In Situ Radical Polymerization and Grafting Reaction Simultaneously Initiated by Fluorinated Graphene

Fluorinated graphene (FG) showed interesting electrochemical, electronic, and mechanical properties, as well as chemical reactivity for multifarious functionalization of graphene material. This work reported a free radical polymerization and grafting from polymerization of a styrene monomer directly initiated by FG, which simultaneously provided free polymers and functionalized graphene with polymer chains grafted. The FG exhibited an almost comparative initiation efficiency to equivalent commercial initiator azodiisobutyronitrile under similar conditions, resulting in a high yield of free polystyrene (40.9%) with a high molecular weight (M_n = 114.7 kg/mol). It was demonstrated that FG-triggered polymerization presented some special characteristics, such as a long lifetime of chain radical centers even when the reaction was stopped and insensitivity to oxygen molecules. The mechanistic study indicated that the polymerization was initiated by single-electron transfer reaction between FG and a monomer leading to formation of primary radicals; in addition, FG also played an important role in chain transfer and termination reactions during the polymerization process.