Hierarchical Self-Assembly of Triphilic Main-Chain-Type Semifluorinated Alternating Graft Copolymers in Aqueous Solution.

Fluorinated copolymers can self-assemble in solution and form micelles with rare properties due to the peculiar behavior of fluorinated groups. However, the process description of the self-assembly is still largely phenomenological and difficult to explain due to the tendency of the fluorinated segments to segregate from both the hydrophilic and lipophilic segments, which can result in various morphologies. Herein, the controlled formation of ellipsoidal micelles, disklike micelles, and sheets by hierarchical self-assembly of triphilic main-chain-type semifluorinated alternating graft copolymers (AB) A-g-mOEG is presented (where A represents unit of α,ω-diiodoperfluoroalkane, B represents the unit of α,ω-unconjugated diene, and mOEG represents methoxy oligo(ethylene glycol)), which are synthesized by step transfer-addition and radical-termination (START) polymerization and azide-alkyne click chemistry. Furthermore, the possible self-assembly mechanism of these micron-level aggregates is proposed, which is ascribed to the hierarchical self-assembly, crowding effect of hydrophilic chains and the interfacial tension between the fluoroalkane and alkane segments. This study can provide a facile and highly efficient approach to the synthesis of main-chain-type fluorinated graft copolymers and expand the research field for the solution self-assembly of fluorinated copolymers.