Recent advances in the controlled radical (co) polymerization of fluoroalkenes and applications therefrom

• Synthesis of fluorinated poly(VDF-co-monomer) copolymers by controlled radical copolymerization (CRP).
• Fluorinated copolymer from ITP or MADIX.
• High Tech materials achieved from CRP: O-ring and elastomers; fuel cell membranes hybrid materials.
• Block copolymers as precursors of surfactants, thermoplastic elastomers.

Since late 1970s, extensive studies on controlled (or pseudoliving) radical polymerizations (CRP) have been reported, especially from mid-1990s. Though many works have been investigated, the unexpected scientific growth of CRP contrasts with few commercially available products derived from these techniques. But, for fluoropolymers, the situation appears reversed since iodine transfer polymerization of fluoroalkenes already yielded commercially available thermoplastic elastomers as soon as 1984. These proceedings display a brief overview or CRP of fluorinated monomers (with a real challenge for gaseous fluoroalkenes such as vinylidene fluoride, chlorotrifluoroethylene, 3,3,3-trifluoropropene, hexafluoropropylene, perfluoromethyl vinyl ether). These monomers can be (co)polymerized via the iodine transfer polymerization or from techniques that involve either borinates or xanthates (named MADIX). These technologies enable one to generate copolymers that exhibit well-defined architectures, such as telechelic, block and graft copolymers and open up High Tech applications such as potentially non-bioaccumulable surfactants, elastomers endowed with low Tgs and that can be crosslinked, thermoplastic elastomers which can be used in a wide range of temperatures, fuel cell membranes being processed either by casting or by reactive extrusion.