Radical solution copolymerisation of vinylidene fluoride with hexafluoropropene

The radical copolymerisation in solution of vinylidene fluoride (or 1,1-difluoroethylene (VDF)) with hexafluoropropylene (HFP) initiated by di- tert-butyl peroxide is presented. A series of eight copolymerisation reactions was investigated with initial [VDF] o/[HFP] o molar ratios ranging from 5.0/95.0 to 85.2/14.8. Both co-monomers copolymerised in this range of copolymerisation. Moreover, only VDF homopolymerised in these conditions. The copolymer compositions of these random-type copolymers were calculated by means of 19F NMR spectroscopy which allowed the respective amount of each monomeric unit in the copolymer to be quantified. The Tidwell and Mortimer method led to the assessment of the reactivity ratios, r i , of both co-monomers showing a higher incorporation of VDF in the copolymer ( r HFP = 0.12 ± 0.05 and r VDF = 2.9 ± 0.6 at 393 K). Alfrey–Price's Q and e values of HFP were calculated to be 0.002 (from Q VDF = 0.008) or 0.009 (from Q VDF = 0.015) and +1.44 (versus e VDF = 0.40) or +1.54 (versus e VDF = 0.50), respectively, indicating that HFP is an electron-accepting monomer. The thermal properties of these fluorinated copolymers were also determined. Except for those containing a high amount of VDF, they were amorphous. Each showed one glass transition temperature ( T g) only, and from known laws of T g, that of the homopolymer of HFP was assessed. It was compared with that obtained from the literature after extrapolation and is discussed. The kinetics of radical copolymerisation of vinylidene fluoride (VDF) with hexafluoropropylene (HFP), initiated by di- tert-butyl peroxide, led to the assessment of the reactivity ratios: r VDF = 2.9 ± 0.6 and r HFP = 0.12 ± 0.05 at 393 K. Glass transition temperatures ( T g) of the resulting copolymers were assessed and enabled determination of the T g of poly(HFP). ▪