Gradient Copolymer Synthesis through Self-Assembly.

Polymerization-induced self-assembly (PISA) is typically performed to produce polymer nanoparticles featuring specific assembly morphologies. Herein, we demonstrate the use of PISA as a synthetic tool to direct gradient copolymer synthesis. Specifically, we leverage hydrophobicity-induced reaction selectivity and the rate acceleration typically associated with polymer compartmentalization upon assembly during PISA to bias reaction selectivity. In the chain extension of a poly(ethylene glycol) macrochain transfer agent, the selectivity of diacetone acrylamide (DAAm) and ,-dimethylacrylamide (DMA), two monomers with near-identical reactivity in water, can be modulated such that DAAm is preferentially incorporated over DMA upon self-assembly. By increasing the feed ratio of DAAm, monomer differentiation can be further biased toward DAAm due to the locus of polymerization becoming increasingly hydrophobic. This change in selectivity affords the autonomous generation of DAAm-DMA gradient sequences, otherwise inaccessible without outside intervention. Finally, a mild hydrolysis protocol can then be employed to harvest DAAm-DMA sequences, yielding compositionally unique gradient copolymers.