Synthesis and Polymerization of Fluorinated Monomers Bearing a Reactive Lateral Group. 9. Bulk Copolymerization of Vinylidene Fluoride with 4,5,5-Trifluoro-4-ene Pentyl Acetate

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Abstract

Bulk copolymerization of vinylidene fluoride (or 1,1-difluoroethylene (VDF)) with 4,5,5-trifluoro-4-ene pentyl acetate (FAc) initiated by di-tert-butyl peroxide is presented. A series of nine copolymerization reactions was investigated from initial [VDF]0/[FAc]0 molar ratios ranging from 32/68 to 95/5. Both these comonomers copolymerized in this range of copolymerization. Moreover, these comonomers homopolymerized separately in these conditions. The copolymer compositions of these random-type copolymers were calculated by means of 1H and 19F NMR spectroscopies and allowed one to quantify the respective amount of each monomeric unit in the copolymer. From the Tidwell and Mortimer method, the reactivity ratios, ri, of both comonomers were determined showing a higher incorporation of FAc in the copolymer (rFAc = 3.26 ± 1.49 and rVDF = 0.17 ± 0.10 at 120 °C). Alfrey−Price's Q and e values of trifluorovinyl acetoxy monomer FAc were calculated to be 0.060 (from QVDF = 0.008) or 0.040 (from QVDF = 0.015) and +1.14 (vs eVDF = 0.40) or +1.23 (vs eVDF = 0.50), respectively, indicating that FAc is an electron-accepting monomer. The normalized monomer-diad and -triad fractions as a function of the polymer composition were obtained from the comonomer sequence distribution theory and this was evidenced by 19F NMR analysis.

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