Homogenous, stabilized, reduced metal addition polymerization catalysts, process for preparation and method of use
AssigneeThe Dow Chemical Company
InventorsRobert K. Rosen, David D. Devore, Peter N. Nickias, James C. Stevens, Francis J. Timmers
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Abstract
Complexes useful as addition polymerization catalysts, a process for their manufacture and addition polymerization processes wherein the complex comprises a Group 4 metal in the .sup.+ 3 oxidation state, a delocalized n-bonding moiety, and at least one stabilizing ligand.
Claims10
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 .sup.+ 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 .eta.3 bond with M;
- and an activating cocatalyst.
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.sub.3-15 hydrocarbyl groups comprising an ethylenic unsaturation able to form an .eta..sup.3 bond with M;
- and
- 2) an activating cocatalyst.
An addition polymerization catalyst comprising a complex selected from the group consisting of (tert-butylamido)dimethyl(tetramethyl-.eta..sup.5 -cyclopentadienyl)silane 2-(dimethylamino)benzyl titanium (III), (tert-butylamido)dimethyl(tetramethyl-.eta..sup.5 -cyclopentadienyl)silane allyl titanium (III), and (tert-butylamido)dimethyl(tetramethyl-.eta..sup.5 -cyclopentadienyl)silane 1,2,3-trimethylallyl titanium (III), and tris(pentafluorophenyl)boron activating cocatalyst.
Dependencies are inferred from the claim text.