One-Pot Synthesis of Block Copolymers by Orthogonal Ring-Opening Polymerization and PET-RAFT Polymerization at Ambient Temperature

Well-defined poly(ε-caprolactone)- b -poly(methyl acrylate) (PCL- b -PMA) block copolymers were synthesized at ambient temperature by one-pot combination of diphenyl phosphate (DPP)-catalyzed ring-opening polymerization (ROP) and photoinduced electron/energy transfer-reversible addition–fragmentation chain transfer (PET-RAFT) polymerization. Full orthogonality of PET-RAFT polymerization and DPP-catalyzed ROP was confirmed by kinetic studies, which allowed facile synthesis of PCL- b -PMA block copolymers without a specific polymerization sequence. The resulting PCL- b -PMA block copolymers synthesized by either sequential or simultaneous ROP and PET-RAFT polymerization showed remarkably low molecular weight distributions (≤1.15), indicating that both ROP and PET-RAFT polymerizations proceeded in a controlled manner. In contrast to previous synthetic methods to prepare block copolymers, this facile one-pot method allows for rapid synthesis of block copolymers controlled via visible light.