Synthesis and properties of poly(hydroxyurethane)s

Bis(cyclic Carbonate)s 1 were prepared by the reaction of bis(epoxide)s and atmospheric pressure of CO2 in the presence of sodium iodide and triphenylphosphine as catalysts at 100°C in high yield. Polyaddition of 1 and hexamethylenediamine (2a) or dodecamethylenediamine (2b) in dimethylsulfoxide or N,N-dimethylacetamide (DMAc) at 70 or 100°C for 24 h afforded corresponding poly(hydroxyurethane)s with Mn 20,000–30,000. When ethylenediamine (2c) or 1,3-propanediamine (2d) was used as a diamine, poly(hydroxyurethane)s with lower molecular weight were obtained. The presence of water, methanol, or ethyl acetate in the solvent had little effect on the Mn of the polymer obtained, because of the high chemoselectivity of the reaction of the five-membered cyclic carbonate and amine. Polyaddition of bis(cyclic carbonate) bearing ester groups and 2a also afforded the corresponding poly(hydroxyurethane) without aminolysis of the ester groups. Poly(hydroxyurethane) 3 obtained from the bis(cyclic carbonate) derived from bisphenol A was less soluble in organic solvents than model polyurethane 8 having no hydroxy groups obtained from 4,4′-isopropylidenebis(2-hydroxyethoxybenzene) and hexamethylene diisocyanate, and was thermally stable as well as 8.3 easily undertook crosslinking at room temperature by the treatment with hexamethylene diisocyanate or aluminium triisopropoxide in DMAc or tetrahydrofuran. The gel crosslinked by aluminium triisopropoxide regenerated the original polymer at room temperature by treatment with 1.5 equiv of 1.2M HCl in N-methylpyrollidinone for 1 h. © 1993 John Wiley & Sons, Inc.