Addition polymerization process using stabilized reduced metal catalysts
AssigneeThe Dow Chemical Company
InventorsRobert K. Rosen, Peter N. Nickias, David D. Devore, 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 .pi.-bonding moiety, and at least one stabilizing ligand.
Claims4
A catalyzed addition polymerization process comprising contacting under addition polymerization conditions a polymerizable monomer with a catalyst comprising a metal complex corresponding to the formula:
- ##STR7## wherein:
- M is titanium in the .sup.+ 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 from 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.3 bond with M,
- and an activating cocatalyst.
A catalyzed addition polymerization process comprising contacting under addition polymerization conditions a polymerizable monomer with a catalyst comprising a metal complex corresponding to the formula:
- ##STR8## wherein:
- M is titanium in the +3 oxidation state;
- R' is hydrogen, or a group selected from silyl, hydrocarbyl, and combinations thereof having up to 30 carbon or silicon atoms, or two R' groups together form a divalent derivative of such group;
- E is silicon or carbon;
- R" independently each occurrence is hydrogen or a group selected from silyl, hydrocarbyl and combinations thereof, said R" having up to 30 carbon or silicon atoms;
- Y' is nitrogen;
- R'" is a group selected from silyl, hydrocarbyl and combinations thereof, said group or combination having up to 30 carbon or silicon atoms;
- m is 1 or 2;
- 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.3 bond with M,
- and an activating cocatalyst.
Dependencies are inferred from the claim text.