The synthesis of [1-(fluoromethyl)vinyl]benzene (or alpha-(fluoromethyl)styrene, FMB) and its radical copolymerization with chlorotrifluorethylene (CTFE), initiated by tert-butyl peroxypivalate (TBPPi) are presented. The allyl monomer [H2C = C(CH2F)C6H5] was obtained by electrophilic fluorodesilylation of trimethyl(2-phenylprop-2-en-1-yl)silane in 93% yield. A series of seven copolymerization reactions were carried out starting from initial FCTFE](0)/([FMB](0) + [CTFE](0)) molar ratios ranging from 19.6 to 90.0 mol %. The molar compositions of the obtained poly(CTFE-co-FMB) copolymers were assessed by means of F-19 nuclear magnetic resonance spectroscopy. Statistic copolymers were produced with molar masses ranging between 13,800 and 25,600 g/mol. From the Kelen and Tudos method, the kinetics of the copolymerization led to the determination of the reactivity ratios, r(i), of both comonomers (r(CTFE) = 0.4 +/-0.2 and r(FMB) = 3.7 +/- 1.8 at 74 degrees C showing that FMB is more reactive than CTFE as well as other halogenated or nonhalogenated monomers involved in the radical copolymerization with CTFE. (C) 2007 Wiley Periodicals, Inc.