Controlled thioacyl group transfer (TAGT) polymerization of cyclic sulfide: Novel approach to AB diblock copolymers by the combination of RAFT and TAGT polymerizations

The thioacyl group transfer (TAGT) polymerization of propylene sulfide (PS) by using dithiocarbonyl compounds as initiator and the synthesis of AB diblock polymers by the combination of reversible addition-fragmentation chain transfer (RAFT) and TAGT polymerizations have been demonstrated. Ring-opening polymerization of PS was conducted with benzyl dithiobenzoate (BDB) and benzyl 1-pyrrolecarbodithioate (BPC) as initiators in the presence of tetraphenylphosphonium salts as catalysts. The synthesis of diblock copolymers using PS was conducted by the polymerizations of PS using the BDB-terminated polystyrene and BPC-terminated poly(N,N-dimethyl acryamide) (PolyDMAm) as macroinitiators in the presence of tetraphenylphosphonium chloride (TPPC). This approach is proving to be a promising approach to design macromolecular architecture, such as block copolymer with a versatile combination of functional blocks.