Abstract
Controlled radical polymerizations (CRP) were pioneered in the late 1970s. Since then, 7 tremendous investigations have been developed, especially from mid-1990s which generated much enthu- 8 siasm on CRP. However, the extraordinary scientific development of CRP contrasts with the limited number 9 of commercially available products derived from these technologies. But, for fluoropolymers, the situation is 10 different since iodine transfer polymerization of fluoroalkenes led to commercially available thermoplastic 11 elastomers as soon as 1984.Abrowse or CRPof fluorinated monomers is presented and is classified into three 12 families: (i) the CRP of fluorine-containing styrenic monomers mainly occur from nitroxide-mediated 13 polymerization (NMP) or by atom radical transfer polymerization (ATRP); (ii) that of fluorinated 14 (meth)acrylic monomers from NMP, ATRP, and in the presence of iniferters; and finally (iii) fluoroalkenes 15 (which is a real challenge since these monomers are gaseous) can be (co)polymerized by iodine transfer poly- 16 merization or by processes that required either borinates or xanthates (MADIX).Apeculiar interest lies in the 17 CR copolymerization of fluoroalkenes with other comonomers (such as vinylidene fluoride, chlorotri- 18 fluoroethylene, 3,3,3-trifluoropropene, hexafluoropropylene, perfluoromethyl vinyl ether, orR-trifluoromethacrylic 19 acid) in the presence of either xanthates, borinates, or iodo compounds. These technologies enable one to generate 20 copolymers that exhibit well-defined architectures, such as telechelic, block, and graft copolymers. Merits and 21 limitations of CRP of F-monomers are also reported. Finally, this Perspective is illustrated by several 22 properties and applications of these fluorinated copolymers (such as surfactants, thermoplastic elastomers, 23 fuel cell and ultrafiltration membranes, dielectrical polymers, optical storage devices, or polycondensates, the 24 fluorinated segments of which bring softness and thermal stability). Hence, CRP can be regarded as a 25 revolutionary method to produce precisely controlled, next-generation specialty fluorinated (co)polymers.