Synthesis and copolymerisation of fluorinated monomers bearing a reactive lateral group: Part 21. Radical copolymerisation of vinylidene fluoride with 2-hydroperfluorooct-1-ene

Abstract

The synthesis and the radical copolymerisation of 2-hydroperfluorooct-1-ene (HPO) with vinylidene fluoride (VDF), initiated by tertio-butyl peroxypivalate (TBPPI) at 75 °C, are presented. That fluorinated alkene (HPO) was synthesised in two steps starting from the thermal or redox telomerisation of VDF with C 6F 13I (after purification of the monoadduct compound by rectification) followed by a dehydroiodination in the presence of various alkalies. Their influences are discussed toward the yield of the reaction. The compositions of the resulting random-type copolymers were calculated by means of 19F NMR spectroscopy and allowed one to quantify the respective amounts of each monomeric unit in the copolymer. From the Tidwell and Mortimer method, the reactivity ratios ( r i ) of both comonomers for this copolymerisation were determined showing a higher incorporation of VDF: r VDF = 12.0 ± 3.0 and r F 2 C CH C 6 F 13 = 0.9 ± 0.4 at 74 °C.