Synthesis and characterization of poly(fluorinated vinyl ether‐alt‐tert‐butyl α‐trifluoromethacrylate) copolymers

Radical copolymerizations of electron acceptor tert‐butyl α‐trifluoromethacrylate (MAF‐TBE) and electron donor 1,1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8‐heptadecafluoro‐10‐(vinyloxy)decane (FAV8) initiated by tert‐butyl 2,2‐dimethylperoxypropanoate were investigated. Although none of both monomers underwent radical homopolymerization under classical conditions, they readily copolymerized, producing a soluble copolymer containing 60–65 mol % of MAF‐TBE. The reactivity ratios determined by the Kelen‐Tüdos method were found to be rMAF‐TBE = 0.03 ± 0.01 and rFAV8 = 0 at 74 °C, indicating the synthesis of alternated copolymers. The copolymer compositions were assessed from 19F‐NMR spectroscopy and correlated with thermogravimetric analysis. Molecular weights and polydispersity indexes of poly(MAF‐TBE‐alt‐FAV8) copolymers were both low and ranged from 5.5 to 6.9 × 103 g mol−1 and from 1.08 to 1.23, respectively. Copolymers were amorphous, and Tg were about 55 °C for all copolymers. TGA analyses showed the release of isobutene from MAF‐TBE units in copolymers before a degradation of the resulting poly(α‐trifluoromethacrylic acid‐alt‐FAV8) copolymers, occurring at 250–260 °C.