Patent GB-904459-A (GB)
Title: Process for the production of highly elastic fibres by the isocyanate polyaddition process
IPC: C08L75/00
Filed: 1960-04-14
Abstract: Highly elastic fibres are made by heating a reaction product containing free NCO groups and obtained by reacting a polyhydroxy compound having a molecular weight of 200 with 3,000 with an excess of a polyisocyanate, with a quantity of an alcohol and/or amine which alcohol and/or amine has at least two active hydrogen atom containing groups the quantity being less than that required for the complete reaction with the NCO groups which are present, the heating taking place in a solvent which is inert with respect to NCO groups in the presence of a catalyst causing the polymerization of NCO groups and being continued until no more free NCO groups are present, and spinning the viscous solution which is obtained through a nozzle, if necessary after dilution with a solvent.  Specified polyhydroxy compounds of which many are listed are polyesters, polesteramides, polyesterurethanes, polyetheresters, polyethers and polythioethers; polyisocyanates specified for reaction therewith being 4:41-diphenylmethane, 1:5-naphthylene and 2:21-diphenylpropane-4:41-diisocyanate.  Specified solvents are methylethylketone, diethylketone, methylpropyl ketone, dipropyl ketone, methyl isobutyl ketone, butyl acetate, dipropyl ether, chlorobenzene, dioxane, tetrahydrofuran and dichlorobenzene. Specified polyfunctional alcohols and amines are butanediol, decanediol, hexanediol, thiodiglycol, 1:4-phenylene-bis-oxyethylether, trimethylol propane, 3:31-dichlorobenzidine, 3:31-dinitrobenzidine and toluylene diamine. Specified catalysts are tertiary amines, alkali alcoholates, alkali phenolates, fatty acid salts and heavy metal compounds.  The reaction may be terminated by the addition of an alcohol and/or amine containing not more than one active hydrogen containing group, e.g. diisobutylamine, N-methylaniline and ethanol.  In the examples, polyurethanes are made by reacting in the presence of:-(1) to (8), (10) to (12) and (14) to (21) methylethyl ketone, (9) n-butyl acetate and (13) methyl isobutyl ketone:-(1), (2) and (4) an ethylene glycol/adipic acid polyester, 4:41-diphenylmethane diisocyanate, butane-1:4-diol and dimethylcyclohexylamine; (3) as in (1) with the addition of titanium dioxide to the reactants; (5) poly-1:4-butylene glycol ether, 4:41-diphenylmethane diisocyanate, butane-1:4-diol, trimethylol propane, dimethylcyclohexylamine and diisobutylamine; (6) an ethylene glycol/adipic acid polyester, 1:5-naphthylene diisocyanate, butanediol and dimethylcyclohexylamine; (7) a polythioether, 4:41-diphenylmethane diisocyanate, butane-1:4-diol and dimethylcyclohexylamine; (8) an ethylene glycol/adipic acid polyester, 4:41-diphenylmethane diisocyanate, 1:10-decanediol, dimethylcyclohexylamine; (9) an ethylene glycol/adipic acid polyester, 4:41- diphenyl methane diisocyanate, butane-1:4-diol and dimethyl cyclohexylamine; (10) an ethylene glycol adipic acid polyester, 4:41-diphenylmethane diisocyanate, butane-1:4-diol and dimethyl cyclohexylamine; (11) an adipic acid/ethylene glycol polyester, 4:41-diphenylmethane diisocyanate, 1:4-butane diol, dimethylcyclohexylamine and glycol carbonate; (12) an adipic acid/ethylene glycol polyester, 4:41-diphenylmethane diisocyanate, 1:4-butane diol, dimethyl cyclohexylamine, diisobutylamine and 1:4-phenylene bis-oxyethyl ether or terephthalic acid bis-oxyethyl ester or 4:41-diphenylmethane bis-oxybutylurethane or N-(naphthyl)-N-(1:3-dihydroxy-2-methylpropyl-2) urea; (13) an adipic acid/ethylene glycol polyester, 4:41-diphenylmethane diisocyanate, 1:4-butane diol, diisobutylamine and N-methylaniline; (14) an ethylene glycol/adipic acid polyester, 4:41-diphenylmethane diisocyanate, 1:4-butane diol, diazo-bicyclooctane and diethanolamine; (15) a 1:6-hexane diol/adipic acid polyester, 4:41-diphenylmethane diisocyanate, 1:4-butane diol, dimethyl cyclohexylamine and diethanolamine; (16) an ethylene glycol/propylene glycol/adipic acid polyester, 4:41-aiphenylmethane diisocyanate, 1:4-butanediol, dimethylcyclohexylamine and diethanolamine; (17) an adipic acid/ethylene glycol polyester, 4:41-diphenylmethane diisocyanate, 4:41-diamino diphenyl methane and diethanolamine; (18) an adipic acid/ethylene glycol polyester, 4:41-diphenyl methane diisocyanate, 1:4-butanediol, dimethylcyclohexylamine and diethanolamine; (19) a polyacetal from bis-oxyethyl-1:4-butylene ether and formaldehyde, 4:41-diphenylmethane diisocyanate, 1:4-butane diol and diethanolamine and (20) and (21) a polyacetal from 1:6-hexanediol and formaldehyde, 4:41-diphenylmethane diisocyanate, 1:4-butane diol and diethanolamine and, in (21), dimethylcyclohexylamine.  The resultant solutions are spun into filaments having been (except in Example 11) diluted with dimethyl formamide.