Polyaddition of bis(cyclic thiocarbonate) with diamines. Novel efficient synthetic method of polyhydroxythiourethanes

The polyaddition of a five-membered bis(cyclic thiocarbonate), 2,2-bis[p-(1,3-dioxolane-2-thione-4-yl-methoxy)phenyl] propane (B5CTC) with diamines, 4,9-dioxa-1,18-dodecanediamine (DODDA), and p-xylylenediamine (p-XDA) was carried out to afford the corresponding polyhydroxythiourethanes with number-average molecular weights of 11 000-44 000 in good yields. The rate of polyaddition of B5CTC was extremely larger than the corresponding five-membered bis(cyclic carbonate), 2,2-bis[p-(1,3-dioxolan-2-one-4-yl-methoxy)phenyl]propane (B5CC). Also, B5CTC gave higher molecular weight polymers than B5CC. These differences were discussed based on the reaction process of a monofunctional five-membered cyclic thiocarbonate and a cyclic carbonate with amines.