Patent GB-790585-A (GB)
Title: Acrylyl dicyandiamides and polymers thereof
IPC: C07C279/28
Filed: 1956-03-13
Abstract: The invention comprises acrylyl and methacrylyl dicyandiamides and the preparation thereof by reacting a compound of the formula: CH2 = C(R)COCl where R is H or CH3, with dicyandiamide in presence of an alkali metal or alkaline earth metal hydroxide or oxide.  The reaction is preferably conducted at temperatures between - 5 DEG  and + 50 DEG  C. and in presence of a small amount of water together with an organic solvent miscible therewith.  The desired product is isolated from the reaction mixture by neutralization with an acid.ALSO:Shrink-resistance and stiffness, crease-resistance and crush-resistance are imparted to wool and to cotton and rayon textiles by impregnating with homopolymers of acrylyl and methacrylyl dicyandiamides, or with copolymers of these monomers with one or more other monoethylenically unsaturated compounds, or with reaction products of such homopolymers and copolymers with hydrogen sulphide, formaldehyde, acetaldehyde, glyoxal and urea-formaldehyde, thiourea-formaldehyde and melamine-formaldehyde preliminary condensation products, or with a mixture of one of the above classes of compounds with a urea-formaldehyde or melamine-formaldehyde condensate.  The polymers and their derivatives may be applied to the textiles as solutions.  The monoethylenically unsaturated comonomer may be an ester of acrylic or methacrylic acid or of the dimer of methacrylic acid with a monohydric alcohol such as methanol, ethanol, butanol, octanol, dodecanol, cyclohexanol, cyanoethanol, benzyl alcohol or phenylethyl alcohol; a diester of itaconic, maleic or fumaric acid with any of the above alcohols; vinyl acetate, propionate or butyrate; a vinyloxyalkyl ester such as vinyloxyethyl acetate; a vinyl ether or sulphide such as ethyl vinyl ether, ethyl vinyl sulphide, butyl vinyl ether or octyl vinyl ether; acrylonitrile or methacrylonitrile; acrylamide, methacrylamide or an N-alkyl-substituted derivative thereof; vinyl toluene; a vinyl naphthalene such as 4-chloro-1-vinyl naphthalene; styrene; N - (b  - methacrylamidoethyl) - N : N1 - ethylene-urea or mixtures thereof.ALSO:Acrylyl and methacrylyl dicyandiamides alone or admixed with one or more other monoethylenically unsaturated monomers are polymerized in aqueous emulsion or in an organic solvent in the presence of a polymerization catalyst.  The comonomers may be esters of acrylic acid or of methacrylic acid or of the dimer of methacrylic acid with monohydric alcohols such as methanol, ethanol, butanol, octanol, dodecanol, cyclohexanol, cyanoethanol, benzyl alcohol and phenylethyl alcohol; diesters of itaconic, citraconic, maleic and fumaric acids with the above alcohols; vinyl esters of acetic, propionic and butyric acids; vinyloxyalkyl esters such as vinyloxyethyl acetate; vinyl ethers and sulphides such as ethyl vinyl ether, ethyl vinyl sulphide, butyl vinyl ether and octyl vinyl ether; acrylonitrile and methacrylonitrile; acrylamide, methacrylamide and N-alkyl-substituted derivatives thereof; vinyl toluene; vinyl naphthalenes such as 4-chloro-1-vinyl naphthalene; styrene; N - (b  - methacrylamidoethyl) - N:N1 - ethyleneurea or mixtures thereof.  In aqueous emulsion the emulsifier may be sodium lauryl sulphate, sodium tert. - octylbenzenesulphonate, octylphenoxypolyethoxyethanols having C7-18 alkyl groups and 6-60 oxyethyleneoxide units, octylbenzyl trimethylamine chloride, dodecyl trimethylammonium chloride or mixtures thereof.  Specified solvents are methanol, ethanol, n-butanol, acetonitrile, dimethylformamide, dimethylacetamide or aqueous solutions thereof.  The catalyst may be azodiisobutyronitrile, dimethyl azodiisobutyrate, benzoyl peroxide or ammonium persulphate in conjunction with sodium hydrosulphite and triethanolamine.  Mercaptoethanol may be employed as a chain transfer agent.  The polymers may be modified by reaction with aldehydes, such as formaldehyde, glyoxal, acetaldehyde and revertible polymers of formaldehyde, and also with resin-forming heat-convertible preliminary condensation products of such aldehydes (particularly formaldehyde) with urea, thiourea and triazines such as melamine. The polymers may also be reacted with hydrogen sulphide to convert the acrylyl or methacrylyl dicyandiamide groups therein to acrylyl or methacrylyl guanyl thiourea groups having the formula: <FORM:0790585/IV (a)/1> wherein R is H or methyl.  The polymers may be employed to form films, fibres, moulded masses and coatings and are used for the coating or impregnation of paper, textiles and leather.  Thus, when added to paper pulps they impart increased wet strength to sheets formed therefrom, when applied to cotton or rayon they impart stiffness, crease-resistance and crushresistance thereto, and when applied to wool fabrics they impart shrink-resistance thereto.  The polymers may also be employed for the foregoing purposes in conjunction with aminoplast condensates such as urea-formaldehyde or melamine-formaldehyde condensates.  Articles coated or impregnated with the above polymers are preferably subjected to a subsequent curing or baking operation.  In examples, acrylyl and methacrylyl dicyandiamides are homopolymerized using dimethyl azodiisobutyrate and mercaptoethanol in a dimethylformamide solvent; methacrylyl dicyandiamide and N - (b -methacrylamidoethyl) - N:N1 - ethyleneurea are copolymerized in aqueous dimethylformamide using dimethyl azodissobutyrate, and the product is heated with aqueous formaldehyde before adding to unbleached kraft pulp; methacrylyl dicyandiamide and methyl methacrylate are copolymerized in n-butanol using azodiisobutyronitrile and the product is either mixed with mono butyl phosphate, cast on a glass plate and baked to give a transparent film, or mixed with bis-methoxymethyl-N:N1-ethyleneurea and para-toluenesulphonic acid, cast on a glass plate and baked to give a transparent film; acrylyl dicyandiamide and methyl methacrylate are copolymerized in n-butanol using azodiisobutyronitrile; a mixture of methacrylyl dicyandiamide, methyl methacrylate and butyl acrylate is polymerized in ethanol using azodiisobutyronitrile, and the product is either mixed with monobutyl phosphate, cast on a glass plate and baked to give a transparent film, or mixed with bis-methoxymethyl - N:N1 - ethyleneurea and monobutyl phosphate, cast on a glass plate and baked to give a film; a dispersion of a copolymer is prepared by emulsifying ethyl acrylate and acrylyl dicyandiamide in water containing sodium lauryl sulphate and an octylphenoxypolyethoxyethanol, and adding thereto a mixture of ammonium persulphate, sodium hydrosulphite and triethanolamine thereto; red iron oxide is dispersed in water containing sodium lauryl sulphate and tert.-octylphenoxypolyethoxyethanol, methyl cellulose and the above prepared ethyl acrylate-acrylyl dicyandiamide copolymer emulsion is added thereto and the resulting pigmented dispersion is swabbed on to full grain upholstery leather and dried at 50 DEG  C.