Photo-Mediated RAFT Step-Growth Polymerization With Diacrylate Monomers: Investigating Versatility and Oxygen Tolerance.

Photomediated reversible addition fragmentation chain transfer (RAFT) step-growth polymerization is performed using a trithiocarbonate-based chain transfer agent (CTA) and acrylate-based monomers both with and without a photocatalyst. The versatility of photo-mediated RAFT step-growth is demonstrated by one-pot synthesis of a graft copolymer via sequential monomer addition. Furthermore, oxygen-tolerant photo-mediated RAFT step-growth is demonstrated, facilitated by the appropriate selection of photocatalyst and solvent pair (zinc tetraphenyl porphyrin [ZnTPP] and dimethyl sulfoxide [DMSO]), enabling ultralow volume polymerization under open-air conditions.