# US 4,397,764 A · Polymer-supported ethylene polymerization catalyst

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- Number: US 4,397,764 A
- Document ID: US4397764A
- Status: Granted
- Kind: A
- Application number: 06/362,182
- Filed: 1982-03-26
- Granted: 1983-08-09
- Earliest claimed: 1982-03-26
- Assignees: Conoco Inc.
- Inventors: Mark L. Shannon
- Web page: https://patentgrep.com/patent/US4397764A

## CPC

- C08F 10/02: Ethene
- C08F: MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS

## Abstract

A polymer-supported ethylene polymerization catalyst prepared by a method comprising (a) a polymer supported titanium-based catalyst consisting of (1) a polymer resin containing an amino borane reducing agent; (2) a titanium tetrahalide; (3) and a suitable organometallic and/or organic metallic co-catalyst. The polymers produced are resins of high density and melting point.

## Claims

### Claim 1

A catalyst system comprising
(a) a polymer supported titanium containing catalyst comprising
(1) a polymeric resin containing bound therein an amino borane reducing agent, and
(2) titanium tetrahalide; together with
(b) an organometallic co-catalyst, an organometallic hydride co-catalyst, an organometallic halide co-catalyst or mixtures of these.

### Claim 2 (depends on 1)

The catalyst system of claim 1 wherein the polymeric resin is selected from the group consisting of polystyrene, polyvinylchloride, polyvinyl alcohol, polyethylene, polybutene, and copolymers, alloys, blends, derivatives and analogues of these.

### Claim 3 (depends on 2)

The catalyst system of claim 2 wherein the titanium tetrahalide is titanium tetrachloride.

### Claim 4 (depends on 3)

A catalyst system of claim 3 wherein the co-catalyst is selected from the group consisting of Grignard reagents, dibutyl magnesium, butyl ethyl magnesium, diethylaluminum chloride, triethylaluminum, diisobutylaluminum iodide, diisobutylaluminum hydride, and lithium triethyl borohydride.

### Claim 5

A method for preparing a catalyst for olefin polymerizations comprising reacting under an inert atmosphere
(1) a polymeric resin containing bound therein an aminoborane reducing agent, said resin suspended in an inert diluent, and
(2) a titanium tetrahalide compound, then
(3) allowing reaction to proceed between 1 and 2 to produce a solid, then recovering said solid, and
(4) combining said solid with an organometallic, organometallic halide or an organometallic hydride co-catalyst or mixtures of these prior to carrying out a polymerization.

### Claim 6 (depends on 5)

A method as described in claim 5 wherein the reaction between 1 and 2 is allowed to proceed at temperatures of from about 0.degree. to about 100.degree. C.

### Claim 7 (depends on 6)

A method as described in claim 6 wherein the resin is selected from the group consisting of polystyrene, polyvinyl alcohol, polyvinyl chloride, polyethylene, polybutene, and alloys, copolymers, blends, derivatives and analogues of these.

### Claim 8 (depends on 7)

A method as described in claim 7 wherein the diluent is a dry, organic compound having atmospheric oxygen removed therefrom.

### Claim 9 (depends on 8)

A method as described in claim 8 wherein the diluent is selected from the group consisting of hexane, cyclohexane, toluene, ether, N,N-dimethylformamide, acetone or acetonitrile as well as mixtures and analogues of these.

### Claim 10 (depends on 9)

A method as described in claim 9 wherein the co-catalyst is selected from the group consisting of dibutyl, magnesium, butyl ethyl magnesium, Grignard reagents, diethylaluminum chloride, triethylaluminum, diisobutylaluminum iodide, diisobutylaluminum hydride, lithium triethyl borohydride, or mixtures of these.

### Claim 11 (depends on 10)

A method as described in claim 10 wherein the co-catalyst is combined with the reaction product (a) prior to contacting with olefins and carrying out polymerization.

### Claim 12 (depends on 10)

A method as described in claim 10 wherein the co-catalyst is added to a polymerization mixture of olefin and the reaction product of (a).

### Claim 13 (depends on 3)

A catalyst as described in claim 3 wherein the aminoborane reducing agent on the polymer is selected from the group consisting of H.sub.3 B.N(Et).sub.3, ##STR5## H.sub.3 B.NH.sub.3, and mixtures of these.