Patent GB-822267-A (GB)
Title: Monomeric polymerizable ureido and thioureido compounds, methods for producing them and polymers thereof
IPC: C08F20/36
Filed: 1956-04-12
Abstract: Homopolymers and copolymers of compounds of general formula <FORM:0822267/III/1> in which Y is O or S, A is phenylene or an alkylene group having 2-4 carbon atoms of which a chain of at least 2 extend between the adjoining atoms Y and N, R1 is H, cycloalkyl or a C1-C12 alkyl group, X is O or S, and R2 is an alkyl group, dissolved in water or organic solvents may be dyed, pigmented, or provided with extenders or fillers, and may be combined with other film-forming or coating resins for application to various substrates such as porcelain and metals and heated to give a baked enamel finish. Pigments such as titanium dioxide, lithopone, barium sulphate and ultramarine blue may be added.  In the examples: (a) a polymer is obtained by heating N-vinyl oxyethyl-N1-butoxy-methylurea and dimethyl formamide in the presence of dimethyl azoisobutyrate, which in solution in butanol containing butyl acid phthalate is cast as a film on glass and on metal plates, air-dried and baked to give a hard solvent-resisting coating; (b) films are prepared on glass and metal by casting wet films in glass or metal of a polymer made by heating dimethylformamide and N - methyl - N - vinylthioethyl - N1 - n - propoxymethylurea in the presence of dimethyl azoisobutyrate and baking; if desired the solution may be treated before casting with butyl phosphoric acid; (c) a polymer obtained by heating butyl methacrylate, methyl methacrylate and N-methyl-N-vinylthioethyl-N1-n-propoxymethylurea is used as a coating material for baking enamels; it may be pigmented with an equal weight of titania pigment; and (d) a polymer obtained by heating methyl methacrylate, xylene ethyl acrylate and N-methoxymethyl - N1 - vinyl - oxyethylthiourea in the presence of azoisobutyronitrile is used alone or with the addition of resin solids of butyl acid phthalate to form films on glass and metal which harden on baking.ALSO:Copolymers and homopolymers of compounds of the formula <FORM:0822267/IV(c)/1> in which Y is O or S; A is phenylene or an alkylene group having 2-4 carbon atoms, of which a chain of at least 2 extends between the adjoining atoms Y and N; R1 is H, a cycloalkyl group or a C1-C12 alkyl group; X is O or S; and R2 is an alkyl group; may be applied to textiles as coatings, adhesives or impregnants.  For example, they may be applied to wool, rayon or cotton fabrics to reduce water-sensitivity; to cotton and rayon fabrics to make crush-proof and crease-proof; and to textiles, especially cotton and rayon, when the polymers are formed from monomers in which the R1 group is a longchained group containing 8-12 carbon atoms, to impart water-repellency.  In the examples: (a) an aqueous solution of N-(2-vinyloxyethyl)N1-methoxymethylurea, dimethylolurea and ethanolamine hydrochloride is used to treat rayon challis by padding so as to give a retention of 2% solids; the fabric is dried and cured at 220 DEG  F. and is rendered crease-proof and shrink-proof; (b) cotton twill is immersed in a chloroform solution containing <FORM:0822267/IV(c)/2> and p-toluene sulphonic acid so that a resin pick-up of 4-5% is obtained; the fabric is dried and cured at 300 DEG F. for 5 mins. and is rendered resistant to wetting; and (c) a woollen fabric is padded through an emulsion of a polymer prepared from N-butoxymethyl-N1-vinyloxyethylurea and butyl acrylate; the fabric is dried and cured at 250 DEG  F. for 5 minutes and, as a result, has a greater resistance to shrinkage.ALSO:Compounds of the formula <FORM:0822267/IV (a)/1> in which Y is O or S, A is X phenylene or an alkylene group having 2 to 4 carbon atoms, of which a chain of at least 2 extends between the adjoining atoms Y and N; R1 is H, a cycloalkyl group or a C1-C12 alkyl group; X is O or S; and R2 is an alkyl group; may be polymerized in the presence of an acid catalyst, or of an acyclic azo compound, in the presence of an inert solvent.  They may also be copolymerized with other polymerizable olefinically unsaturated compounds in the presence of a polymerization catalyst such as a peroxide or azo catalyst. Unsaturated compounds which may be used for forming copolymers are, for example, esters of acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid or citraconic acid with monohydric alcohols; vinyl esters of carboxylic acids; vinyloxyalkyl esters; vinyl ethers including aminoalkyl vinyl ethers; methacrylonitrile or acrylonitrile; acrylamide or methacrylamide and other N-substituted amides; vinyl bromide, vinylidene chloride, 1-chloro-1-fluoroethylene or ethylene; 1-acetoxy-1.3-butadiene; styrene, 2-vinylpyridine, 4 - vinyl pyridine, N - vinylpyrrolidone, formamidoethyl vinyl ether or divinyl benzene; ethylene diacrylate or dimethacrylate; bis-(vinoxyethyl) urea; and vinoxyethyl and vinoxypropyl acrylate. Copolymerization may be effected in bulk, in solution or in dispersion.  Suitable solvents are benzene, toluene, methanol, ethanol, butanol, acetone, methyl ethyl ketone, dimethylformamide, ethyl acetate and ethylene dichloride.  Polymerization may also be carried out by dispersion in an aqueous system using an emulsifier and/or dispersing agent if required.  The polymers may be dissolved in a suitable solvent containing an acidic catalyst and then applied to paper, leather, textiles, wood, metal, glass and plastics as coatings, adhesives and impregnants which can then be dried and directly converted to insoluble and infusible condition by heating. Suitable catalysts are ammonium phosphate and thiocyanate, the hydrochloride and other acid salts of hydroxy aliphatic amines, ammonium chloride, pyridine hydrochloride and benzyldimethylamine oxalate.  The homopolymers and copolymers may be used to form films, sheets, rods, tubes and other shaped articles by casting, moulding or extrusion of fused masses of the polymers or solutions in suitable solvents, e.g. dimethylformamide and acetone.  The compositions containing the polymers dissolved or suspended in water or organic solvents may be dyed, pigmented, or provided with extenders or fillers and may be combined with other film-forming or coating resins, such as aminoplasts, including urea-formaldehyde or melamine-formaldehyde resins, alkyds or vinyl polymers.  Such compositions may be applied to various substrates and subsequently converted by heating to a baked enamel finish, as on porcelain and metals. Pigments such as titanium dioxide, lithopone, barium sulphate and ultramarine blue may be used for this purpose.  In the examples: (a) N - (2 - vinyloxyethyl) - N1 - n - butoxymethyl - urea (CH2=CHOCH2CH2NHCONHCH2OC4H9) and butyl acid phthalate are added to a condensate of urea, formaldehyde and butanol in a butanol-xylene solution to give a film which on baking has improved flexibility and tensile properties; (b) N-(2-vinyloxyethyl)-N1-methoxymethylurea and ethanolamine hydrochloride are added to a dimethylolurea solution to give a product used for treating rayon challis; (c) N-vinyloxyethyl - N1 - methoxy - methyl urea is polymerized by treating with dimethyl azoisobutyrate; the polymer is used as an additive to fibre and film dopes of cellulose acetate for imparting decreased water pick-up and improved tensile properties; (d) N-vinyloxyethyl-N1-butoxymethylurea and dimethylformamide are heated in the presence of dimethylazoisobutyrate; a solution of the resulting polymer in butanol containing butyl acid phthalate is baked as a film on glass and metal plates to give hard coatings; the polymer is also used to modify other coating resins, such as those derived from urea or melamine; (e) a polymer is formed from N-methyl-N-vinylthioethyl-N1-n-propoxymethylurea by heating with dimethylformamide in the presence of dimethyl azoisobutyrate and films are formed as in (d), but in one case the solution is catalysed before filming with butyl phosphoric acid; (f) polymers are obtained by heating (i) N-(2-vinylthiophenyl)-N1-methoxymethylthiourea and dimethylformamide, (ii) N - (2 - vinylthiophenyl) - N1 - methoxymethylthiourea, and (iii) N-(2-vinyl-thiophenyl) - N1 - methoxymethylthiourea, methyl methacrylate and toluene, in the presence of dimethyl azoisobutyrate; (g) a polymer is obtained by heating N-methoxymethyl-N1-vinyloxyethylthiourea with dimethylformamide in the presence of dimethyl azoisobutyrate; (h) N - (2 - vinyloxyethyl) - N1 - n - butoxy - methylurea is heated with methyl methacrylate and ethoxyethyl acetate in the presence of azoisobutyronitrile to give a polymer which when baked as a film on metal gives a clear hard coating; if p-toluenesulphonic acid is added to the mixture an insoluble film is obtained; (j) a coating material for baking enamels is obtained by heating methyl methacrylate, N - methyl - N - vinylthioethyl - N1 - n-propoxymethylurea, butyl methacrylate and methyl methacrylate; it may be pigmented with an equal weight of titania pigment; (k) N - methoxymethyl - N1 - vinyloxyethylthiourea, methyl methacrylate and xylene are heated in the presence of azoisobutyronitrile to to give a polymer solution which, on its own or with the addition of butyl acid phthalate, forms films on glass and metal which can be hardened by baking; (1) acrylonitrile, ethyl acrylate and N - butoxymethyl - N1 - vinyloxyethylthiourea are emulsified in dilute soap solution and potassium chloride, tetraethylenepentamine, and diisopropylbenzene hydroperoxide are added to give a stable polymer emulsion which may be used in the preparation of fibres and films which may be thermoset; (m) a polymer is formed as in (1) but using N-butoxymethyl - N1 - vinyloxyethylurea as starting material; (n) N - vinyloxyethyl - N1-methoxymethylurea and water are heated in the presence of dimethylazoisobutyrate and the resulting polymer is used as a tyre cord adhesive by sizing the tyre cord with a rubber latex containing 10% of the polymer and incorporating the cords into a styrene-butadiene rubber.  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