Controlled Radical (Co)polymerization of Fluoromonomers

Controlled radical polymerizations (CRP) were pioneered in the late 1970s Since then, tremendous investigations have been developed especially from mid 1990s which generated much enthusiasm on CRP However, the extraordinary scientific development of CRP contrasts with the limited number of commercially available products derived from these technologies But, for fluoropolymers, the situation is different since iodine transfer polymerization of fluoroalkenes led to commercially available thermoplastic elastomers as soon as 1984 A browse or CRP of fluorinated monomers is presented and is classified into three families (i) the CRP of fluorine-containing styrenic monomers mainly occur from nitroxide-mediated polymerization (NMP) or by atom radical transfer polymerization (ATRP), 00 that of fluorinated (meth)acrylic monomers from NMP, ATRP, and in the presence of iniferters, and finally (m) fluoroalkenes (which is a real challenge since these monomers are gaseous) can be (co)polymerized by iodine transfer polymerization or by processes that required either borinates or xanthates (MADIX) A peculiar interest lies in the CR copolymerization of fluoroalkenes with other comonomers (such as vinylidene fluoride, chlorotrifluoroethylene, 3,3 3-trifluoropropene, hexafluoropropylene, perfluoromethyl vinyl ether, or alpha-trifluoromethacrylic acid) in the presence of either xanthates, borinates, or iodo compounds These technologies enable one to generate copolymers that exhibit well-defined architectures, such as telechelic block, and graft copolymers Merits and limitations of CRP of F-monomers are also reported Finally, this Perspective is illustrated by several properties and applications of these fluorinated copolymers (such as surfactants, thermoplastic elastomers fuel cell and ultrafiltration membranes dielectrical polymers, optical storage devices or polycondensates, the fluorinated segments of which bring softness and thermal stability) Hence, CRP can be regarded as a revolutionary method to produce precisely controlled, next-generation specialty fluorinated (co)polymers