Isocyanate derivatives

摘要

1,139,552. Isocyanate derivatives. UNION CARBIDE CORP. 8 Nov., 1965 [9 Nov., 1964], No. 34456/68. Divided out of 1,139,551. Heading C2C. [Also in Divisions B2, C3 and D1] Isocyanate derivatives, e.g. compounds containing urea and/or urethane groups are prepared by reacting a compound which contains at least one hydrogen atom reactive with isocyanate groups with an organic diisocyanate of the general formula wherein R represents a divalent substituted or unsubstituted aliphatic, alicyclic or aromatic group containing 2 to 12 carbon atoms and R 1 represents a divalent olefinically unsaturated aliphatic group containing 2 to 24 carbon atoms, with the provisos that (1) when both R variables represent alkylene groups, R 1 is not the cis-vinylene group and (2) each isocyanato moiety, individually, is at least 2 carbon atoms removed from the moiety of the above formula. The diisocyanate preferably used is bis - (2 - isocyanatoethyl) - fumarate, and the reactive hydrogen groupcontaining compound may suitably be an alcohol, amine, water, a thiol or aminoalcohol. Depending on the quantities of diisocyanate and reactive hydrogen group-containing compounds used, the resulting product may be terminated with isocyanate groups or the reactive hydrogen containing groups. In examples bis- (2-isocyanatoethyl)-fumarate is reacted with (1) n-butanol, (2) n-butylamine, (3) allyl alcohol, (4) phenol, (5) 2-mercaptoethanol, (6) 2-butene- 1,4-diol, (9) piperazine, (14) 1,6-hexanediamine, (16) 2-mercaptoethanol, (17) piperazine and (18) water to produce respectively (1) bis-[2-(nbutoxyformamido)-ethyl]-fumarate, (2) bis-[2- (n-butyl-ureylene)-ethyl]-fumarate, (3) bis-[2 - (allyloxyformamido) - ethyl] - fumarate, (4) bis- [2 - (phenoxyformamido) - ethyl] - fumarate, (5) bis - [2 - (2 - hydroxyethylthiolcarbamido)- ethyl] - fumarate, (6) bis - [2 - (4 - hydroxy - 2 - butenoxyformamido) - ethyl] - fumarate, (9) bis - [2 - (1 - piperazinoforrnamido) - ethyl] - fumarate, (14) 2,21. - (hexamethylenediureylene) - diethyl bis - (2 - isocyanatoethyl fumarate), (16) 2,21 - (ethyleneoxythiodiformamido) - diethyl bis - (2 - isocyanatoethyl fumarate), (17) 2,21 - (piperazin - 1,4 - ylenediformamido) - diethyl bis - (2 - isocyanatoethyl) - fumarate and (18) 2,2 - (ureylene) - diethyl bis - (2 - isocyanatoethyl fumarate). In Example 26, bis-(2-isocyanatoethyl)-fumarate is prepared by slurrying bis-(2-aminoethyl)-fumarate dihydrochloride in o-dichlorobenzene, passing phosgene into the slurry, removing the solvent by vacuum distillation and recovering the product by evaporative distillation.