GB1299761A - The polymerization of ethylenically unsaturated monomers - Google Patents

Abstract

1299761 Polymerization of unsaturated monomers CHATILLON SOC ANON ITALIANA PER LE FIBRE TESSILI ARTIFICIALI SpA 26 Feb 1970 [28 Feb 1969] 9435/70 Heading C3P Ethylenically unsaturated monomers of the formula in which R<SP>1</SP> to R<SP>4</SP> each represents independently of one another a H, F or Br atom, an aliphatic group (e.g. an optionally substituted alkyl group), an alicyclic group (e.g. an optionally substituted cycloalkyl group), an aromatic group (e.g. an aryl group), a monovalent heterocyclic group, an alkoxy group, a carboxylic group, an amide group, an alkoxy carbonyl group, an aryloxy carbonyl group, a nitrile group, a ketone group, an alkyl or aryl sulphide group, a sulphone group, an aldehyde group, an alkylcarbonyloxy group or an arylcarbonyloxy group, or at least two of R<SP>1</SP> to R<SP>4</SP> represent Cl atoms, are polymerized in bulk or in solution in the presence of a catalytic system consisting of an organic hydroperoxide of the formula R<SP>7</SP>-O-O-H, where R<SP>7</SP> represents a linear or branched alkyl group, a cycloalkyl group, an aryl group or an arylalkyl group, activated by a sulphur compound of the formula in which R represents an optionally substituted, linear or branched alkyl group having from 1 to 12 carbon atoms, or an optionally substituted cycloalkyl group having from 3 to 12 carbon atoms and X represents the chemical equivalent of a metal of the first or second group of the Periodic system or of aluminium, or any of the groupings represented by R in which case there is also present in the polymerization either a C 1 -C 6 alcoholate of an alkali metal, or an alkali metal hydroxide in solution in an aliphatic alcohol. If desired, the sulphur compound may be formed in situ in the polymerization mixture, e.g. by reacting an alcoholic solution of SO 2 with an appropriate metal alcoholate, oxide or hydroxide. The above monomers may be homopolymerized, or copolymerized with each other and/or other comonomers and/or unsaturated resins, e.g. unsaturated polyesters. Alkyl mercaptans may be employed to regulate the molecular weight of the polymer products. Examples illustrate the homopolymerization of styrene, ethyl vinyl ether, 2-hydroxyethyl acrylate, t-butylamino-ethyl methacrylate, vinyl acetate, vinyl formate, acrylic acid and acrylamide. Other monomers disclosed include vinyl propionate and benzoate, vinylidene formate, acetate, propionate and benzoate, acrylonitrile and methacrylonitrile, vinyl ethyl sulphide, divinylbenzene, ethylene and propylene.