Abstract
A persistent perfluoroalkyl branched radical (PPFR), perfluoro-3-ethyl-2,4-dimethyl-3-pentyl, was shown to be a good source of *CF3 radicals able to initiate the radical copolymerization of vinylidene fluoride (VDF) with tert-butyl α-trifluoromethacrylate (MAF-TBE). NMR characterizations of the resulting poly(VDF-co-MAF-TBE) copolymers showed that copolymerization was exclusively initiated by *CF3 radicals, as evidenced by the thermal decomposition of PPFR above 80 °C. The addition of *CF3 radical onto VDF/MAF-TBE system was regioselective leading to CF3-CH2-CF2* radical that further cross propagated onto MAF-TBE unit and the α,ω-trifluoromethyl group acted as an efficient label to assess the molecular weights of the resulting copolymers by 19F NMR spectroscopy. Three [PPFR]0/([VDF]0 + [MAF-TBE]0) initial molar ratios (2.0, 1.0, and 0.5%) led to various molecular weights ranging from 21300 to about 105000 g*mol−1. When that ratio decreased, both the molecular weights and the thermostability of these original poly(VDF-co-MAF-TBE) copolymers increased.