Facile grafting modification of main-chain-type semi-fluorinated alternating fluoropolymers via simultaneous CuAAC reaction and ATRP in one pot at ambient temperature

Abstract

Grafting modification is a useful strategy to endow new functions to fluoropolymers with a fluorinated backbone and expand their potential application fields. Herein, we report a facile method to synthesize graft copolymers with a semi-fluorinated alternating backbone via simultaneous copper-catalyzed azide–alkyne cycloaddition (CuAAC) reaction and atom transfer radical polymerization (ATRP) in one pot. The fluorinated backbone with multiple structures synthesized from step transfer-addition and radical-termination (START) polymerization could be introduced to the fluorinated graft copolymers due to the powerful tolerance and designability of semi-fluorinated alternating copolymers ((AB)_nA, where A represents α,ω-diiodoperfluoroalkane and B represents α,ω-unconjugated diene). Importantly, the CuAAC reaction enables ATRP to proceed smoothly even at ambient temperature without additional light irradiation or heating, which is difficult to accomplish for conventional ATRP. Therefore, this strategy can provide a new and facile approach for the synthesis of fluorinated graft copolymers with a semi-fluorinated backbone under very mild conditions.