Patent GB-806093-A (GB)
Title: Unsaturated ureido compounds and polymers and copolymers thereof
IPC: C07C275/10
Filed: 1956-06-01
Abstract: Polymers and copolymers of compounds of the formula CH2=CR1-CO-X-A-NH-CO-NH-R, where A is an alkylene group of 2-4 carbon atoms, R is a t-alkyl group of 4-24 carbon atoms, R1 is H or methyl and X is -O- or -NH-, are used to produce protective coatings, particularly on wood, glass or metal.  When prepared below 175 DEG C. the films are insolubilized by loss of the compound R-NH-CO-NH-R and cross-linking, and become tough and either hard or rubbery.  The first stage films may be applied from solution to the surfaces of refrigerator cabinets, washing machines, stoves, kitchen cabinets, &c. to form a coating which can be cross-linked in situ as the main component of an enamel containing also pigments, dulling agents, &c. The tough films are useful as wire coatings, e.g. in drying racks. Particularly suitable films are made from copolymers of 5-20 mol. per cent of one of the above compounds and 80-95 mol. per cent of an alkyl acrylate or methacrylate having 1-18 carbon atoms in the alkyl group.  In general the other components of the copolymers may be ethylenic compounds such as vinyl or allyl esters or ethers, acrylic or methacrylic esters or amides, maleic or itaconic esters, vinyl-aromatic hydrocarbons, maleic anhydride or acrylonitrile.  In the examples, films of the above types are made from (1) N - b  - methacrylamidoethyl - N1 - t - octylurea and methyl methacrylate; (2) N-b -methacryloxyethyl-N1-t-octylurea and ethyl acrylate; (3) N - g - methacryloxypropyl - N1 - t - octadecylurea and vinyl dodecyl ether; (4) N-b -acryloxypropyl - N1 - t - tetradecylurea and methyl methacrylate; (5) N-b -acryloxy-t-butyl-N1-t-butylurea and dodecyl maleate; (6) as in (1) containing also ethyl acrylate.  In a further example a dispersion in water of a copolymer of N-b -methacrylamidoethyl-N1-t-octylurea and ethyl acrylate prepared with a t-octylphenyl polyglycol ether is added to a smooth paste of titanium dioxide and zinc oxide dispersed in water with the aid of diethylene glycol, the sodium salt of a maleic anhydride di-isobutylene copolymer and an octylphenyl polyglycol ether.  The result is a primer for the surfaces of household appliances which are subsequently coated with enamel or lacquer and baked.ALSO:The invention comprises polymers and copolymers of compounds of the formula <FORM:0806093/IV (a)/1> where A is an alkylene group of 2-4 carbon atoms, R is a t-alkyl group of 4-24 carbon atoms, R1 is H or methyl and X is -O- or -NH-.  The monomers may be polymerized alone or with other ethylenic compounds, e.g. vinyl and allyl esters and ethers, acrylic and methacrylic amides and esters, maleic and itaconic esters, vinyl-aromatic hydrocarbons, maleic anhydride or acrylonitrile, preferably using a polymerization catalyst.  The temperature should not exceed 175 DEG  C., and there is then produced a viscous or solid product that can be applied from solution to give a film on a metal, glass or wooden surface.  On drying such a film at 125 DEG  C. it is still removable with solvents but after heating at 175-300 DEG  C. a cross-linked insoluble coating is obtained by splitting out the compound <FORM:0806093/IV (a)/2> In the examples: (1) N-(b -methacrylamidoethyl) - N1 - t - octyl - urea is polymerized, alone or with methyl methacrylate, in b -ethoxyethyl acetate using azo-di-isobutyronitrile as initiator; (2) N-(b 1methacryloxyethyl)-N1-t-octyl-urea is polymerized, alone or with ethyl acrylate or octadecyl itaconate, in toluene with benzoyl peroxide as initiator.  Other examples describe copolymers of N-(g -methacrylpropyl)-N1-t-octadecyl-urea with vinyl dodecyl ether or butyl methacrylamide, N-(g -methacrylamidopropyl) - N1 - t - octyl - urea with butyl methacrylamide, N-(b -acryloxypropyl)-N1-t-tetradecyl-urea with methyl methacrylate, N - (b  - acryloxy - t - butyl) - N1 - t-butyl-urea with dodecyl maleate, and N-(b -methacrylamidoethyl) - N1 - t - octyl - urea with vinyl-toluene, ethyl acrylate or the latter mixed with methyl methacrylate.  Boron triflouride may be used as initiator.  In a final example a copolymer is made from N-(b -methacrylamidoethyl) - N1 - t - octyl - urea and ethyl acrylate in water using t-octylphenol polyglycol ether as emulsifier and ammonium persulphate with sodium hydrosulphite as initiator; it is then ground in water with titanium dioxide and zinc oxide using diethylene glycol, a maleic anhydride/di-isobutylene copolymer and t-octylphenol polyglycol ether as dispersing agents, to give a white primer which forms a film on baking.  The monomers of the invention may be present to the extent of 5-95 per cent in the copolymers.ALSO:The invention comprises compounds of the formula CH2 = CR-CO-X-A-NH-CO-NH-R where A is an alkylene group of 2-4 carbon atoms, R is a t-alkyl group of 4-24 carbon atoms, R1 is H or methyl and X is -O- or -NH-.  The esters (X = O) are made by reacting RNH2 with the isocyanates CH2 = CR1-COO-A-NCO of Specification 759,860.  The amides (X = NH) are prepared by acylating with an acrylyl or methacrylyl halide the ureas NH2-A-NH-CO-NH-R obtained (together with some bis-ureas) from RNCO and alkylene diamines NH2-A-NH2.  Examples show the production of N-(b -methacryloxyethyl) N1 - t - octyl - urea, N - (b  - acryloxyethyl) - N1 - t - butyl - urea, N - (b  - methacryloxyethyl) N1 - t - alkyl - urea where the alkyl is a mixture of C18-C24 residues, N-(b -methacryloxy - t - isobutyl) N1 - t - octyl - urea, N-(b  - methacrylamidoethyl) N1 - t - octyl - urea, N - (b  - acrylamidoethyl) N1 - t - octyl - urea, N-(b  - methacrylamidoethyl) N1 - t - butyl - urea and N - (b  - acrylamido - t - butyl) N1 - t - octyl-urea.  N - (b  - aminoethyl) N1 - t - octyl - urea is isolated as an intermediate.  A may also be propylene, trimethylene, tetramethylene and various other butylene groups, and R1 may be tertiary hexyl, decyl, dodecyl, tetradecyl, hexadecyl or octadecyl.