Patent GB-1104344-A (GB)
Title: Unsaturated amides and polymers thereof
IPC: C08L1/00
Filed: 1965-05-12
Abstract: Unsaturated amides of the formula <FORM:1104344/C3/1> wherein A is a C2- 3 alkylene group, R is H, -CH2OH or -CH2OR, R1 is C1- 4 alkyl and X is O or S, are polymerized alone or with one or more other ethylenically unsaturated compounds (many examples listed) in bulk, solution, emulsion or suspension, in the presence of polymerization catalysts, various peroxy and azo catalysts being specified.  The above polymers may also be obtained by reacting an amine of the formula <FORM:1104344/C3/2> with a polymer of crotonic acid or ester thereof or with a copolymer of crotonic acid or an ester thereof with other ethylenically unsaturated monomers such as vinyl acetate, acrylic or methacrylic acid or ester, nitrile or amide thereof, styrene or vinyl toluene.  In examples unsaturated amides of the first formula above are (8) copolymerized with ethyl acrylate and methyl methacrylate in the presence of toluene, di-tert.-butyl peroxide and benzoyl peroxide; (9) copolymerized with ethyl acrylate and methyl methacrylate in presence of water, ammonium persulphate, ferrous sulphate, sodium metabisulphite, sodium tert.-octyl-phenoxy-diethoxyethyl sulphonate and sec.-butyl hydroperoxide, and the resulting polymer further admixed with the ammonium salt of a maleic anhydride/diisobutylene copolymer, titanium dioxide, mica, hydroxyethyl cellulose, ethylene glycol, preservative and anti-foamer to form a pigmented primer; (10) copolymerized with ethyl acrylate and vinyl acetate as in (9) and formed into a pigmented primer as in (9); (11) copolymerized with butyl acrylate, styrene, acrylonitrile and methacrylic acid as in (8); (12) copolymerized with ethyl acrylate and vinyl acetate as in (9), except that the emulsifier is replaced by sodium lauryl sulphate solution, and the resulting polymer modified by heating with a mixture of formaldehyde and sodium hydroxide; (14) copolymerized with a mixture of ethyl acrylate and aminoethyl vinyl sulphide in presence of toluene and a ,a 1-azodiisobutyronitrile. In a further example (13) styrene is copolymerized with methyl crotonate in the presence of toluene and a ,a 1-azobisbutyronitrile and the resulting polymer is heated with N-aminoethyl - N,N1 - ethyleneurea to provide a modified polymer corresponding to a copolymer of styrene and an unsaturated amide of the first formula above.  Unsaturated amides of the first formula above may be added to melts, solutions or dispersions of vinyl polymers or copolymers or copolymers of acrylonitrile with ethylene or isobutylene which are subsequently formed into fibres, sheets, films, rods or other shaped structures having modified dyeing characteristics or improved anti-static properties. They may also be added to glycerine or glycols to provide softening compositions for regenerated cellulose or hydroxyethyl cellulose products.  The unsaturated amide monomers may be further used as modifiers in urea-formaldehyde and melamine-formaldehyde condensates. Homopolymers of unsaturated amides of the first formula may be admixed with starch or gelatine to form coatings, films or warp sizes. Copolymers of such amides may be spun into fibres, cast into films, used as warp sizes, wet strength resins, thickeners, coatings for various substrates, ingredients for lacquers, enamels and water-base paints, shrinkproofing agents for wool fabrics, and bonding agents for "non-woven" fibres.  They may also be added to melts or solutions of copolymers of acrylonitrile with vinyl chloride or vinyl acetate to give fibres formed therefrom modified dyeing properties.ALSO:Clays or finely divided minerals produced in the grinding of ores are flocculated in aqueous media by the addition of homopolymers of unsaturated amides of the formula <FORM:1104344/C1/1> wherein A is a C2- 3 alkylene group, R is H, -CH2OH or -CH2OR1, R1 is C1- 4 alkyl and X is O or S, having molecular weights of at least 20,000 to 50,000.ALSO:Novel unsaturated amides of the formula <FORM:1104344/C2/1> wherein A is a C2- 3 alkylene group, R is H, -CH2OH or -CH2OR1, R1 is C1- 4 alkyl and X is O or S, are prepared by reacting crotonic acid or a halide or ester thereof with an amine of the formula <FORM:1104344/C2/2> Compounds in which R is H may be subsequently methylolated or alkoxymethylated.ALSO:Textile, leather, paper, wood, steel, copper, aluminium, glass or previously primed metal substrates are coated with polymers of unsaturated amides of the formula:- <FORM:1104344/B1-B2/1> wherein A is a C2-3 alkylene group, R is H, -CH2OH or -CH2OR\sv, R\sv is C1-4 alkyl and X is O or S.  The pre-priming may be with alkyd, aminoplast or epoxy-containing primers.  Textiles such as wool fabrics may be shrink-proofed by depositing aqueous dispersions of the above polymers thereon followed by drying and subsequent heating to 240 DEG  to 350 DEG F.  In examples (8) to (10) N-[b -N\sv,N"-ethyleneureido)-ethyl]-crotonamide or N-[b -N\sv,N"-propylenethioureido) propyl]- crotonamide are copolymerized with ethyl acrylate and methyl methacrylate or ethylacrylate and vinyl acetate respectively in toluene or water and the resulting solutions applied to cold-rolled steel panels and baked at 150 DEG C. or brushed on to various wood panels. Alternatively the resulting solutions are admixed with the ammonium salt of a maleic anhydride/diisobutylene copolymer, rutile titanium dioxide, water ground mica, hydroxyethyl cellulose and ethylene glycol to form a pigmented primer which is brushed on to various wood panels.  In both instances the treated wood panels may be further coated with two coats of water-base acrylic polymer exterior paint.  In a further example (11) a mixture of butyl acrylate, styrene, acrylonitrile, methacrylic acid and the N-methylol derivative of N-[b -(N\sv,N"-ethyleneureido)-ethyl]-crotonamide is polymerized and used to coat copper wire which is dried and subsequently cured by heating to 150 DEG C.ALSO:Fibres are bonded in "non-woven" fabrics and increased wet strength is imparted to paper by treatment with polymers of unsaturated amides of the formula:- <FORM:1104344/D1-D2/1> wherein A is a C2-3 alkylene radical, R is H, -CH2OH or -CH2OR\sv, R\sv is C1-4 alkyl and X is O or S. In an example (12) an aqueous dispersion of an emulsion copolymer of N-[b - (N\svN\yF-ethyleneureido)ethyl] - crotonamide, ethyl acrylate and vinyl acetate is methylolated and padded on to a carded viscose web which is subsequently air dried and then cured at 150 DEG C.