Hybrid Block Copolymer Synthesis by Merging Photoiniferter and Organocatalytic Ring-Opening Polymerizations

Access to block copolymers from monomers that do not polymerize via a common mechanism requires initiation from a multifunctional species that allows orthogonal polymerization chemistries. We disclose a strategy to provide well-defined polyacrylamido-b-polyether block copolymers by a one-pot combination of photoiniferter polymerization and organocatalytic ring-opening polymerization (ROP) using a hydroxy-functionalized trithiocarbonate photoiniferter as the dual initiator at ambient temperature. Our results reveal good compatibility between the two polymerization systems and highlight that they can be performed in arbitrary order or simultaneously with good retention of the thiocarbonylthio functionality. We also demonstrate selective temporal control over the photoiniferter polymerization during concurrent ROP. We harnessed the efficiency of combining these polymerization systems to provide tailor-made block copolymers from chemically distinct monomers.