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US 5,425,872 AGranted
Electrochemical preparation of addition polymerization catalysts
AssigneeThe Dow Chemical Company
InventorsDavid D. Devore, Robert D. Mussell, James C. Stevens, Francis J. Timmers
Life of this patent
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Abstract
Group 4 metal complexes useful as addition polymerization catalysts are prepared by electrolysis of cyclopentadienyl metal complexes under inert electrolysis conditions.
Claims21
A process for the preparation of metal complexes corresponding to the formula:
- Cp.sub.a Z.sub.b M(IV)X.sub.c.sup.+ A.sup.-, (1)
- wherein:
- Cp independently each occurrence is a cyclopentadienyl group .pi.-bound to M;
- a hydrocarbyl, silyl, germyl, halo, cyano, or halohydrocarbyl substituted derivative of said cyclopentadienyl group;
- or such a substituted cyclopentadienyl group wherein two such substituents together form a multiple ring structure, said Cp containing up to 50 nonhydrogen atoms, and when more than one Cp is present, different Cp moieties may be joined by a linking group;
- Z is a divalent moiety bound to both Cp and M(IV) comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally nitrogen, phosphorus, sulfur or oxygen, said moiety having up to 30 non-hydrogen atoms, and optionally Cp and Z together form a fused ring system;
- M(IV) is a Group 4 metal in the +4 oxidation state;
- X independently each occurrence is hydride;
- halide;
- or a covalently bonded ligand group selected from hydrocarbyl, silyl, germyl, and combinations thereof, said X having up to 50 carbon, silicon or germanium atoms, and oxygen, nitrogen, phosphorus or sulfur containing derivatives thereof;
- a is 1 or 2;
- if a is 1, b is 0 or 1, if a is 2, b is 0;
- c is 1 or 2;
- the sum of a+b+c equals 3;
- and
- A.sup.- is an inert, compatible, noncoordinating anion,
- the steps of the process comprising electrolyzing under inert, noncoordinating, electrolysis conditions at least one initial complex corresponding to the formula:
- Cp.sub.a Z.sub.b M(III)X.sub.c or (1a)
- Cp.sub.a Z.sub.b M(IV)X.sub.c+1, (1b)
- in the presence of an electrolyte comprising A.sup.- to produce complexes of formula (1);
- wherein:
- M(III) is a Group 4 metal in the +3 oxidation state;
- and Cp, Z, M(IV), X, a, b, and c, are as previously defined above.
20 more elements
An addition polymerization process comprising contacting one or more addition polymerizable monomers under addition polymerization conditions with a catalyst comprising the reaction product resulting from electrolyzing under inert electrolysis conditions at least one complex corresponding to the formula:
- Cp.sub.a Z.sub.b M(III)X.sub.c or Cp.sub.a Z.sub.b M(IV)X.sub.c+1,
- wherein:
- Cp independently each occurrence is a cyclopentadienyl group .pi.-bound to M;
- a hydrocarbyl, silyl, germyl, halo or halohydrocarbyl substituted derivative of said cyclopentadienyl group;
- or such a substituted cyclopentadienyl group wherein two such substituents together form a multiple ring structure, said Cp containing up to 50 nonhydrogen atoms, and when more than one Cp is present, different Cp moieties may be joined by a linking group,
- Z is a divalent moiety bound to both Cp and M(III) or M(IV) comprising boron, or a member of Group 14 of the Periodic Table of the Elements, and optionally nitrogen, phosphorus, sulfur or oxygen, said moiety having up to 30 non-hydrogen atoms, and optionally Cp and Z together form a fused ring system;
- M(III) is a Group 4 metal in the +3 oxidation state;
- M(IV) is a Group 4 metal in the +4 oxidation state;
- X independently each occurrence is hydride;
- halide;
- or a covalently bonded ligand group selected from hydrocarbyl, silyl, germyl, and combinations thereof, said X having up to 50 carbon, silicon or germanium atoms, and oxygen, nitrogen, phosphorus or sulfur containing derivatives thereof;
- a is 1 or 2;
- if a is 1, b is 0 or 1, if a is 2, b is 0;
- c is 1 or 2;
- and
- the sum of a+b+c equals 3.
13 more elements
Dependencies are inferred from the claim text.