Free radical copolymerization of 2,2,2-trifluoroethyl a-fluoroacrylate and tert-butyl a-trifluoromethylacrylate: Thermal and optical properties of the copolymers

Abstract : The radical copolymerization of 2,2,2-trifluoroethyl a-fluoroacrylate (FATRIFE) with tert-butyl a-trifluoromethylacrylate (MAF-TBE) initiated by tert-butyl 2,2-dimethylperoxypropanoate was investigated in acetonitrile solution. A series of poly(FATRIFE-co-MAF-TBE) copolymers were synthesized with MAF-TBE compositions, determined by 19F NMR, ranging from 12 to 44 mol %. MAF-TBE incorporation was less than 50 mol % as this monomer underwent no radical homopolymerization. The obtained copolymers exhibited number-average molecular weights and polydispersity indexes ranging from 1.5 × 104 to 9.6 × 104 g/mol and from 1.5 to 3.1, respectively. The reactivity ratios were determined by the Kelen-Tüdos method (rFATRIFE = 1.71 ± 0.01 and rMAF-TBE = 0 at 74 °C) leading to random copolymers and alternating copolymers when the MAF-TBE molar ratio in copolymer is close to 50 mol %. Thermal and optical properties of the resulting polymers were examined. Glass transition temperatures of copolymers were varying from 89 to 108 °C. Modifying the compositions of these copolymers allowed a precise control over the refractive index measured at 633, 1320, and 1550 nm.
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Submitted on : Monday, March 30, 2009 - 3:12:12 PM
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Jean-Marc Cracowski, Véronique Montembault, Isabelle Hardy, Dominique Bosc, Bruno Ameduri, et al.. Free radical copolymerization of 2,2,2-trifluoroethyl a-fluoroacrylate and tert-butyl a-trifluoromethylacrylate: Thermal and optical properties of the copolymers. Journal of Polymer Science Part A: Polymer Chemistry, Wiley, 2008, 46 (13), pp.4383-4391. ⟨10.1002/pola.22761⟩. ⟨hal-00371819⟩

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