The oxygen tolerant radical copolymerization of fluorinated monomers with vinyl ethers at room temperature in the presence of tri-nbutylborane methoxypropylamine (TBBMOPA)/CH 3 COOH system is presented. The combination of commercially available fluoroolefins (FO) [perfluoromethyl vinyl ether (PMVE) and hexafluoropropylene (HFP)] and vinyl ethers (VE) [ethyl vinyl ether (EVE) and 2-(perfluorohexyl)ethyl vinyl ether (FAVE6)] was used for the synthesis of different alternating poly(FOalt-VE) copolymers (up to 43 % yield). The resulting copolymers were characterized by FT-IR, 19 F NMR and 1 H NMR spectroscopy techniques. Thermomechanical properties (T g = -16 to 18 °C) of these polymers were also studied and justified in terms of structure-properties relationships. Their stabilities were investigated as a function of temperature by thermogravimetric analyses. Then, their degradation temperatures related to a weight loss of 5%, (T d5% ) were evaluated as being comprised between 262 and 316 °C while poly(PMVE-alt-EVE) copolymer was characterized by a higher thermostability (T d5% = 382 °C). Their surfaces were found to be hydrophobic, evidenced by water contact angle measured from 95 to 110 °. When soluble in SEC solvent, these fluorinated copolymers reached M n up to 169,200 g mol -1 . Because of these features, such fluorinated copolymers may find applications in paints and coatings or as elastomers.

2-Trifluoromethacrylic acid (MAF) is a peculiar fluorinated functional monomer. Though it is known to polymerise via C=C bond cleavage under anionic initiation, its oxa-Michael addition polymerisation afforded polyesters bearing trifluoromethyl...