Patent GB-764301-A (GB)
Title: Improved polymers prepared from acrylonitrile
IPC: C08F265/10
Filed: 1953-10-21
Abstract: Graft polymers are prepared by polymerizing, in the presence of a catalyst, in solution or dispersion from 5 to 95 parts of a monomer mixture consisting of from 1 to 99 per cent of a monomer (1) selected from acrylonitrile, dimethyl fumarate, methyl aminoacrylate, methyl acetaminoacrylate, and those represented by the formul <FORM:0764301/IV(a)/1> (acrylamides) <FORM:0764301/IV(a)/2> (maleamides) <FORM:0764301/IV(a)/3> (fumaramides) <FORM:0764301/IV(a)/4> (itaconamides) <FORM:0764301/IV(a)/5> (citraconamides) <FORM:0764301/IV(a)/6> (maleamates) <FORM:0764301/IV(a)/7> (fumaramates) <FORM:0764301/IV(a)/8> and <FORM:0764301/IV(a)/9> (itaconamates) <FORM:0764301/IV(a)/100> and <FORM:0764301/IV(a)/111> (citraconamates) <FORM:0764301/IV(a)/122> (acrylates), and <FORM:0764301/IV(a)/133> (vinyl and isopropenyl carboxylic esters) wherein each R and R1 represents a member selected from the group consisting of a hydrogen atom and an alkyl group containing from 1 to 4 carbon atoms, R2 represents an alkyl group containing 1 to 4 carbon atoms, R3 represents a member selected from the group consisting of a hydrogen atom and a methyl group, and R4 represents an alkyl group containing from 1 to 3 carbon atoms, and from 99 to 1 per cent of a different monomer (2) selected from those represented by the above formul , to produce a copolymer, adding to the reaction mixture containing the unseparated copolymer from 95 to 5 parts of a different monomer mixture consisting of from 85.0 to 99.5 per cent of acrylonitrile and from 15.0 to 0.5 per cent of a different monoethylenicallyunsaturated polymerizable monomer (3) containing a -CH=C< group, and then polymerizing the reaction mixture.  In an alternative procedure a reverse process is employed in which monomers (1) and (2) are copolymerized in the presence of a preformed copolymer of acrylonitrile and a monomer containing a -CH=C< group which has not been separated from its polymerization medium.  Lists of monomers (1) are provided in the Specification. Monomers specified containing the -CH=C> group are those enumerated under heading (1), other than acrylonitrile, and also styrene, p-acetaminostyrene, alpha-acetoxystyrene, vinyl chloride, vinylidene chloride, ethyl vinyl ether, isopropyl vinyl ether, isopropenyl methyl ketone, isopropenyl ethyl ketone, methyl vinyl ketone, ethyl vinyl ketone, dimethyl, diethyl, and diisopropyl fumarates and maleates, fumaronitrile, acrylic and methacrylic acids, N-vinyl phthalimide, vinyl sulphonamide, ethylene, and isobutylene. Polymerization catalysts specified are peroxides such as benzoyl, acetyl, acetyl benzoyl, lauryl, oleoyl, triacetone, urea, and hydrogen peroxides, t.-butyl hydroperoxide, sodium and potassium perborates, sodium, potassium, and ammonium persulphates, and azines and ketazines; the persulphate catalysts may be used in conjunction with potassium or sodium bisulphite. Polymerization may be carried out in acetonitrile or aqueous acetone, but is preferably effected in an aqueous medium in the presence or absence of emulsifiers such as sodium lauryl sulphate, sodium isobutylnaphthalene sulphonate, alkali metal or amine salts of sulphosuccinic acid esters, potassium laurate, sulphonated fatty acid amides, alkali metal salts of alkane sulphonic acids, 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 vinyl or isopropenyl acetate, and the solutions used in the production of films and fibres.  Solvents specified are dimethyl formamide, dimethyl acetamide, dimethyl cyanamide, dimethyl cyanoacetamide, dimethyl-beta-cyanopropionamide, gamma-butyrolactone, N-methyl-2-pyrrolidone, glyconitrile, malonitrile, ethylene carbonate, ethylene carbamate, ethylene cyanohydrin, dimethyl sulphoxide, dimethyl sulphone, tetramethylene sulphoxide, tetramethylene sulphone, N-formyl pyrrolidine, N-formyl morpholine, and tetramethylene methanephosphonamide.  Specifications 764,296, 764,297 and 764,298 are referred to.