Homogenous, stabilized, reduced metal addition polymerization catalysts, process for preparation and method of use

Claim 2

An addition polymerization catalyst comprising in combination: a metal complex corresponding to the formula Cp'ML'.sub.2, wherein: Cp' is a cyclopentadienyl group n-bound to M, or a hydrocarbyl, silyl, halo, halohydrocarbyl, or hydrocarbylmetalloid substituted derivative thereof, said Cp' containing up to 50 nonhydrogen atoms; M is titanium in the + 3 oxidation state; L' independently each occurrence is hydride, halo, or a monovalent anionic ligand selected from the group consisting of hydrocarbyl, silyl, amido, phosphido, alkoxy, aryloxy, and sulfido groups; mixtures thereof; and amine, phosphine, ether, and thioether derivatives of the foregoing, said ligand having up to 50 nonhydrogen atoms, with the proviso that in at least one occurrence L' is a stabilizing ligand comprising an amine, phosphine, ether or thioether functionality able to form a coordinate-covalent bond or chelating bond with M, or comprising an ethylenic unsaturation able to form an η3 bond with M; and an activating cocatalyst.

Claim 3

A catalyst as claimed in claim 1, wherein M is titanium, and L is 2-(dimethylamino)benzyl or allyl.

Claim 4

A catalyst according to claim 1 wherein the ratio of metal complex to activating cocatalyst is from 1:0.01 to 1:10 6 .

Claim 5

A catalyst as claimed in claim 1 wherein the activating cocatalyst is selected from the group consisting of alkylalumoxanes, aluminum alkyls, aluminum halides, alkylaluminum halides, Lewis acids other than any of the foregoing, and mixtures thereof.

Claim 6

A catalyst as claimed in claim 4, wherein the activating cocatalyst is tris(4-fluorophenyl)boron, tris(2,4-difluorophenylboron), tris(3,5-bis(trifluoromethyl)phenyl)boron, tris(pentafluorophenyl)boron, pentafluorophenyl diphenylboron, triphenyl boron or bis(pentafluorophenyl)phenylboron.

Claim 7

A catalyst as claimed in claim 2, wherein the activating cocatalyst is tris(pentafluorophenyl)boron.

Claim 8

An addition polymerization catalyst comprising: 1) a complex corresponding to the formula: ##STR7## wherein: M is titanium in the +3 oxidation state; Cp" is a cyclopentadienyl group, or a hydrocarbyl, silyl, halo, halohydrocarbyl, or hydrocarbylmetalloid substituted derivative thereof, said Cp" containing up to 50 nonhydrogen atoms; Z is a divalent moiety comprising oxygen, nitrogen, phosphorous, boron, or a member of Group 14 of the Periodic Table of the Elements said moiety having up to 30 nonhydrogen atoms; Y is a linking group comprising nitrogen, phosphorus, oxygen or sulfur covalently bonded to M and Z through said nitrogen, phosphorus, oxygen or sulfur atom, the ligand moiety consisting of --Cp"--Z--Y-- being dianionic and having the ionic charges residing formally on Cp" and Y; and L" is a monovalent anionic stabilizing ligand selected from the group consisting of: a) alkyl, cycloalkyl, aryl, silyl, amido, phosphido, alkoxy, aryloxy, sulfido groups and mixtures thereof, and being further substituted with an amine, phosphine, ether, or thioether containing substituent able to form a coordinate-covalent bond or chelating bond with M, said ligand having up to 50 nonhydrogen atoms; and b) C 3-15 hydrocarbyl groups comprising an ethylenic unsaturation able to form an η 3 bond with M; and 2) an activating cocatalyst.

Claim 9

An addition polymerization catalyst comprising: 1) a complex corresponding to the formula: ##STR7## wherein: M is titanium in the +3 oxidation state; Cp" is a cyclopentadienyl group, or a hydrocarbyl, silyl, halo, halohydrocarbyl, or hydrocarbylmetalloid substituted derivative thereof, said Cp" containing up to 50 nonhydrogen atoms; Z is a divalent moiety comprising oxygen, nitrogen, phosphorous, boron, or a member of Group 14 of the Periodic Table of the Elements said moiety having up to 30 nonhydrogen atoms; Y is a linking group comprising nitrogen, phosphorus, oxygen or sulfur covalently bonded to M and Z through said nitrogen, phosphorus, oxygen or sulfur atom, the ligand moiety consisting of --Cp"--Z--Y-- being dianionic and having the ionic charges residing formally on Cp" and Y; and L" is a monovalent anionic stabilizing ligand selected from the group consisting of: a) alkyl, cycloalkyl, aryl, silyl, amido, phosphido, alkoxy, aryloxy, sulfido groups and mixtures thereof, and being further substituted with an amine, phosphine, ether, or thioether containing substituent able to form a coordinate-covalent bond or chelating bond with M, said ligand having up to 50 nonhydrogen atoms; and b) C 3-15 hydrocarbyl groups comprising an ethylenic unsaturation able to form an η 3 bond with M; and 2) an activating cocatalyst.

Claim 10

An addition polymerization catalyst according to claim 7, wherein the activating cocatalyst is selected from the group consisting of alkylalumoxanes; aluminum alkyls; aluminum halides; alkylaluminum halides, Lewis acids other than any of the foregoing; and mixtures thereof.

Claim 11

An addition polymerization catalyst as claimed in claim 8, wherein the activating cocatalyst is tris(4-fluorophenyl)boron, tris(2,4-difluorophenylboron), tris(3,5-bis(trifluoromethyl)phenyl)boron, tris(pentafluorophenyl)boron, pentafluorophenyl diphenylboron, triphenyl boron or bis(pentafluorophenyl)phenylboron.

Claim 12

An addition polymerization catalyst comprising a complex selected from the group consisting of (tert-butylamido)dimethyl(tetramethyl-η 5 -cyclopentadienyl)silane 2-(dimethylamino)benzyl titanium (III), (tert-butylamido)dimethyl(tetramethyl-η 5 -cyclopentadienyl)silane allyl titanium (III), and (tert-butylamido)dimethyl(tetramethyl-η 5 -cyclopentadienyl)silane 1,2,3-trimethylallyl titanium (III), and tris(pentafluorophenyl)boron activating cocatalyst.

Claim 13

An addition polymerization catalyst comprising a complex selected from the group consisting of (tert-butylamido)dimethyl(tetramethyl-η 5 -cyclopentadienyl)silane 2-(dimethylamino)benzyl titanium (III), (tert-butylamido)dimethyl(tetramethyl-η 5 -cyclopentadienyl)silane allyl titanium (III), and (tert-butylamido)dimethyl(tetramethyl-η 5 -cyclopentadienyl)silane 1,2,3-trimethylallyl titanium (III), and tris(pentafluorophenyl)boron activating cocatalyst.