Abstract
The synthesis of PVDF-g-oligo(HFPO) graft copolymers,where VDF and HFPO stand for vinylidene fluoride and hexafluoropropyleneoxide, respectively, is presented. First, an oligo(HFPO)−OCFCF2 macromonomer was prepared from two methods startingfrom oligo(HFPO) acyl fluoride in 34 to 54% yield. Then, the radicalcopolymerization of VDF with that comonomer, initiated by tert-butylperoxypivalate (TBPPi) or perfluoro-3-ethyl-2,4-dimethyl-3-pentyl persistentradical (PPFR) was studied under various conditions. The resultingPVDF-g-oligo(HFPO) graft copolymers were produced in good isolatedyields (74 to 89%). The molar percentages and molecular weights of thegraft copolymers were assessed by 19F and 1H NMR spectroscopy. Molarpercentages of VDF and oligo(HFPO)−OCFCF2 comonomers reachedup to 99% and 11%, respectively, while the molecular weights ranged from25 000 to 77 000 g/mol. Their thermal properties were also studied and showed: (1) satisfactory thermostability (Td) in the 410to 494 °C range under air and (2) melting temperature (Tm) between 138 to 159 °C, while (3) the glass transition (Tg) ranged from -79 to -54 °C