Patent GB-702017-A (GB)
Title: Improvements relating to acrylonitrile compositions
IPC: C08F220/44
Filed: 1951-11-29
Abstract: Copolymers are made from a mixture of monomers comprising acrylonitrile and one or more dialkylaminopropylacrylamides of the general formula <FORM:0702017/IV(a)/1> in which R and R1 are alkyl radicals, such as N-(3-dimethylaminopropyl) acrylamide.  Other monomers may be present, such as vinyl acetate, vinyl propionate, vinyl butyrate, vinyl isobutyrate, vinyl valerate, vinyl acrylate, vinyl methacrylate, styrene, dialkyl styrenes, isopropenyl toluene, acrylic, methacrylic, ethacrylic, and phenylacrylic acids and their methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, amyl, hexyl, heptyl, octyl, decyl, and dodecyl esters, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, methacrylamide, ethacrylamide, N-methylol acrylamide and the N-monoalkyl, N-dialkyl, N-monoaryl, and N-diaryl acrylamides and methacrylamides, specified alkyl and aryl groups being methyl, ethyl, propyl, butyl, and phenyl. Copolymerization may be carried out batchwise or continuously in bulk, or in solution in an organic solvent, but preferably in an aqueous medium, optionally with the aid of an emulsifying agent such as the sodium sulphate of a long chain aliphatic hydrocarbon, or by conventional bead polymerization methods.  Copolymerization may be accelerated by heat and/or light, and with the aid of catalysts such as hydrogen, barium and magnesium peroxides, ethyl, propyl, tert.-butyl, tert.-amyl, lauryl, stearyl, oleyl, caprylyl, and hydroxyheptyl peroxides, acetyl, propionyl, lauroyl, stearoyl, malonyl, succinyl, phthaloyl, benzoyl, p-chlorobenzoyl, and 2, 4 - dichlorobenzoyl, peroxides, tert.-butyl, tert.-amyl, cumene, and "Tetralin" (Registered Trade Mark), hydroperoxides, tert.-butyl diperphthalate, tert.-butyl perbenzoate, urea peroxide, 2, 2-bis (tert.-butylperoxy) butane, the diperoxide of benzaldehyde, coconut oil acid peroxides, acetyl benzoyl peroxide, propionylbenzoyl peroxide, ascaridole, ammonium, potassium, and sodium persulphates, sodium and potassium percarbonates, perborates, and perphosphates, and alpha, alpha1-azodiisobutyronitrile.  The persulphate catalysts may be employed in conjunction with sodium metabisulphite.  The copolymers, which are dyeable with acid dyes, may be dissolved in an aqueous solution of sodium thiocyanate and spun into fibres which may be stretched and then bleached prior to dying with acid dyes, by boiling in aqueous hydrogen peroxide followed by boiling in dilute nitric acid, or the copolymers may be used in moulding compositions, which may contain fillers such as alpha-cellulose pulp, asbestos fibres, cotton flock, chopped cloth cuttings, glass fibres, wood flour, antimony oxide, titanium dioxide, sand, clay, mica dust, and diatomaceous earth.  The copolymers may also be employed as adhesives or coating compositions, in which case polymerization may be carried out in situ on the material to be coated.  Specification 586,881 is referred to.ALSO:Dialkylaminopropylacrylamides of the general formula: <FORM:0702017/IV(b)/1> in which R and R1 are alkyl radicals, are prepared by reacting acrylyl chloride with a dialkylaminopropylamine. The dialkylaminopropylamine intermediate may be prepared by reacting acrylonitrile with a dialkyl secondary amine to form a nitrile of the general formula: <FORM:0702017/IV(b)/2> and hydrogenating to form the corresponding dialkylaminopropylamine.  In an example dimethylaminopropylamine is added gradually to acrylyl chloride dissolved in acetonitrile containing hydroquinone, a polymerization inhibitor, the reaction mixture being maintained at 44 DEG -53 DEG C.  At the termination of the reaction aqueous sodium hydroxide is added to the reaction mixture, the sodium chloride filtered off, and the solvent removed with a water aspirator.  Distillation yields crude N-(3-dimethylaminopropyl) acrylamide which is purified by redistillation to give a liquid boiling at 106 DEG -108 DEG  C. Specification 586,881 is referred to.ALSO:Copolymers of acrylonitrile with one or more dialkylaminopropylacrylamides such as N-(3-dimethylaminopropyl) acrylamide, are formed into fibres which are bleached by boiling in aqueous hydrogen peroxide followed by boiling in dilute nitric acid, and then dyed with acid dyestuffs in an aqueous dye-bath acidified with sulphuric acid.  Specification 586,881 is referred to.