Patent GB-787045-A (GB)
Title: Vinyl ethers of substituted biurets, their polymers, and their preparation
IPC: C07C275/62
Filed: 1955-10-06
Abstract: The invention comprises substituted biurets of the formula CH2 = CH.O.A.NR.CO.NH.CO.NH2 where A is C2-C18 straight or branched alkylene or cycloalkylene which may contain unsaturated substituents, and R is H, C1-C18 alkyl, cycloalkyl or aralkyl.  These may be made (1) by reacting amines CH2 = CH.O.A.NRH with allophanates R1O.CO.NH.CO.NH2(R1 = alkyl), preferably in the presence of a small amount of water at 20-100 DEG  C., e.g. 60-80 DEG  C.; or (2) in the case where A is of the form -Y-C(CH3)2- by reacting isocyanates CH2 = CH.O.Y.C(CH3)2.NCO with urea, preferably at 20-100 DEG  C. in the presence of a solvent and a basic catalyst.  The isocyanates can be prepared as in Specification 763,635, [Group IV (b).  Examples show the production of compounds where A is ethylene, trimethylene, a  - propyl - ethylene, a  - vinyl - ethylene, a -dodecyl - ethylene, a  - hexadecyl - ethylene and cyclohex-1 : 4-ylene, and R is H, methyl, dodecyl, octadecyl, cyclohexyl and benzyl.  The products form salts with alkali metals which may be alkylated with alkyl halides.  The biuret group will also react with aldehydes, epoxides, isocyanates and acid chlorides.  Other starting materials are specified in which A is also propylene, gem-dimethylethylene, tetramethylene, trimethyl - trimethylene, trimethyl - heptamethylene and b ,b  - dimethyltrimethylene, and R is also ethyl, butyl or methylbenzyl.ALSO:Textiles are treated with polymers or copolymers (or methylol derivatives thereof) of compounds of the formula CH2=CH.O.A.NR.CO.NH.CO.NH2 where A is an alkylene or cycloalkylene group which may contain unsaturated substituents and has 2-15 carbon atoms in all, there being at least two between the O and N atoms, and R is hydrogen, C1-C18 alkyl, cycloalkyl or aralkyl.  In examples: (1) wool is shrink-proofed by treatment with an aqueous dispersion of the copolymer of butyl acrylate and 1-methyl-1-(b -vinyloxyethyl)-biuret containing an octylphenol polyglycol ether; (2) rayon is crease-proofed and shrink-proofed by application of the methylol derivative of polymerized 1-methyl-1-(b -vinyloxypentyl)-biuret and heating to insolubilize on the fabric.  Other suitable monomers and co-monomers are mentioned.ALSO:The invention comprises polymers and copolymers of biurets of the formula CH2 = CH.O.A.NR.CO.NH.CO.NH2 where A is C2-C18 straight or branched chain alkylene or cycloalkylene which may contain unsaturated substituents, and R is H, C1-C18 alkyl, cycloalkyl or aralkyl.  The other constituents of the copolymers may be acrylic or methacrylic acid or their nitriles, amides or esters; itaconic, maleic, fumaric or citraconic esters; vinyl ethers and esters; ethylene; vinyl and vinylidene halides; 1-acetoxy-butadiene; styrene or divinylbenzene; vinylpyridines; many compounds of these types are listed.  The polymers can be methylolated or insolubilized by treatment with formaldehyde, the former products being useful adjuncts for aminoplast resins.  The polymers can also be hydrolysed to poly-primary amines which are modifying agents for synthetic polymers.  Polymerization may be effected in bulk or in aqueous solution, suspension or emulsion, using azo, peroxide or ammonium persulphate catalysts.  In the examples: (1) polymers are made from 1-(b -vinyloxyethyl) - biuret, 1 - (b  - vinyloxyethyl) - 1 - methyl - biuret, 1 - (b  - vinyloxyethyl) - 1 - cyclohexyl - biuret, 1 - (b  - vinyloxyethyl) - 1 - benzyl-biuret, 1 - (g  - vinyloxypropyl) - biuret and 1 - (b  - vinyloxypentyl) - 1 - methyl - biuret; (2) methylol derivatives are obtained from the first, fifth and sixth of these; (3) a copolymer solution is made from 1-(b -vinyloxyethyl)-biuret, ethyl acrylate, methyl methacrylate and ethoxyethyl acetate; a white enamel is made from this solution with N : N1-bis-methoxymethyl-ethyleneurea, toluene-p-sulphonic acid, titanium dioxide and xylene; (4) an aqueous dispersion is prepared of a copolymer of butyl acrylate with 1 - (b - vinyloxyethyl) - 1 - methyl - biuret and octylphenyl polyglycol ether; (5) a copolymer of acrylonitrile with 1-(g -vinyloxypropyl)-biuret in dimethylformamide is extruded into water in the form of fibres.  Other suitable monomers are mentioned.