Evolution of Morphology of POEGMA-b-PBzMA Nano-Objects Formed by PISA

The evolution of particle morphology occurring during polymerization-induced self-assembly (PISA) of a block copolymer poly(oligo(ethylene glycol) methacrylate)-b-poly(benzyl methacrylate) (POEGMA-b-PBzMA) is studied. A well-controlled reversible addition-fragmentation chain transfer (RAFT) polymerization yields nano-objects with various morphologies: spheres, aggregates, worm-like structures, and vesicles. A comparison of the morphology of the nano-objects formed from two different chain-length stabilizers established that the unreacted monomer played an important role during the morphology transitions, which is contrary to previous observations. In addition, morphology evolution to higher-order structures could be attained simply by extending the reaction time, after reaching full monomer conversion.