Grafting of commercially available amines bearing aromatic rings onto poly(vinylidene‐co‐hexafluoropropene) copolymers

The grafting of poly(VDF‐co‐HFP) copolymers with different amines containing aromatic rings, such as aniline, benzylamine, and phenylpropylamine, is presented. ¹⁹F NMR characterization enabled us to show that the sites of grafting of aromatic‐containing amines were first difluoromethylene of vinylidene fluoride (VDF) in the hexafluoropropene (HFP)/VDF/HFP triad and then that of VDF adjacent to HFP. The kinetics of grafting of benzylamine, monitored by ¹H NMR spectroscopy, confirmed those sites of grafting and showed that all VDF units located between two HFPs were grafted in the first 150 min, whereas those adjacent to one HFP unit were grafted in the remaining 3000 min. Parameters such as the temperature or the molar percentage of HFP in the copolymer had an influence on the maximum rate of grafted benzylamine. The higher the temperature, the higher the molar percentage of grafted benzylamine. Furthermore, the higher the molar percentage of HFP in the copolymer, the higher the molar percentage of VDF in the HFP/VDF/HFP triad, and the higher the molar percentage of grafted benzylamine. The spacer length between the aromatic ring and the amino group had an influence on the kinetics of grafting: aniline (pK_a = 4.5) could not add onto the polymeric backbone, whereas phenylpropylamine was grafted in the first 150 min, and benzylamine required 3000 min to reach the maximum amount of grafting. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1855–1868, 2006