Immortal Ring-Opening Copolymerization of Epoxide and Isocyanate Using a Commercial Manganese Catalyst

Immortal polymerization is a unique strategy for ring-opening copolymerizations (ROCOP) with epoxide monomers. In conjunction with various chain transfer agents (CTAs), the first immortal ROCOP of a typical epoxide (propylene oxide, PO) and isocyanate (p-tosyl isocyanate, TSI) using a commercial manganese catalyst is reported. In addition to precise molecular-weight control, this approach afforded novel polyurethane (PU) with unprecedented functionality, topology, and pinpoint sequence with secondary carbamyl linkage. In addition, a block copolymer of poly­(lactic acid) (PLA) with PU was synthesized via a sequential addition strategy, which offered an attractive access to expanding the scope of copolymers derived from aliphatic polyesters.