Oxygen-Tolerant Alternating Copolymerization of Fluorinated Monomers and Vinyl Ethers at Mild Temperature

The oxygen-tolerant radical copolymerization of fluorinated monomers with vinyl ethers at room temperature in the presence of a tri-nbutylborane methoxypropylamine (TBB-MOPA)/CH3COOH 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(FO-alt-VE) copolymers (up to 43% yield). The resulting copolymers were characterized by FTIR, 19F NMR, and 1H NMR spectroscopy techniques. The thermomechanical properties (Tg = −16 to 18 °C) of these polymers were also studied and confirmed 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% (Td5%) were evaluated as comprised between 262 and 316 °C while the poly(PMVE-alt-EVE) copolymer was characterized by a higher thermostability (Td5% = 382 °C). Their surfaces were found to be hydrophobic, evidenced by water contact angles measured from 95 to 110°. When soluble in a size exclusion chromatography solvent, these fluorinated copolymers reached Mn up to 169,200 g mol–1. Because of these features, such fluorinated copolymers may find applications in paints and coatings or as elastomers.