para-Fluoro/thiol click chemistry-driven pentafluorostyrene-based block copolymer self-assembly: to mimic or not to mimic the solubility parameter?

Abstract

A block copolymer (BCP) consisting of polystyrene (PS) and polypentafluorostyrene (PPFS) blocks is synthesized by nitroxide mediated polymerization (NMP). Then nucleophilic substitution of the labile para-fluorine atom onto the PPFS platform is performed by an organo-catalyzed reaction at ambient temperature using the para-fluoro/thiol click reaction. It is observed that the effect of the substitute chemical nature induces a drastic tuning of the nano-structuration of the block copolymer. Indeed, the para-fluoro/thiol click reaction leads to PS-b-modified PPFS block copolymers with solubility parameter control and drives an order/disorder transition.