Abstract
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.