# US 5,952,456 A · Gas phase process for the co-polymerization of carbon monoxide and ethylenically unsaturated compounds

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- Number: US 5,952,456 A
- Document ID: US5952456A
- Status: Granted
- Kind: A
- Application number: 08/528,831
- Filed: 1995-09-15
- Granted: 1999-09-14
- Earliest claimed: 1994-09-15
- Assignees: Shell Oil Company
- Inventors: Arleen Marie Bradford; Andre Buys
- Web page: https://patentgrep.com/patent/US5952456A

## CPC

- C08G 67/02: Copolymers of carbon monoxide and aliphatic unsaturated compounds
- B01J 31/146: {of boron}
- B01J 31/2409: {with more than one complexing phosphine-P atom}
- B01J 2531/0227: Carbollide ligands, i.e. [nido-CnB(11-n)H11](4-n)- in which n is 1-3
- B01J 2531/824: Palladium
- B01J 2531/845: Cobalt
- B01J 2531/847: Nickel
- C08G: MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- B01J: CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS

## Abstract

A gas phase process for the preparation of co-polymers comprising reacting carbon monoxide and an ethylenically unsaturated compound in the presence of a catalyst system based on (a) a source of cations of a metal of Group VIII of the Periodic Table; (b) a source of anions which comprise a plurality of boron atoms or a source of organic boron containing anions or an aluminoxane; and (c) a source of ligands.

## Claims

### Claim 1

A gas phase process for the preparation of co-polymers comprising reacting carbon monoxide and one or more ethylenically unsaturated compounds in the presence of a catalyst system comprising:
(a) a source of cations of one or more noble metals of Group VIII of the Periodic Table;
(b) a boron containing anion selected from the group consisting of anions containing a plurality of boron atoms and carborates; and
(c) a source of ligands.

### Claim 2 (depends on 1)

The process of claim 1 wherein said boron containing anion is selected from the group consisting of tetraphenylborate, tetrakis(perfluorophenyl)borate and tetrakis›3,5-bis(trifluoromethyl)phenyl! borate anions.

### Claim 3 (depends on 1)

The process of claim 1 wherein said source of cations is a salt of palladium and a carboxylic acid, said source of ligands is a bidentate ligand of the general formula
R.sup.1 R.sup.2 M.sup.1 -R-M.sup.2 R.sup.3 R.sup.4 (I)
wherein M.sup.1 and M.sup.2 represent phosphorus atoms, each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 independently represents a non-substituted or polar substituted aryl group and R represents a bivalent bridging group containing 2 to 4 carbon atoms in the bridge.

### Claim 4 (depends on 3)

The process of claim 3 wherein each of R.sup.1, R.sup.2, R.sup.3 and R.sup.4 represents an ortho-alkoxyphenyl group and R represents a trimethylene group.

### Claim 5 (depends on 1)

The process of claim 1 comprising between about 1.0 and 50 equivalents of boron anions and between about 0.5 and 8 moles of bidentate ligand, all quantities being defined per gram atom of Group VIII noble metal.

### Claim 6 (depends on 1)

The process of claim 1 comprising between about 100 and 2000 gram atoms of aluminumand between about 0.5 and 8 moles of bidentate ligand, all quantities being defined per gram atom of Group VIII noble metal.

### Claim 7 (depends on 1)

The process of claim 1 wherein said source of cations comprises a member of the group of metals consisting of cobalt, nickel, manganese, lead, zinc, magnesium, iron (II), copper (II), lanthanum, neodymium and mixtures thereof.

### Claim 8 (depends on 7)

The process of claim 7 wherein said cation sources comprises a member of the group consisting of cobalt, nickel and manganese.

### Claim 9 (depends on 7)

The process of claim 7 wherein said metals are present in a quantity of 1.0 to 10 gram atom per gram atom of Group VIII noble metal.

### Claim 10 (depends on 1)

The process of claim 1 wherein said Group VIII metal is covalently bonded with a single hydrocarbyl or acyl group.

### Claim 11 (depends on 1)

The process of claim 1 further comprising a promoter selected from the group consisting of benzoquinone, naphthoquinone or anthraquinone, in a quantity of 1 to 50 mol per gram atom of Group VIII noble metal.

### Claim 12 (depends on 1)

The process of claim 1 wherein said catalyst system is supported on a carrier comprising a copolymer of carbon monoxide with one or more ethylenically unsaturated compounds.

### Claim 13 (depends on 1)

The process of claim 1 wherein as ethylenically unsaturated compound ethene or a mixture of ethene with propene or ethene with 1-butene is used, the reaction is carried out at a temperature in the range of 30 to 150 C. and at a pressure in the range of 20 to 100 bar.