Patent GB-676889-A (GB)
Title: Improvements in or relating to polymeric materials
IPC: C08F20/42
Filed: 1949-09-29
Abstract: Acrylonitrile is copolymerized with not more than 10 per cent, based on total monomer weight, of vinyl ethers of amino alcohols, or water soluble salts thereof.  Suitable ethers are those represented by the general formula <FORM:0676889/IV (a)/1> wherein A is an alkylene group, n is an integral number, and X and Y taken singly are hydrogen, alkyl, hydroxy alkyl, alkoxyalkyl, aminoalkyl, cyanoalkyl, cycloalkyl, aralkyl, furfuryl, pyridyl, aryl, or aminoaryl radicals; and X and Y taken jointly with the N atom are divalent radicals which form a heterocycle therewith. Amongst the ethers specified are beta-dimethylaminoethyl vinyl ether, beta-diethylaminoethyl vinyl ether, beta-phenylaminoethyl vinyl ether, beta-benzylaminoethyl vinyl ether, N-beta-dimethylamino beta-aminoethyl vinyl ether, bis-(2-hydroxyethylamino) ethyl vinyl ether, beta-dicyanoethylamino ethyl vinyl ether, the beta-dimethylaminoethyl ether of ethylene glycol vinyl ether, beta-morpholinoethyl vinyl ether, beta-morpholinoethylaminoethyl vinyl ether, and beta-piperidinoethyl vinyl ether; other ethers are listed in the Specification. Water-soluble salts of the amino ethers specified are those formed by reaction with inorganic and organic acids such as hydrochloric, sulphuric, phosphoric, nitric, boric, formic, acetic, propionic, chloroacetic, acrylic, methacrylic, crotonic, lauric, stearic, oleic, glycolic, lactic, benzoic, phenyl acetic, phthalic, naphthenic, furoic, maleic, fumaric, itaconic, citraconic, oxalic, succinic, adipic, and sebacic acids.  The copolymers may be modified by the inclusion in the monomer mixture of quantities of up to 10 per cent of other copolymerizable monomers such as vinyl chloride and fluoride, vinylidene chloride an fluoride, methacrylonitrile, fumaro - dinitrile, acrylamide, methacrylamide, vinyl acetate and other vinyl esters, isopropenyl acetate, vinyl ethyl ether, styrene, vinyl ketones, and acrylic, methacrylic, maleic, fumaric, citraconic and itaconic acids and their esters.  Copolymerization may be carried out in bulk, aqueous emulsion, or solution, using a solvent such as an alkylene carbonate; also present may be catalysts such as ammonium persulphate and benzoyl peroxide, catalyst activators such as sodium bisulphite, and emulsifying agents such as that known under the Registered Trade Mark "Triton 720" which is the sodium salt of an alkyl aryl polyether sulphonic acid.  When the reaction is carried out in aqueous emulsion the monomers may be added to the reaction mixture during the course of the reaction.  The copolymers may be used for forming films and fibres from solution in gamma valerolactone, ethylene carbonate, propylene carbonate, trimethylene carbonate, 1,3-butylene carbonate, and nitro methane.  Fibres may be formed by either wet or dry spinning.  When wet spinning is employed the copolymer solutions may be extruded into hot water or aliphatic hydroxy-containing compounds such as ethylene glycol, 2,3-butylene glycol, 1,3-isohexylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, dipropylene glycol, tripropylene glycol, sorbitol glycerol, polyglycerol, glyceryl monomethyl ether, and glyceryl dimethyl ether.  The fibres and films may be oriented by stretching and heat treatment and dyed with acid dyes.  Specification 611,622 is referred to.ALSO:The preparation of beta-morpholinoethyl vinyl ether, beta-morpholinoethylaminoethyl vinyl ether, and beta-piperidinoethyl vinyl ether is described in examples. Beta-morpholinoethyl vinyl ether is prepared by refluxing with water 2-chloroethyl vinyl ether, morpholine, and sodium hydroxide; on cooling the free base separates as an oily upper layer which is separated and distilled under reduced pressure. Beta-morpholinoethylaminoethyl vinyl ether is prepared by refluxing with water beta-morpholinoethylamine, 2-chloroethyl vinyl ether and sodium hydroxide; the free base is salted out with sodium chloride, extracted with ether and distilled under vacuum. Beta-piperidinoethyl vinyl ether is prepared by refluxing with water piperidine, 2-chloroethyl vinyl ether, and sodium hydroxide. The products are employed as monomers copolymerizable with acrylonitrile. Specification 611,662, [Group IV (a)], is referred to.ALSO:Fibres and films capable of being dyed with acid dyes are made from copolymers of acrylonitrile with not more than 10 per cent of a vinyl ether of an amino alcohol.  Preferred ethers are those of the general formula <FORM:0676889/IV (c)/1> wherein A is an alkylene group, n is an integral number, and X and Y taken singly are hydrogen, alkyl, hydroxyalkyl, alkoxyalkyl, aminoalkyl, cyanoalkyl, cycloalkyl, aralkyl, furfuryl, pyridyl, aryl or aminoaryl radicals; and X and Y taken jointly with the N atom are divalent radicals which form a heterocycle therewith. Also present in the monomer mixture may be up to 10 per cent of another olefinic copolymerizable monomer. Specification 611,662 is referred to.