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