Kinetics of the Radical Copolymerization of 2,2,2-Trifluoroethylmethacrylate with tert-Butyl-a-trifluoromethacrylate

Frédéric Boschet (1) , Georges Kostov (1) , B. Ameduri (1) , Yoshida Toru (2) , Kosuke Kawada (3)

1 ICGM ICMMM - Institut Charles Gerhardt Montpellier - Institut de Chimie Moléculaire et des Matériaux de Montpellier
2 TOSOH F-Tech, Inc.
3 TOSOH F-Tech, Inc.

The radical copolymerization of two different methacrylate monomers, 2,2,2-trifluoroethyl-methacrylate (TFEMA) and tert-butyl-a-trifluoromethacrylate (TBTFMA) in solution was investigated. The resulting statistic poly(TFEMA-co-TBTFMA) copolymers were characterized by NMR spectroscopy to assess their compositions. The kinetics of copolymerization enabled one to determine the reactivity ratios of both comonomers according to the methods of Fineman-Ross, Kelen-Tu¨ dos, and extended Kelen-Tu¨ dos. Excellent correlations were found between these methods leading to the following reactivity ratios: rTFEMA ¼ 4.87 6 1.50 and rTBTFMA ¼ 0.10 6 0.02 at 74 C. These values indicated that the structure of the copolymers was composed of poly(TFEMA) micro-blocks separated by one TBTFMA unit. Both yields and molecular weights (ranging between 1000 and 12,000 g/mol) increased with the TFEMA content. The thermal stability of these (co)polymers showed that the decomposition temperature at 10% weight loss increased both with TFEMA content and increasing molecular weights of the poly(TFEMA-co-TBTFMA) copolymers.

Mots clés: fluoropolymers; gel permeation chromatography; kinetics (polym.); NMR; radical copolymerization; radical polymerization; reactivity ratio; tert-butyl-a-trifluoromethacrylate; thermal properties; thermogravimetric analysis; 2-trifluoroethyl-methacrylate

Domaines: Polymères

Frédéric Boschet, Georges Kostov, B. Ameduri, Yoshida Toru, Kosuke Kawada. Kinetics of the Radical Copolymerization of 2,2,2-Trifluoroethylmethacrylate with tert-Butyl-a-trifluoromethacrylate. Journal of Polymer Science Part A: Polymer Chemistry, 2010, 48, pp.1029-1037. ⟨10.1002/pola.23857⟩. ⟨hal-00447595⟩