The synthesis of polythiolcarbamates

A series of polythiolcarbamates, [—CONH—X—NHCOS—Y—S]m, have been prepared in which X was either aliphatic or aromatic and Y was a wide variety of aliphatic groups. Synthesis of the polymers by two different methods, the tertiary aminecatalyzed solution polymerization of diisocyanates with dimercaptans and the interfacial polycondensation of bischlorothiolformates and diamines, proved that the polymers had the desired thiolcarbamate structure. Greater yields of lower molecular weight polymers were obtained by the diisocyanate method. Polythiolcarbamates were found to be highly insoluble white powders which tend to decompose in light, in hot solvents, and in aqueous base. They melt somewhat higher than their oxygen analogues, but are less thermally stable.