Modular Monomers with Tunable Solubility: Synthesis of Highly Incompatible Block Copolymer Nano-Objects via RAFT Aqueous Dispersion Polymerization.

The high incompatibility of block copolymers consisting of a neutral stabilizer block and a polyelectrolyte core-forming block is exploited to drive phase segregation during polymerization-induced self-assembly (PISA). A modular approach to systematically tune the solubility of ionic monomers/polymers is developed to efficiently identify monomers suitable for aqueous dispersion polymerizations. The strong phase segregation ability of the neutral-polyelectrolyte block copolymers favors the formation of worms over a relatively broad composition range and even at very low solids. These findings suggest that the degree of incompatibility between the stabilizer block and the core-forming block should be considered as one of the key parameters when studying morphological transitions in PISA.