# US 5,347,024 A · Preparation of addition polymerization catalysts via Lewis acid mitigated metal center oxidation

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- Number: US 5,347,024 A
- Document ID: US5347024A
- Status: Granted
- Kind: A
- Application number: 08/034,434
- Filed: 1993-03-19
- Granted: 1994-09-13
- Earliest claimed: 1993-03-19
- Assignees: The Dow Chemical Company
- Inventors: Peter N. Nickias; David D. Devore; Francis J. Timmers; Robert K. Rosen; Robert D. Mussell
- Web page: https://patentgrep.com/patent/US5347024A

## CPC

- C08F 10/00: Homopolymers and copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
- C08F 4/65908: {in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+}
- C08F 4/6592: containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

Addition polymerization catalysts comprising a derivative of a titanium or zirconium in the +4 oxidation state prepared by metal center oxidation and cation complex formation of a reduced metal precursor complex via electron transfer in a single step by use of a neutral organic oxidant, optionally in the presence of a Lewis acid mitigator.

## Claims

### Claim 1

A process for the preparation of a cationic metal complex corresponding to the formula:
[Cp.sub.a (ZY).sub.b ML.sub.c.sup.+ ].sub.q [J.sub.p A].sup.-q,
wherein:
Cp independently each occurrence is a cyclopentadienyl group n-bound to M, or a hydrocarbyl, silyl, halo, halohydrocarbyl, hydrocarbylmetalloid or halohydrocarbylmetalloid substituted derivative of said cyclopentadienyl group, said Cp containing up to 50 nonhydrogen atoms, and, when a is 2, optionally both Cp groups may be joined together by a bridging group;
a is 1 or 2;
b is 0 or 1;
cis 1 or 2;
the sum of a, b and c is 3;
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;
L independently each occurrence is hydride, halo, or a monovalent anionic ligand selected from covalently bonded hydrocarbyl, silyl, amido, phosphido, alkoxy, aryloxy, and sulfido groups optionally being further substituted with one or more amine, phosphine, ether, or thioether groups, said ligand having up to 50 nonhydrogen atoms;
M is titanium or zirconium in the +4 oxidation state;
p is an integer from 0 to 4;
q is 1 or 2;
J is the Lewis acid mitigating agent, and
A is a reduced remnant of a neutral organic oxidizing agent and may be ligating or nonligating,
the steps of the process comprising contacting in a noninterfering, noncoordinating solvent at a temperature from-100.degree. C. to 300.degree. C.:
1) a reduced metal precursor complex corresponding to the formula: Cp.sub.a (ZY).sub.b M*L.sub.c, wherein Cp, Z, Y, L, a, b, and c are as previously defined, and M* is the same metal as M but in a +3 oxidation state;
2) a neutral organic oxidizing agent, A*, capable of accepting one or more electrons and oxidizing M* to M and which in reduced form is A;
and, if A is a ligating group,
3) a Lewis acid mitigating agent, J.

### Claim 2 (depends on 1)

A process according to claim 1, wherein the organic oxidizing agent has an electrochemical reduction potential from 0.30 volts more negative than the electrochemical oxidation potential of the desired oxidation to any value more positive than the electrochemical oxidation potential of the desired oxidation.

### Claim 3 (depends on 1)

A process according to claim 1 wherein the organic oxidizing agent is an organic compound containing quinone functionality containing up to 50 carbons or a fullerene.

### Claim 4 (depends on 1)

A process according to claim 1 wherein the organic oxidizing agent is 2,3,5,6tetramethylbenzoquinone, 2,3,5,6-tetratertbutylbenzoquinone, 2,2',6,6'-tetramethyldiphenoquinone, and 2,2',6,6'-tetratert-butyldiphenoquinone.

### Claim 5 (depends on 1)

A process according to claim 1 wherein the Lewis acid mitigating agent is tris(pentafluorophenyl) borane, tris (2,3,5,6-tetrafluorophenyl)borane, tris(2,3,4,5-tetrafluorophenyl)borane, tris(3,4,5-trifluorophenyl)borane, tris(1,2,2-trifluoroethenyl) borane, phenylbis(perfluorophenyl)borane, tris(perfluorophenyl) borate, or triethyl borane.

### Claim 6 (depends on 1)

A process according to claim 1 wherein M is titanium.

### Claim 7 (depends on 1)

A process according to claim 1 wherein L is a monovalent anionic stabilizing ligand selected from the group consisting of:
1) covalently bonded hydrocarbyl, silyl, amido, phosphido, alkoxy, aryloxy, sulfido groups and mixtures thereof, said group 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
2) C.sub.3-40 hydrocarbyl radicals comprising an ethylenic unsaturation able to form an .eta.3 bond with M.

### Claim 8 (depends on 1)

A process according to claim 1 wherein the complex corresponds to the formula: ##STR8## wherein: L independently each occurrence is a covalently bonded hydrocarbyl group 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, or a C.sub.3-40 hydrocarbyl radical comprising an ethylenic unsaturation able to form an .eta.3 bond with M;
Cp is a cyclopentadienyl or substituted cyclopentadienyl group bound in an .eta..sup.5 bonding mode to M;
Z is a divalent moiety comprising carbon or silicon; and
Y is a linking group comprising nitrogen or phosphorus;
J is as previously defined;
A' is a nonligating form of A; and
A" is a ligating form of A.

### Claim 9 (depends on 8)

A process according to claim 8 wherein: ##STR9## wherein, R' each occurrence is independently selected from the group consisting of hydrogen, silyl, alkyl, aryl and combinations thereof having up to 10 carbon or silicon atoms;
E is silicon or carbon; and
a is 1 or 2.