Patent GB-723273-A (GB)
Title: Improvements in or relating to polymerization products
IPC: C08F8/14
Filed: 1952-08-21
Abstract: Films and fibres dyeable with acid, basic, vat, and acetate dyestuffs are made from acrylonitrile polymeric materials containing in polymer form a plurality of units of the formula:  <FORM:0723273/IV (c)/1> and a plurality of polymer units derived from a polymerizable ethylenic acid selected from acrylic, methacrylic, beta-cyanoacrylic, maleic, fumaric, citraconic, mesaconic, and itaconic acids, and the inner anhydrides of maleic, citraconic, and itaconic acids, in which at least some of the acid groups of the polymerized acid have been reacted with a monomeric nitrogen compound selected from the amino and hydroxy derivatives of pyridines, pyrimidines, and N,N-dialkyl anilines, and diamino-1,2,4-triazoles, whereby these compounds become attached to the polymeric ethylenic acid through an amide or ester linkage.ALSO:Polymeric acrylonitrile materials having an affinity for acid dyes are produced from polymers containing a plurality of units of the formula <FORM:0723273/IV (a)/1> and a plurality of units derived from acrylic, methacrylic, beta-cyanoacrylic, maleic, fumaric, citraconic, mesaconic, or itaconic acid, or the inner anhydrides of maleic, citraconic, and itaconic acids, by reacting at least some of the acid groups with a monomeric nitrogen compound selected from the amino and hydroxy derivatives of pyridines, pyrimidines, and N,N-dialkyl anilines, and diamino-1,2,4-triazoles, whereby these compounds become attached to the polymeric ethylenic acid through an amide or ester linkage, numerous compounds of these classes being specified.  The polymeric materials may consist of copolymers of acrylonitrile with the ethylenic acids, or blends of polymers or copolymers of acrylonitrile with polymers or copolymers of the ethylenic acids. Monomers specified which may be copolymerized with the acrylonitrile or ethylenic acids are methyl acrylate, methyl methacrylate, methyl beta-cyanoacrylate, methacrylonitrile, acrylamides, methacrylamides, beta - cyanoacrylamide, dimethyl and diethyl itaconates, itaconamide, fumaronitrile, vinyl acetate, vinyl and vinylidene fluorides and chlorides, tetrafluorethylene, trifluorochloroethylene, styrene, alpha-methyl styrene, ortho-, meta-, and parachloro-, -fluoro-, -trifluoromethyl-, and -cyanostyrenes, the various isomeric dichlorostyrenes, trichlorostyrenes, dicyanostyrenes, mono- and di-methylstyrenes, mono- and di-isopropylstyrenes, para-phenylstyrene, para-cyclohexylstyrene, difluorostyrenes, di-(trifluoromethyl)-styrenes, and vinyl naphthalenes.  The blending of the acrylonitrile and ethylenic acid polymers is preferably carried out in a mutual solvent such as dimethyl formamide, dimethyl acetamide, butyrolactone, ethylene carbonate, ethylene carbamate, N,N-dimethyl methyl urethane, N,N-dimethyl cyanamide, N,N-dimethyl cyano-acetamide, N,N-dimethyl methoxy-acetamide, methylene dinitrile, methylene dithiocyanate, formyl caprolactam, formyl morpholine, tetramethylene sulphone, and nitromethane.  The amidation or esterification of the ethylenic acid portions of the polymers may be carried out by heating the reactants together in a mutual solvent, or, in the case of fibres or films, by heating in a solvent for the nitrogenous compound which is a non-solvent for the polymer.  In a modification the polymeric material may be refluxed with sulphonyl chloride to convert the acid groups to acid chloride groups prior to amidation or esterification.  The polymeric materials may be prepared by polymerization in mass, suspension, emulsion, or solution; specified are emulsion polymerization in an aqueous medium of a pH of 3, and solution polymerization in butyrolactone, which may be assisted by catalysts such as benzoyl, naphthyl, phthalyl, and hydrogen peroxides, tert.-butyl hydroperoxide, tert.-butyl perbenzoate, azo compounds, and, in aqueous media, a mixture of ammonium persulphate and sodium bisulphite.  The polymeric materials may be formed either before or after amidation or esterification into fibres and films which are dyeable with acid, basic, and acetate dyestuffs.