3-g and

(III) R"_s (C₅ 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, (C₅ 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 C₄ -C₆ ring, R" is a C₁ -C₄ alkylene radical, a dialkyl germanium or silicon or an alkyl phosphine or amine radical bridging two (C₅ 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.

7. 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.

8. 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.

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

10. A method for preparing 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 method comprising adding to a slurry of the support which is a porous inorganic metal oxide of a Group 2a, 3a, 4a, or 4b metal, in an inert hydrocarbon solvent, an alumoxane in an inert hydrocarbon solvent and a metallocene in an amount of from about 0.001 to about 10 millimoles of said metallocene per gram of support.

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

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

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

14. 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.

15. 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.

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