Patent GB-1158296-A (GB)
Title: Unsaturated Hydrocarbon Polymers
IPC: C08F2/00
Filed: 1967-09-22
Abstract: 1,158,296. Unsaturated monomer polymerization. JAPAN SYNTHETIC RUBBER CO. Ltd. 22 Sept.. 1967 [26 Sept., 1966(2); 15 July, 1967], No. 43310/67. Heading C3P. Unsaturated monomers containing 4-10 carbon atoms, and of general formula CH 2  = CH-CR<SP>1</SP> = CR<SP>2</SP>R<SP>3</SP> wherein R<SP>1</SP> represents a hydrogen atom or methyl group and R<SP>2</SP> and R<SP>3</SP> represent a hydrogen atom, an alkyl group having 1-6 carbon atoms, or alkenyl group having 2-6 carbon atoms are polymerized to polymers of high 1,2- vinyl configuration by contacting with a catalyst prepared by mixing the following:- (A) a cobalt compound (B) a phosphine compound, PR<SP>4</SP>R<SP>5</SP>R<SP>6</SP>, wherein R<SP>4</SP>, R<SP>5</SP> and R<SP>6</SP> represent an alkyl or aryl group or a hydrogen atom (C) an organo aluminium compound, AlR<SP>7</SP> R<SP>8</SP>R<SP>9</SP>, wherein R<SP>7</SP>, R<SP>8</SP> and R<SP>9</SP> represent alkyl or aryl groups, and (D) water in an amount of 0À25-1À50 mols per one mol of said organo aluminium compound, in a hydrocarbon or halogenated hydrocarbon solvent. Preferred monomers are butadiene, isoprene, 1,3-pentadiene, 4-methyl pentadiene-1,3 and 5-methyl heptatriene-1,3,6. The cobalt compound may be an inorganic acid salt, organic acid salt or complex such as cobalt bis-acetylacetonate, cobalt bromide, cobalt octenoate, dicobalt octacarbonyl, cobalt trisacetylacetonate, tris-#-allyl-cobalt or cyclopentadienyl cobalt dicarbonyl. The phosphine may be triphenyl phosphine, triethylphosphine, diethyl phenyl phosphine, ethyldiphenyl phosphine, tricyclohexyl phosphine, tri-n-butyl phosphine or tri-n-propyl phosphine. The organo aluminium compound may be triethyl, tri-isobutyl or trihexyl aluminium. The molar ratio of cobalt compound to organoaluminium compound is preferably from 1: 1 to 1: 2000, and the molar ratio of the cobalt compound to the phosphine is preferably from 1: 0À5 to 1: 100. The amount of catalyst present is preferably from 0À001 to 1 millimol, based on the amount of the cobalt compound per one mol of the monomer. The catalyst may be prepared at 0‹ to 50‹ C. and the monomer contacted with it at 20 to 100‹ C. The components (A) and (B) may be added as a complex COX 2 (PR<SP>4</SP>R<SP>5</SP>R<SP>6</SP>) 2  wherein X represents a halogen atom and R<SP>4</SP>, R<SP>5</SP> and R<SP>6</SP> represent an alkyl or aryl group or a hydrogen atom. Such complexes are bis-triphenyl phosphine cobalt bromide, bis-triethyl phosphine cobalt bromide, bis-diethyl phenyl phosphine cobalt bromide, bis-ethyldiphenyl phosphine cobalt bromide, bis-triphenyl phosphine cobalt chloride, bis-triethyl phosphine cobalt chloride, bistriphenyl phosphine cobalt iodide and bistriethyl phosphine cobalt iodide. In the examples. butadiene, 1,3 pentadiene, methyl pentadiene 1,3 and isoprene are polymerized, to form crystalline polymers in methylene dichloride or toluene, under a nitrogen atmosphere, and the reactions are terminated using methanol containing a small amount of an antioxidant, phenyl-#-naphthylamine; a hydrochloride methanol solution containing anti-oxidant may also be used. The catalyst systems used, comprise triphenylphosphine, triethyl aluminium, water and one of the following:-cobalt bis-acetylacetonate. anhydrous cobalt bromide, cobalt octenoate, cobalt trisacetylacetonate tris-#-allyl cobalt, cyclopentadienyl cobalt dicarbonyl; As alternative phosphines, one of the following may be used:- triethyl, diethylphenyl, diphenyl ethyl, triphenyl, tricyclohexyl, n-butyl and n-propyl phosphine. Triisobutyl or trihexyl aluminium may be used instead of triethyl aluminium. Further examples illustrate the use of cobalt halidephosphine complexes in the catalyst system. Such complexes used are. bis-triethyl phosphine cobalt bromide, chloride or iodide, bis-diethylphenyl phosphine cobalt bromide, bis-diphenylethylphosphine cobalt bromide, bis-triphenyl phosphide cobalt bromide, chloride or iodide.