New supported polymerization catalyst

• US 5,077,255 A
• Filed: 09/10/1986
• Issued: 12/31/1991
• Est. Priority Date: 09/09/1986
• 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): Smith, Edward J.
• Application Number:
  US06/906,103
• Time in Patent Office: 1,938 Days
• Field of Search: 502/104, 502/117, 502/120, 502/129, 502/113, 502/132
• 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 4/65904 in combination with another component of C08F4/64
• 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: Y10S 526/943 Polymerization with metallocene catalysts

Abstract

An olefin polymerization supported catalyst comprising the supported reaction product of at least one metallocene of a metal of Group IVB, VB, and VIB of the Periodic Table, a non-metallocene transition metal containing compound of a Group IBV, VB, or VIB metal and an alumoxane, said reaction product formed in the presence of the support. The supported product is highly useful for the polymerization of olefins especially ethylene and especially for the copolymerization of ethylene and other mono and diolefins.

Claims

1. An olefin polymerization supported catalyst comprising a supported reaction product obtained by reacting at least one metallocene of a metal of Group IVB, at least one non-metallocene transition metal compound of a metal of Group IVB, VB, and VIB and an alumoxane in the presence of a support material consisting essentially of silica, alumina or silica-alumina.

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, zirconium, hafnium, metallocenes and mixtures thereof.

4. The olefin polymerization supported catalyst in accordance with claim 3 wherein the non-metallocene transition metal compound is selected from titanium tetrachloride, vanadium tetrachloride, and vanadium oxytrichloride and mixtures thereof.

5. The olefin polymerization supported catalyst in accordance with claim 4 wherein the metallocene is selected from titanium and zirconium metallocenes and mixtures thereof.

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

7. The olefin polymerization supported catalyst in accordance with claim 1 wherein the aluminum to transition metal molar ratio in the supported product is in the range of 1:

1 to about 300;

1.

8. The olefin polymerization supported catalyst in accordance with claim 7 wherein the molar ratio is in the range of 50:

1 to 5;

1.

9. The olefin polymerization supported catalyst in accordance with claim 1 wherein the metallocene is represented by the formulas ##STR6## 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, (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 radicals 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, alkylaryls, 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 and wherein the non-metallocene transition metal compound is represented by TrX'"'"'_4-q (OR'"'"')_q, TrX'"'"'_4-q R_q², VOX'"'"'₃, and 0≦

q≦

4, VO(OR'"'"')₃, wherein Tr is a Group IVB, VB, OR VIB metal, X'"'"' is a halogen and R¹ is an alkyl, aryl, or cycloalkyl group having from 1-20 carbon atoms, and R² is an alkyl, aryl, or aralkyl, and substituted aralkyl group having from 1-20 carbon atoms.

10. The olefin polymerization supported 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 as selected from titanium tetrachloride, vanadium tetrachloride, and vanadium oxytrichloride.

11. A method for preparing an olefin polymerization supported catalyst comprising the supported reaction product of at least one metallocene of a metal of Group IVB, a non-metallocene compound of a metal of Group IVB, VB, and VIB, and an alumoxane, said method comprising adding to a slurry of a support material consisting essentially of silica, alumina or silica-alumina in an inert hydrocarbon solvent, an alumoxane in an inert hydrocarbon solvent, at least one metallocene, and at least one non-metallocene transition metal compound.

12. The method in accordance with claim 11 wherein the molar ratio of the alumoxane to metallocene based on the aluminum and metal is in the range of 300:

1 to about 1;

1 and the molar ratio of the metallocene compound to the non-metallocene transition metal compound is in the range of about 100 to about 0.01 moles metallocene per mole of non-metallocene transition metal compound.