GB1149961A - Polymerisation process using metal carbonyl catalysts - Google Patents

Abstract

1,149,961. Polymerisation process using metal carbonyl catalysts. IMPERIAL CHEMICAL INDUSTRIES Ltd. 24 June, 1966 [6 July, 1965], No. 28576/65. Headings C3G and C3P. Ethylenically unsaturated compounds are polymerized by contacting with a transition metal carbonyl in the presence of a halogenated organic compound and in the presence of more than 100 p.p.m. by volume of atmospheric oxygen. Unsaturated compounds specified are acrylic and methacrylic acids and their esters, e.g. methyl methacrylate, 2-hydroxyethyl methacrylate or 2-t-butylaminoethyl methacrylate, amides and nitriles, styrene, vinyl chloride, vinyl pyridine, vinyl acetate, vinyl perfluorobutyrate and vinylidene chloride. The carbonyl may be of Fe, Co, Mo, Cr, W, Mn or Ru, and may include additional groups, e.g. halogen, cyclopentadienyl, =SÀCH 3 and =SÀC 6 H 5 groups. Halogenated compounds specified are carbon tetrachloride, chloroform, trichlorobromomethane, bromoform, carbon tetrabromide, trichlorofluoromethane, chloral, trichloroacetonitrile, benzotrichloride, methylene chloride and chloroacetamide (the last two compounds being rather less effective than the others); also suitable are compounds of the formula X 3 C-Y-SiX 3 (where X is halogen and Y is a divalent organic radical or a direct link), e.g. p-trichloromethylphenyl-trichlorosilane; the halogen-containing compound may also be a polymer such as poly(vinyl trichloracetate) or poly(vinyl monochloracetate), in which case the process of the invention can yield a graft polymer (see Examples 8 and 10). Polymerization can be effected in the presence or absence of a liquid diluent, which may be aqueous or non- aqueous; when it is aqueous an emulsifier, e.g. sodium dodecylbenzenesulphonate may be present. The polymerization can be assisted by application of heat, visible or UV radiation.