# US RE31,331 E · Group Va and VII oxygen mineral acids as catalyst modifiers

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- Number: US RE31,331 E
- Document ID: USRE31331E
- Status: Granted
- Kind: E
- Application number: 06/271,563
- Filed: 1981-06-08
- Granted: 1983-08-02
- Earliest claimed: 1978-09-29
- Assignees: Standard Oil Company (Indiana)
- Inventors: Nikolaous K. Balint
- Web page: https://patentgrep.com/patent/USRE31331E

## Abstract

A propylene polymerization catalyst is formed by incorporation into a catalytic mixture, comprising a transition metal compound and an organoaluminum compound, effective amounts of Group Va or Group VII oxygen mineral acids whereby the amount of n-hexane-soluble polymeric product is decreased.

## Claims

### Claim 1

A polymerization process comprising contacting, under polymerization conditions, propylene or a mixture of propylene and one or more copolymerizable alpha-olefins with a catalyst comprising a titanium trihalide; an organoaluminum compound; and an effective amount of a [Group Va] nitrogen or a group VII oxygen mineral acid in aqueous solution in a molar ratio to titanium trihalide from about 0.01 to 1 to about 0.7 to 1 whereby the amount of n-hexane soluble polymeric product produced is decreased.

### Claim 2 (depends on 1)

The process of claim 1 wherein the organoaluminum compound is diethylaluminum halide, triethylaluminum, a mixture thereof or a mixture of triethylaluminum with ethylaluminum dihalide.

### Claim at position 3 (depends on 1)

[3. The process of claim 1 wherein the oxygen mineral acid is phosphoric acid, phosphorous
acid, or perchloric acid.] 4. The process of claim 1 wherein the mineral acid is nitric acid.

### Claim at position 4 (depends on 1)

[5. The process of claim 1 wherein the mineral acid is phosphoric acid.]

### Claim at position 5 (depends on 1, 2)

[6. The process of claim 1 wherein the mineral
acid is phosphorous acid.] 7. The process of claim 1 wherein the mineral
acid is perchloric acid. 8. The process of claim 2 wherein the organoaluminum compound is diethylaluminum chloride, triethylaluminum, a mixture thereof or a mixture of triethylaluminum with ethylaluminum dichloride.

### Claim at position 6 (depends on 3, 4)

[9. The process of claim 3 wherein the molar ratio of oxygen mineral acid to titanium trihalide is about 0.02 to 1 to about 0.5 to
1.] 10. The process of claim 4 wherein the molar ratio of nitric acid to titanium trihalide is about 0.02 to 1 to about 0.5 to 1.

### Claim at position 7 (depends on 5)

[11. The process of claim 5 wherein the molar ratio of phosphoric acid to titanium trihalide is about 0.02 to 1 to about 0.5 to 1.]

### Claim at position 8 (depends on 6, 7)

[12. The process of claim 6 wherein the molar ratio of phosphorous acid to titanium trihalide
is about 0.02 to 1 to about 0.5 to 1.] 13. The process of claim 7 wherein the molar ratio of perchloric acid to titanium trihalide is about 0.02 to 1 to about 0.5 to 1.

### Claim at position 9 (depends on 3)

[14. The process of claim 3 wherein the organoaluminum compound is diethylaluminum dichloride.]

### Claim 15

A polymerization process comprising contacting under polymerization conditions, propylene or a mixture of propylene and one or more copolymerizable alpha-olefins with a catalyst comprising a titanium trihalide; a dialkyl aluminum halide; and a phosphorous mineral acid in aqueous solution in a molar ratio to titanium trihalide from about 0.01 to 1 to about 0.5 to 1.

### Claim 16 (depends on 15)

The process of claim 15 wherein the mineral acid is phosphoric acid.

### Claim 17 (depends on 15)

The process of claim 15 wherein the mineral acid is phosphorous acid.

### Claim 18 (depends on 15)

The process of claim 15 wherein the titanium trihalide is titanium trichloride.

### Claim 19 (depends on 16)

The process of claim 16 wherein the molar ratio of phosphoric acid to titanium trihalide is about 0.02 to 1 to about 0.5 to 1.

### Claim 20 (depends on 17)

The process of claim 17 wherein the molar ratio of phosphorous acid to titanium trihalide is about 0.02 to 1 to about 0.5 to 1.