Synthesis and Self-Assembly of Poly(4-acetoxystyrene) Cubosomes

Polymer cubosomes (PCs) are a recent class of self-assembled nanostructures with great application potential due to their high porosity and surface area. Currently, most reported PCs consist of polystyrene block copolymers (BCPs), for which self-assembly parameters are rather well understood. Changing the block chemistry would be desirable to introduce more functionality; however, knowledge of adapting the self-assembly process to new chemistries remains limited. This work, reports on synthesizing poly(ethylene oxide)-block-poly(4-acetoxystyrene) and its copolymers with styrene, and provide conditions for their self-assembly into PCs with high yield and high inner order. It is shown that the polarity of the starting solvent toward the corona block allows tuning of the final morphology by controlling the corona volume and packing parameter. Polymer cubosomes of poly(4-acetoxystyrene) is realized by RAFT polymerization and subsequent self-assembly in water. By adjusting the solvent conditions, the same polymer could be directed into polymersomes, cubosomes or hexosomes. The study provides new insights into the formation of polymer cubosomes using functional wall chemistries. image