Self-assembly of amphiphilic random co-poly(ionic liquid)s: the effect of anions, molecular weight, and molecular weight distribution

Self-assembly behavior of amphiphilic random co-poly(ionic liquid)s in aqueous solution was investigated in this work. An imidazolium-type homopolymer, poly(1-(4-vinylbenzyl)-3-methyl imidazolium chloride) (denoted as PIL-[Cl]), was synthesized via reversible addition fragmentation chain transfer (RAFT) polymerization of p-chloromethyl styrene, and followed by post-polymerization with methylimidazole (or vinylimidazole). Partial anion-exchange of PIL-[Cl] with PF6− anions yielded amphiphilic random copolymers, PIL-[Cl]x[PF6]y (suffixes x, y represent the relative molar ratio of Cl− and PF6− anions). Self-assembly morphologies of PIL-[Cl]x[PF6]y in aqueous solution as a function of copolymer composition (anions), molecular weight, and molecular weight distribution were investigated. The size of well-defined PIL-[Cl]x[PF6]y spherical micelles increased dramatically with increasing molecular weight distribution, while the anions and molecular weight show little effect on the micelle size. Furthermore, self-assembly of amphiphilic random ionic copolymers with the vinylimidazole groups yielded colloidosomes, which might be due to the polymerization of vinylimidazole groups.