Iron-Catalyzed Atom Transfer Radical Polymerization of Semifluorinated Methacrylates

Fluorinated polymers are an important class of functional materials that exhibit unique properties such as high chemical resistance, thermal stability, and low surface energy. Atom transfer radical polymerization (ATRP) of semifluorinated monomers catalyzed by copper catalysts often requires development of special conditions to control the polymerization and prevent side reactions such as base-catalyzed transesterification between the fluoro-containing monomers and solvents. In this paper, photoinduced iron-catalyzed ATRP was applied to the polymerization of a variety of semifluorinated methacrylate monomers. Polymerizations were initiated by photochemical generation of the Fe catalyst activator under blue light irradiation, enabling temporal control over the growth of polymer chains, and were well-controlled in various solvents, including fluorinated and nonfluorinated solvents, without undergoing any side reactions. Moreover, in situ chain extension and block copolymerization experiments demonstrated the preservation of chain end functionality, enabling facile synthesis of well-controlled block copolymers.