Synthesis and polymerization of fluorinated monomers bearing a reactive lateral group. XIV. Radical copolymerization of vinylidene fluoride with methyl 1,1‐dihydro‐4,7‐dioxaperfluoro‐5,8‐dimethyl non‐1‐enoate

Abstract

AbstractThe radical copolymerization in solution of vinylidene fluoride (VDF; or 1,1‐difluoroethylene) with methyl 1,1‐dihydro‐4,7‐dioxaperfluoro‐5,8‐dimethyl non‐1‐enoate (MDP) initiated by di‐tert‐butyl peroxide is presented. Six copolymerization reactions were investigated with initial [VDF]0/[MDP]0 molar ratios of 35/65 to 80/20. Both of these comonomers copolymerized in this range of copolymerization. Moreover, these comonomers homopolymerized separately under these conditions. The copolymer compositions of these random copolymers were calculated by means of 19F NMR spectroscopy, which allowed the quantification of the respective amounts of each monomeric unit in the copolymers. The Tidwell–Mortimer method was used for the assessment of the reactivity ratios (ri) of both comonomers, which showed a higher incorporation of MDP in the copolymers (rMDP = 2.41 ± 2.28 and rVDF = 0.38 ± 0.21 at 120 °C). The Alfrey–Price Q and e values of the trifluoroallyl monomer MDP were calculated to be 0.024 (from QVDF = 0.008) or 0.046 (from QVDF = 0.015) and 0.70 (vs eVDF = 0.40) or 0.80 (vs eVDF = 0.50), respectively, indicating that MDP was an electron‐accepting monomer. The thermal properties of these fluorinated copolymers were also determined. Except for those containing a high amount of VDF, the copolymers were amorphous. Each showed one glass‐transition temperature (Tg) only, and with known laws of Tg's, Tg of the MDP homopolymer was assessed. It was compared to that obtained from the direct radical homopolymerization of MDP and discussed. Indeed, these two values were close (Tg = −3 °C). Thermogravimetric analyses were performed, and they showed that the copolymers were rather thermostable because the thermal degradation occurred at 280 °C. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 3109–3121, 2003