Patent GB-946472-A (GB)
Title: Colored crosslinkable and crosslinked polymers and their production
Inventor: LANGE GUENTER
IPC: D04H1/645
Filed: 1962-02-23
Abstract: Polymeric compounds united by chemical combination with dyes are made by reacting a homopolymer or copolymer containing groups that enable to be reacted with other compounds by condensation or addition reactions with a dye also containing reactive groups, and cross-linking the polymer by way of the reactive groups of the polymer which are still available, either simultaneously or subsequently.  Monomers containing reactive groups from which such polymers may be prepared are acrolein, acrylamide, N-methylolacrylamide, crotonamide, ethacrylamide, chloroacrylamide, phenylacrylamide, maleic, fumaric, citraconic and itaconic diamides, N-acryloyl and N-methacryloyl ureas and dicyanodiamides amino-allyloxytriazines, glyoxalmonocureine allyl ether, glycidyl acrylate and butanediol monoacrylate.  Such monomers may be copolymerized with monomers such as styrene, butadiene, isoprene, nitriles, amides, esters, anhydrides and salts of acrylic, methacrylic, crotonic, maleic, fumaric, itaconic and citraconic acids, vinyl acetate, propionate or butyrate, vinyl chloride and bromide, allyl esters, vinyl carbazole pyridine, imidazole and quinoline and vinyl pyrrolidone and caprolactam. Alternatively, reactive groups may be introduced into polymers by after-treatment, e.g. by hydrolysis, reduction or halogenation. Dyes containing reactive groups are specified in Specifications 744,877, 779,781, 842,802, 850,977, 900,764 and 946,471. The polymers may contain self cross-linking groups, in which case the action of heat or change in pH value may effect cross-linking, or an external cross-linking agent may be employed. The examples describe the following processes: (1) a copolymer of butyl acrylate, styrene, and N-methylolmethacrylamide in aqueous dispersion is mixed with an aqueous solution of the coupling product of diazotized N-(p-aminophenyl)-glyoxal-diureine and gamma - acetylaminonaphthol-(1)-3,6-di-sulphonic acid and ammonium nitrate, and from the resulting dispersion a violet-red film is produced which cross-links on heating at 140 DEG C.; (2) a non-woven fabric is impregnated with a mixture of an aqueous dispersion of a copolymer of butylacrylate and acrylamide, an aqueous solution of a coupling product of diazotized N-(p-aminophenyl)-glyoxaldiureine with 1-(p-sulphophenyl) -3- methylpyrazolone-(5) which has been reacted with formaldehyde, dimethylol urea and ammonium nitrate, and the impregnated fabric is dried and heated at 150 DEG C.; (3) a mixture of a copolymer of acrolein, butyl acrylate and styrene, 4-azophenylacetoacetic acid and piperazine dissolved in a toluene-butanol solvent is applied to a substrate and heated at 120 DEG C.; (4) an aqueous solution containing a copolymer of acrylamide, tert.-butyl acrylate and ethyl acrylate is mixed with the dye of (2), dimethylolurea and ammonium nitrate, applied to paper and heated at 150 DEG C.; (5) a mixture of a copolymer of acrylamide, N-methylolacrylamide and ethyl acrylate, the dye of (1), the di-N-methylolurethane of 1,4-butanediol and ammonium nitrate is dissolved in water, applied to wood pulp and dried at 150 DEG C.; (6) the dye obtained by coupling diazotized p-aminophenylglyoxaldiureine with 1-naphthol-4-sulphonic acid and reaction with formaldehyde, the dimethylolurethane of 1,4-butanediol and ammonium nitrate are added to an aqueous solution of a copolymer of acrylamide, methacrylamide, and methyl acrylate, the resulting composition is applied to paper and heated at 160-170 DEG C.; and (7) the coupling product of diazotized p-aminophenylurea and 4-tert.-butylphenol and reacted with formaldehyde, and hexamethylene diisocyanate are added to an ethanol solution of a copolymer of butylacrylate, butanediol monoacrylate and acrylamide, and the resulting solution is applied to glass fabric and heated at 160-170 DEG C. Specification 877,102 also is referred to. The Specification describes also the preparation of the copolymers of the above Examples by the following processes: (1) and (2) aqueous emulsion polymerization in the presence of potassium persulphate and the sulphation product of an oxyethylated fatty alcohol; (3) solution polymerization in a toluene-butanol mixture in the presence of benzoyl peroxide; (4) solution polymerization in butanol in the presence of azodiisobutyronitrile; (5) precipitation polymerization in butanol in the presence of benzoyl peroxide and sodium hydroxymethanesulphinate; (6) aqueous solution polymerization in the presence of potassium persulphate and sodium hydroxymethane-sulphinate; and (7) solution polymerization in ethanol in the presence of azodiisobutyronitrile.ALSO:Paper and wood are coated with a toluenebutanol solution of a copolymer of acrolein, butyl acrylate and styrene, 4-azophenylacetoacetic acid anilide as a dyestuff reactive with the copolymer, and piperazine as a cross-linking agent for the copolymer, and then heated at 120  DEG C. to produce transparent yellow coatings.  Specifications 744,877, 779,781, 842,802, 850,977, 877,102, 900,764 and 946,471 are referred to.ALSO:Fabrics are coloured by impregnating them with a mixture comprising a polymer and a dyestuff reactive therewith, and, if the polymer is not self-cross-linking, a cross-linking agent therefor. Examples describe processes in which: (2) a non-woven fabric is impregnated with an aqueous composition comprising the coupling product of diazotized N-(p-aminophenyl)-glyoxaldiureine with 1-(p-sulphophenyl)-3-methylpyrazolone-(5) which has been reacted with formaldehyde, dimethylol urea and a dispersion of a copolymer of butyl acrylate and methacrylamide, followed by drying and heating the fabric at 150 DEG C.; and (7) glass fabric is impregnated with an ethanol solution of a copolymer of butyl acrylate, butanediol monoacrylate and acrylamide containing hexameltrylene diisocyanate and the coupling product of diazotized p-aminophenylurea and 4-tertbutylphenol reacted with formaldehyde, and the dried fabric is heated at 160-170 DEG C. Specifications 744, 877, 779, 781, 842, 802, 850, 977, 877, 102, 900, 764 and 946, 471 are referred to.