Topological engineering of amphiphilic copolymers via RAFT dispersion copolymerization of benzyl methacrylate and 2-(perfluorooctyl)ethyl methacrylate for polymeric assemblies with tunable nanostructures

The influence of polymer topology on the nanostructure of amphiphilic copolymer assemblies has been less studied. In this contribution, we regulated the topology of the solvophobic block of poly(N,N-dimethylamino ethyl methacrylate)-b-poly(benzyl methacrylate-co-2-perfluorooctyl ethyl methacrylate) [PDMA-b-P(BzMA-co-FMA)] by reversible addition–fragmentation chain transfer (RAFT) dispersion copolymerization of BzMA and FMA at varying feed ratios. The influence of the variation in the polymer topology on the nanostructure of the corresponding assemblies was evaluated. With the increment of the FMA wt% within the solvophobic block, the size of the PDMA-b-P(BzMA-co-FMA) vesicles increases accordingly. Besides, for PDMA-b-P(BzMA-co-FMA) copolymers whose molecular weights of the solvophobic block range from 88 to 141k, by adjusting the feed ratio of BzMA/FMA, a rich variety of nanostructures were fabricated, including large compound micelles, large compound vesicles, hexagonally packed hollow hoops and nanoporous spheres. Our results indicate that topological engineering of the amphiphilic copolymers via RAFT dispersion copolymerization could be an efficient approach for regulating the nanostructure of polymer assemblies.