Kinetics of radical copolymerization of [1‐(fluoromethyl)vinyl]benzene with chlorotrifluoroethylene

The synthesis of [1-(fluoromethyl)vinyl]benzene (or α-(fluoromethyl)-styrene, FMB) and its radical copolymerization with chlorotrifluorethylene (CTFE), initiated by tert-butyl peroxypivalate (TBPPi) are presented. The allyl monomer [H 2 C = C(CH 2 F)C 6 H 5 ] 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 [CTFE] 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 19 F 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 °C) showing that FMB is more reactive than CTFE as well as other halogenated or nonhalogenated monomers involved in the radical copolymerization with CTFE.

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