| 摘要 |
1,218,628. A four-component catalyst for conjugated diene polymerization. JAPAN SYNTHETIC RUBBER CO. Ltd. 12 Aug., 1968 [11 Aug., 1967], No. 38396/68. Heading C3P. Conjugated monomers of the formula wherein R<SP>1</SP>, R<SP>2</SP> and R<SP>3</SP> are hydrogen, C 1-6 alkyl or C 2-6 alkenyl, are polymerized in a halogenated hydrocarbon solvent to a polymer having a major proportion of 1,2- or 3,4-units using a catalyst comprising (a) a cobalt compound, (b) a phosphine of the formula 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> are alkyl, cycloalkyl, aryl, hydrogen or halogen, (c) an aluminium compound of the formula AlR<SP>7</SP> m X 3-m , where R<SP>7</SP> is alkyl, X is Cl or F, and m is 0, 1, 1À5 or 2, and (d) an alkoxy alkyl aluminium compound of the formula AlR<SP>#</SP> n (OR<SP>9</SP>) 3-n , where R<SP>8</SP> and R<SP>9</SP> are alkyl and n is 1 or 2. The components (a) and (b) may be in the form of a complex. The process is conducted under otherwise conventional reaction conditions; oily polymers may be obtained. In the examples, butadiene, isoprene and pentadiene-1,3 are homopolymerized in CH 2 Cl 2 or C 6 H 5 Cl using the following catalyst components, (a) and (b) CoBr 2 .Ph 3 P, CoBr 2 .- Et 3 P, CoBr 2 .Ph 2 .Et.P, CoBr 2 .PhEt 2 P, cobalt bisacetylacetonate and Et 3 P, and cobalt octenoate and Ph 3 P, Ph 2 P.Cl or Et 2 PH, (c) AlEt 2 Cl, Al 2 Et 3 Cl 3 , AlEtCl 2 , AlCl 3 , AlEt 2 F, and (i-Bu) 2 - AlCl and (d) AlEt 2 (OEt), AlEt(OEt) 2 , AlEt- (OMe) 2 and Al(OMe) 2 (i-Bu). |
