Patent GB-764300-A (GB)
Title: Improved polymers prepared from acrylonitrile
IPC: C08F267/10
Filed: 1953-10-21
Abstract: Graft polymers are prepared by homopolymerizing, in the presence of a catalyst, in solution or dispersion, from 5 to 95 parts of a monomer (1) selected from those represented by the formul <FORM:0764300/IV(a)/1> (acrylamides) <FORM:0764300/IV(a)/2> (maleamides) <FORM:0764300/IV(a)/3> (fumaramides) <FORM:0764300/IV(a)/4> (itaconamides) <FORM:0764300/IV(a)/5> (citraconamides) <FORM:0764300/IV(a)/6> (maleamates) <FORM:0764300/IV(a)/7> (fumaramates) <FORM:0764300/IV(a)/8> and <FORM:0764300/IV(a)/9> (itaconamates) <FORM:0764300/IV(a)/10> and <FORM:0764300/IV(a)/11> (citraconamates) <FORM:0764300/IV(a)/12> (acrylates) and <FORM:0764300/IV(a)/13> (vinyl carboxylic esters) wherein each R and each R1 represents hydrogen or an alkyl group containing 1 to 4 carbon atoms, R2 represents an alkyl group containing 1 to 4 carbon atoms, R3 represents a hydrogen atom or methyl group and R4 represents an alkyl group containing 1 to 3 carbon atoms, adding to the polymerization mixture containing the unseparated homopolymer from 95 to 5 parts of a monomer mixture consisting of 85 to 99.5 per cent of acrylonitrile and from 15.0 per cent of a different monoethylenically unsaturated polymerizable compound (2) containing a -CH=C< group, and continuing the polymerization.  In an alternative procedure a reverse process is employed in which monomer (1) is homopolymerized in the presence of a preformed copolymer of acrylonitrile and monomer (2) which has not been separated from its polymerization medium.  Lists of monomers (1) are given.  Monomers specified containing a -CH=C< group are those enumerated under heading (1) and also styrene, alphamethyl styrene, alpha-acetoxystyrene, p-acetaminostyrene, vinyl and vinylidene chlorides, ethyl vinyl ether, isopropyl vinyl ether, isopropenyl methyl ketone, ethyl isopropenyl ketone, methyl vinyl ketone, ethyl vinyl ketone, dimethyl, diethyl and diisopropyl fumarates and maleates, fumaronitrile, methacrylonitrile acrylic and methacrylic acids, methyl acetaminoacrylate, N-vinyl phthalimide, vinyl sulphonamide, ethylene and isobutylene.  Polymerization catalysts specified are benzoyl, acetyl, acetyl benzoyl, lauryl, oleyl, triacetone, urea and hydrogen peroxides, t.-butyl hydroperoxide, alkyl percarbonates, sodium and potassium perborates, alkali metal and ammonium persulphates, and azines and ketazines; the persulphate catalysts may be used in conjunction with alkali metal bisulphites. Polymerization may be carried out in solution in organic solvents, in aqueous acetone, or in an aqueous medium in the presence or absence of emulsifiers such as sodium lauryl sulphate, sodium isobutylene naphthalene sulphonate, alkali metal or amine salts of sulphosuccinic acid esters, potassium laurate, sodium 7-ethyl-2 - methyl - undecan - 4 - sulphonate, sulphonated fatty acid amides and aryloxy polyalkylene ether sulphonates. Also present in the reaction mixture may be chain regulators such as hexyl, octyl, lauryl, dodecyl and myristyl mercaptans.  The polymers produced may be dissolved in various solvents, either alone or in admixture with polyacrylonitrile or copolymers containing at least 85 per cent of acrylonitrile, e.g. copolymers with methacrylonitrile or methyl acrylate.  Solvents specified are dimethyl formamide, dimethyl acetamide, dimethyl - beta - cyanopropionamide, dimethyl cyanoacetamide, gamma - butyrolactone, ethylene carbonate, ethylene carbonamate, ethylene cyanohydrin, N - methyl - 2 - pyrolidone, glyconitrile, malononitrile, dimethyl sulphoxide, dimethyl sulphone, tetramethylene sulphoxide, tetramethylene sulphone, N-formyl pyrolidine, N-formyl morpholine and tetramethylene phosphonamide. Specifications 764,296, 764,297 and 764,298 are referred to.