Fluorinated cotelomers based on vinylidene fluoride (VDF) and hexafluoropropene (HFP): Synthesis, dehydrofluorination and grafting by amine containing an aromatic ring

• Published in: Journal of fluorine chemistry Vol. 128; no. 6; pp. 619 - 630
• Main Authors: Taguet, A., Sauguet, L., Ameduri, B., Boutevin, B.
• Format: Journal Article
• Language: English
• Published: LAUSANNE Elsevier B.V 01.06.2007; Elsevier
• Subjects: 19F NMR characterization; Chemical Sciences; Chemistry; Chemistry, Inorganic & Nuclear; Chemistry, Organic; Grafting by amine; Hexafluoropropene (HFP); Physical Sciences; Polymers; Radical telomerization; Science & Technology; Vinylidene fluoride (VDF); Radical telomerization; 19F NMR characterization; Vinylidene fluoride (VDF); Grafting by amine; Hexafluoropropene (HFP); POLYMERIZATION; hexafluoropropene (HFP); RADICAL-ADDITION; MONOMERS BEARING; vinylidene fluoride (VDF); REACTIVE LATERAL GROUP; F-19 NMR characterization; TELOMERS; PART 6; radical telomerization; TELOMERIZATION; TETRAFLUOROETHYLENE; PERFLUOROALKYL IODIDES; COPOLYMERIZATION; grafting by amine
• ISSN: 0022-1139; 1873-3328
• DOI: 10.1016/j.jfluchem.2007.02.005

The synthesis of a model molecule ( 11 trans) for the grafting of an amine containing an aromatic ring onto a cotelomer containing vinylidene fluoride (VDF) and hexafluoropropene (HFP) is presented: ▪ The synthesis of C 6F 13CH 2C(CF CFCF 3) N–C 2H 4–C 6H 5 ( 11) from the addition of H 2N–C 2H 4–C 6H 5 onto C 6F 13CH 2CF 2CF 2CFHCF 3 ( 3) is presented. C 6F 13CH 2CF 2CF 2CFHCF 3 ( 3) and C 6F 13CH 2CF 2CF(CF 3)CF 2H ( 3′) isomers were obtained from the thermal stepwise cotelomerization of vinylidene fluoride and hexafluoropropene with C 6F 13I, followed by the selective reduction of the iodine end atom. At 200 °C, the 3/ 3′ molar ratio reached 9.0. In contrast to selective reduction, dehydrofluorination led to various derivatives, which were characterized by 1H NMR and 19F NMR spectroscopy, and hence a reaction pathway could be suggested. The grafting of an amine containing an aromatic ring onto the cotelomers based on VDF and HFP occurred selectively on VDF/HFP diad and, in some instances a further step involving the formation of an imine was observed. The addition of 2-phenylethylamine onto the dehydrofluorinated intermediates was found to be quantitative.