Olefin polymerization catalysts

• US 5,055,438 A
• Filed: 06/04/1990
• Issued: 10/08/1991
• Est. Priority Date: 09/13/1989
• Status: Expired due to Term

• Current Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Original Assignee: Exxon Chemical Patents Inc. (Exxon Mobil Corporation)
• Inventors: Canich, Jo Ann M.
• Primary Examiner(s): Garvin, Patrick P.
• Application Number:
  US07/533,245
• Time in Patent Office: 491 Days
• Field of Search: 502/103, 502/117, 502/121, 502/122, 502/123, 502/124, 502/125
• US Class Current: 502/117
• CPC Class Codes: C07F 17/00 Metallocenes
• CPC Class Codes: C07F 7/10 containing nitrogen having a Si-N linkage
• 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 10/06 Propene
• CPC Class Codes: C08F 110/02 Ethene
• CPC Class Codes: C08F 110/06 Propene
• CPC Class Codes: C08F 210/06 Propene
• 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 232/08 having condensed rings coumarone-indene polymers C08F244/00
• CPC Class Codes: C08F 236/20 unconjugated
• CPC Class Codes: C08F 2500/01 High molecular weight, e.g. >800,000 Da.
• CPC Class Codes: C08F 2500/03 Narrow molecular weight distribution, i.e. Mw/Mn < 3
• CPC Class Codes: C08F 2500/10 Short chain branches
• CPC Class Codes: C08F 2500/17 Viscosity
• CPC Class Codes: C08F 2500/24 Polymer with special particle form or size
• CPC Class Codes: C08F 2500/25 Cycloolefine
• CPC Class Codes: C08F 4/65908 in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
• 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

The invention is a polymerization catalyst system including an alumoxane and a Group IV B metallocene having a heteroatom ligand. The catalyst system can be employed to polymerize olefins to produce a high molecular weight polymer.

Claims

1. A catalyst system comprising:

(A) a Group IV B transition metal component of the formula;

##STR5## wherein M is Zr, Hf or Ti;

(C₅ H_5-y-x R_x) is a cyclopentadienyl ring which is substituted wit from zero to five groups R, "x" is 0, 1, 2, 3, 4 or 5 denoting the degree of substitution, and each R is, independently, a radical selected from a group consisting of C₁ -C₂₀ hydrocarbyl radicals, C₁ -C₂₀ substituted hydrocarbyl radicals wherein one or more hydrogen atoms are replaced by a halogen atom, C₁ -C₂₀ hydrocarbyl-substituted metalloid radicals wherein the metalloid is selected from the Group IV A of the Periodic Table of Elements and halogen radicals or (C₅ H_5-y-x R_x) is a cyclopentadienyl ring in which two adjacent R-groups are joined forming C₄ -C₂₀ ring to give a saturated or unsaturated polycyclic cyclopentadienyl ligand;

(JR'"'"'_z-l-y) is a heteroatom ligand in which J is an element with a coordination number of three from Group V A or an element with a coordination number of two from Group VI A of the Periodic Table of Elements, each R'"'"' is, independently a radical selected from a group consisting of C₁ -C₂₀ hydrocarbyl radicals, substituted C₁ -C₂₀ hydrocarbyl radicals wherein one or more hydrogen atoms is replaced by a halogen atom, and "z" is the coordination number of the element J;

each Q is, independently any univalent anionic ligand or two Q'"'"'s are a divalent anionic chelating agent;

"y" is 0 or 1 when w is greater than 0;

y is 1 when w is 0, when "y" is 1, T is a covalent bridging group containing a Group IV A or V A element;

L is a Lewis base where "w" denotes a number from 0 to 3; and

(B) an alumoxane.

2. The catalyst system of claim 1 wherein the heteroatom ligand group J element is nitrogen, phosphorous, oxygen or sulfur.

3. The catalyst system of claim 2 wherein the heteroatom ligand group J element is nitrogen.

4. The catalyst system of claim 1 wherein M is zirconium or hafnium.

5. The catalyst system of claim 1 wherein the mole ratio of Al:

M is from 10;

1 to about 20,000;

1.

6. The catalyst system of claim 1 wherein Q is independently halogen, hydride, or a substituted or unsubstituted C₁ -C₂₀ hydrocarbyl, alkoxide, aryloxide, amide arylamide, phosphide or arylphosphide, provided that where any Q is a hydrocaryl such Q is different from (C₅ H_4-x R_x) or both together are an alkylidene or a cyclometallated hydrocarbyl.

7. The catalyst system of claim 6 wherein Q is a halogen or hydrocarbyl radical.