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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.