Patent GB-976240-A (GB)
Title: A process for the production of polymers comprising urethane and semi-carbazide groupings
IPC: C08G18/10
Filed: 1962-12-28
Abstract: Polymers containing urethane and semi-carbazide groupings are prepared by reacting a linear prepolymer having a MW of 500-5,000 and containing terminal NCO groups with 10 to 90% (calculated on the NCO content of the prepolymer) of a polyhydric alcohol and then reacting the prepolymer with 90 to 110% (calculated on the remaining -NCO content) of one or more compounds of formula  (1) R-NH-NR1-A-(XA)n-NR1-NHR (2) RNH-X-A-NR1-NHR or (3) HO-X-A-NR1-NHR, in which A is -CO-, -CS- or -SO2- group, R and R1 are hydrogen atoms or alkyl or aryl radicals; X is an alkylene, arylene or aralkylene radical which may be interrupted by hetero atoms or X is an -OYO or -NH-Y-NH- radical in (1) or a -YO- or -Y-NH- radical in (2) or (3); Y is a divalent organic radical and n is 0 or 1. The prepolymer may be derived from polyesters, polyethers, polythioethers, polyacetals, polyester acetals of M.W. 500-5,000. Hydrazides specified are: carbodihydrazide, oxalic acid hydroxy hydrazide, the dihydrazides of oxalic acid, malonic, succinic, adipic, isophthalic, piperazine-dicarboxylic, iminodicarboxylic, ethylene and butylene bis carbaninic, acids; hexane, butane, xylylene 1, 3 bis semicarbazides; diguanyl ethylene, o -aminocaproic, o -hydroxy butyric, tartaric acid hydrazides and o -hydroxy butyric acid b -hydroxy ethyl hydrazide. Polyhydric alcohols and polyisocyanates used in the first stage are listed.  The first stage is effected at 50-150 DEG C. in a solvent, and the second stage at 0-50 DEG C.  Pyrocarbonic acid diethyl ester is added to remove excess hydrazide.  Additives may be: TiO2, talcum and kaolin.  In an example (1) a prepolymer derived from diphenylmethane diisocyanate and adipic acid-ethylene glycol polyester was reacted with butane 1, 4 diol, carbodihydrazides, hydrazodicarboxylic acid and diethyl pyrocarborate.  Specifications 908,188, 914,609 and 917,450 are referred to.ALSO:Polyurethanes containing semi-carbazide groups are employed as coatings for textiles, natural and synthetic fibres, metals and plastics.  The polyurethane is prepared by reacting a linear prepolymer of molecular weight 500-5000 containing terminal isocyanate groups with a polyhydric alcohol and then with one or more of the compounds of formulae:  (1) R-NH-NR1-A-(XA)n-NR1-NHR,  (2) RNH-X-A-NR1-NHR, or (3) HO-X-A-NR1-NHR, in which A is -CO-, -CS- or -SO2- group, R and R1 are hydrogen atoms or alkyl or aryl radicals; X is alkylene, arylene or aralkylene radical which may be interrupted by hetero atoms, or X is an -OYO or -NH-Y-NH- radical in (1) or an -YO- or -Y-NH- radical in (2) or (3); Y is a divalent organic radical and n is 0 or 1 (see Division C3.  The coating may be applied by a doctor blade, rollers, dipping, impregnating, pouring or spraying, and the solvent evaporated by heating to 60-150  DEG C.  In examples a cotton fabric was coated.  Pigments and fillers, e.g. TiO2, talcum or kaolin, age resistors and ultraviolet absorbers may be incorporated, also can spirit-soluble and fat-soluble dyestuffs. By using solvents which can be emulsified with water, the elastic material may be used as an emulsion or solution to treat fibre fleeces of wool, cotton, staple rayon or other natural or synthetic fibres by dipping, saturating, spraying or impregnating and to obtain unwoven textile sheet fabrics. Coats may be applied to synthetic plastics, e.g. softened polyvinyl chloride foils, or metallic containers lined.  Stocking made from polyamide may be given a ladder-proof finish and nets and yarns coated to give high knot-strength.  The products are suitable for waterproof clothing, tarpaulins and as packing material. Specifications 908,188, 914,609 and 917,450 are referred to.