Research progress in highly efficient reversible deactivation radical polymerization of vinylidene fluoride

Polyvinylidene fluoride (PVDF)-based polymers are extensively utilized in various fields such as building and large bridge coatings, lithium battery binders and separators, solar panel membranes, and water treatment membranes owing to their exceptional performance. They rank as the second largest commercially used fluorinated polymer next to polytetrafluoroethylene. Reversible Deactivated Radical Polymerization (RDRP) serves as an efficient strategy for synthesizing well-defined structurally and functionally tailored PVDF-based polymers. Notably, Iodine Transfer Polymerization (ITP), Reversible Addition Fragmentation Chain Transfer/Macromolecular Design via the Interchange of Xanthates (RAFT/MADIX), and Organometallic-Mediated Radical Polymerization (OMRP) represent the most suitable methods for engaging in reversible inactivated radical polymerization of vinylidene fluoride. This paper reviews the reaction mechanism of three controlled polymerization methods for PVDF, along with the research progress of initiators and initiator systems, and suitable chain transfer agents for VDF controlled polymerization. It also delineates and contrasts their respective characteristics and advantages, while looking ahead to their prospective directions for improvement and trends in research.