Reversible addition-fragmentation chain transfer (RAFT)-mediated polymerization-induced self-assembly (PISA) mediated by a binary mixture of a star-like macro-RAFT agent and a linear macro-RAFT agent is developed, allowing for the synthesis of a diverse set of self-assembled star/linear block copolymer blends.

Comprehensive Summary

Reversible addition-fragmentation chain transfer (RAFT)-mediated polymerization-induced self-assembly (PISA) of star block copolymer and linear block copolymer using a binary mixture of a star-like macro-RAFT agent and a linear macro-RAFT agent is reported. With this formulation, star block copolymer and diblock copolymer were formed simultaneously to generate colloidally stable star/linear block copolymer assemblies. Size exclusion chromatography (SEC) analysis confirmed the presence of two types of polymers in the final samples. The molar ratio of the star-like macro-RAFT agent and the linear macro-RAFT agent has a significant impact on the morphology of polymer assemblies. It was found that increasing the amount of star-like macro-RAFT agent facilitated the formation of higher-order morphologies. Additionally, effects of other reaction parameters including the length/number of the arm of the star-like macro-RAFT agent, degree of polymer (DP), monomer concentration on the morphology of star/linear block copolymer assemblies were also investigated. We expect that this work will offer new possibilities for the scalable preparation of polymer assemblies with unique structures and functions.