Controlled radical fluorination of poly(meth)acrylic acids in aqueous solution

Fluorinated alkenes exhibit very poor reactivity in copolymerization with non-fluorinated polar monomers such as acrylates. Herein we describe a convenient method for the synthesis of poly(vinyl fluoride-co-acrylic acid) and poly(2-fluoropropene-co-methacrylic acid) copolymers. Thus, the silver-catalyzed decarboxylative radical fluorination of poly(acrylic acid) with Selectfluor in water at room temperature affords poly(vinyl fluoride-co-acrylic acid) copolymers in high yields with well-defined molecular weights and polydispersities. A linear correlation is observed between the extent of fluorination and the amount of Selectfluor, indicating that the copolymer of virtually any monomer ratio can be readily accessed by controlling the amount of Selectfluor. This controlled decarboxylative fluorination is extended to poly(methacrylic acid), leading to well-defined poly(2-fluoropropene-co-methacrylic acid) copolymers.