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

• Published in: Journal of polymer science. Part A, Polymer chemistry Polymer chemistry, 2007-09, Vol.45 (17), p.3843-3850
• Main Authors: Kostov, G., Tredwell, M., Gouverneur, V., Ameduri, B.
• Format: Article
• Language: English
• Subjects: Applied sciences; Chemical Sciences; Copolymerization; Exact sciences and technology; fluoropolymers; fluoropolymers; radical copolymerization; high performance polymers; kinetics; NMR; Organic polymers; Physicochemistry of polymers; Polymers; Preparation, kinetics, thermodynamics, mechanism and catalysts; radical copolymerization
• ISSN: 0887-624X; 1099-0518
• DOI: 10.1002/pola.22134

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 [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 [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 19F 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, ri, of both comonomers (rCTFE = 0.4 ± 0.2 and rFMB = 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. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3843–3850, 2007 The synthesis of [1‐(fluoromethyl)vinyl]benzene and its radical copolymerization with chlorotrifluorethylene initiated by tert‐butyl peroxypivalate are presented. The kinetics of that copolymerization led to the determination of the reactivity ratios of both comonomers.