RAFT Polymerization-Induced Self-Assembly as a Strategy for Versatile Synthesis of Semifluorinated Liquid-Crystalline Block Copolymer Nanoobjects.

Polymerization-induced self-assembly is demonstrated as a powerful platform for the synthesis of block copolymers comprising a semifluorinated liquid-crystalline block. This strategy transforms the deficiency of polymer insolubility encountered in traditional homogeneous solution protocols to the strength for dispersion polymerization, thus, enabling direct access to polymorphic block copolymer nanoobjects at high concentrations and with quantitative conversions. The versatility of this strategy is highlighted by polymerizations in a wide selection of inexpensive solvents, from nonpolar to highly polar, to afford various block copolymers with distinct combinations of amorphous/crystalline or hydrophilic/hydrophobic/fluorinated segments. The utility of the nanoparticles is demonstrated as robust Pickering emulsifiers for commonly considered good solvents.