Macromolecular engineering approach for the preparation of new architectures from fluorinated olefins and their applications

An overview on fluorinated olefin-based architectures prepared by reversible deactivation radical polymerization (RDRP) techniques and their applications is presented. Controlled syntheses of well-defined fluoropolymers are discussed as a route to prepare tailored macromolecules of various architectures, such as homopolymers, block copolymers (BCPs), graft copolymers, and star/miktoarms. Primary examples of different strategies of synthesis include (a) Iodine Transfer Polymerization (ITP), (b) Reversible Addition-Fragmentation Chain Transfer/Macromolecular Design via the Interchange of Xanthates (RAFT/MADIX) polymerization, (c) Atom Transfer Radical Polymerization (ATRP), (d) Nitroxide Mediated Polymerization (NMP), (e) Organometallic-Mediated Radical Polymerization (OMRP) and (f) Others systems (based on tellurium, cobalt and other complexes). Synthesis of BCPs and graft copolymers of vinylidene fluoride (VDF), chlorotrifluoroethylene (CTFE) and other fluorinated monomers are also discussed, as along with those synthesized via Copper(I)-catalyzed azide-alkyne cycloaddition (click chemistry). Phase behavior and self-assembly of the fluorinated block copolymers are also reported. Special attention is devoted to the applications of fluoropolymer architectures in producing thermoplastic elastomers, medical tactile sensors, fuel cells membranes, functional coatings, electroactive polymers (e.g. piezoelectric/ferroelectric/dielectric devices and actuators), high energy storage capacitors, surfactants and composites.