Radical copolymerizations of electron acceptor tert-butyl alpha-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-Tudos method were found to be r(MAF-TBE) = 0.03 +/- 0.01 and r(FAV8) = 0 at 74 degrees C, indicating the synthesis of alternated copolymers. The copolymer compositions were assessed from F-19-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 x 10(3) g mol(-1) and from 1.08 to 1.23, respectively. Copolymers were amorphous, and Tg were about 55 degrees C for all copolymers. TGA analyses showed the release of isobutene from MAF-TBE units in copolymers before a degradation of the resulting poly(alpha-trifluoromethacrylic acid-alt-FAV8) copolymers, occurring at 250-260 degrees C. (C) 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 6116-6123, 2009