Polymerization-Induced Self-Assembly Driven by the Synergistic Effects of Aromatic and Solvophobic Interactions

Polymerization-induced self-assembly (PISA) has been established as an efficient method to fabricate polymeric vesicles. In most PISA cases, the formation of vesicles is solely driven by the solvophobic interactions. Besides solvophobic effects, many other noncovalent interactions can also drive/influence self-assembly of block copolymers. In this work, PISA driven by the synergistic effects of solvophobic and aromatic interactions is investigated. 7-(2-Methacryloyloxyethoxy)-4-methylcoumarin (CMA) is selected as a model monomer for RAFT dispersion polymerization to fabricate vesicles with both solvophobic and aromatic interactions existing in the membrane-forming blocks. Controlling vesicular size in the range of sub-100 nm to micrometer in PISA is realized by copolymerization of CMA with three different comonomers (aromatic or not) in various proportions to adjust the intermolecular interactions. Moreover, polymeric tubes with adjustable aspect ratios (from about 2 to 20) are produced by applying the cooperativity of aromatic and solvophobic interactions.