Radical copolymerization of chlorotrifluoroethylene with 4‐bromo‐3,3,4,4‐tetrafluorobut‐1‐ene

Abstract

The radical copolymerization of chlorotrifluoroethylene (CTFE) with 3,3,4,4‐tetrafluoro‐4‐bromobut‐1‐ene (BTFB) initiated by tert‐butylperoxypivalate is presented. The microstructures of the obtained copolymers are determined by means of NMR spectroscopies and elemental analysis and show that random copolymers were obtained. A wide range of poly(CTFE‐co‐BTFB) copolymers is synthesized, containing from 17 to 89 mol % of CTFE. In all the cases, CTFE is the less reactive of both comonomers. Td10% values, ranging from 163 up to 359 °C, are dependent on the BTFB content. These variations of thermal property are attributed to the increase in the number of C‐H and C‐Br bonds breakdown when the BTFB molar percentage in the copolymer is higher. Tg values range from 19 to 39 °C and a decreasing trend is observed when increasing the amount of BTFB in the copolymer. This observation arises from the higher flexibility of the copolymer when increasing the number of fluorobrominated lateral chains. These original fluoropolymers bearing reactive pendant bromo groups are suitable candidates for various applications. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2014, 52, 1714–1720

Synthesis and microstructural characterization of poly(chlorotrifluoroethylene-co-vinylidene chloride) copolymers

“…11 These authors determined the following reactivity ratios of both comonomers: r CTFE = 0.02 and r VDC = 17.14 at 60 °C. Indeed, except in the case of the radical copolymerization of CTFE with vinyl ethers (which leads to alternating copolymers 6,[51][52][53] ) such a trend seems similar to those of all other radical copolymerizations of CTFE with various comonomers 51 such as styrene, 12 MMA, 12 vinyl chloride, 11 N-vinyl pyrrolidone, 13 vinyl acetate, 14 vinyl triethoxysilane, 15 diallyldimethylammonium chloride (DADMAC), 16 or 4-bromo-3,3,4,4tetrafluorobut-1-ene (BTFB) 54 although VDC seems more reactive than these above monomers.…”

Controlled copolymerization of n-butyl acrylate with semifluorinated acrylates by RAFT polymerization

“…By copolymerizing vinylidene fluoride with a synthesized 2-trifluoromethacrylate monomer containing a C 6 F 13side chain (monomer: 3,3,4,4,5,5,6,6,7,7,8,8,8-tridecafluorooctyl 2-(trifluoromethyl)acrylate) the superior thermostability and hydrophobicity of the obtained copolymers were demonstrated by the same group 42 very recently, initiating the first radical copolymerization of chlorotrifluoroethylene and 3,3,4,4-tetrafluoro-4-bromobut-1-ene with tert-butylperoxypivalate. 43 Urban and co-workers 44 reported the conventional radical copolymerization of methyl methacrylate and nBuA † Electronic supplementary information (ESI) available: A synthetic route to semifluorinated homopolymer PHFBA, partial SEC traces of normalized UV signals for the obtained semifluorinated copolymers, ESI-TOF MS results of poly(nBuA-co-HFBA), poly(nBuA-co-PFPA) and poly(nBuA-co-TFEA), the different parameters to determine the reactivity ratios for the RAFT copolymerization of nBuA with HFBA, PFPA or TFEA, as well as the Fineman-Ross graphic method [G = f(H)], and the Kelen-Tüdos graphic method for each pair of co-monomers. See DOI: 10.1039/c4py01084a Institute of Chemistry, Chair of Macromolecular Chemistry, Faculty of Natural Sciences II (Chemistry, Physics and Mathematics), Martin-Luther University Halle-Wittenberg, von Danckelmann-Platz 4, Halle 06120, Germany.…”