Synthesis of New Fluoroboronated Materials by Chemical Modification of Fluorinated Functional Polymers

New fluoroboronated materials were obtained by chemical modification of poly-(VDF-co-MAF) copolymers synthesized by the radical copolymerization of vinylidene fluoride (VDF) with 2-(trifluoromethyl) acrylic acid (MAF). Two copolymers were first synthesized in dimethylcarbonate (DMC) or 1,1-difluoro-1-chloroethane as the solvents in 60% yields with molar masses of 22,000 and 12,000 g·mol^-1, respectively. Although MAF does not homopolymerize under radical initiation, this is a suitable comonomer for VDF. The transfer rates were 0.40 and 0.21 for reactions carried out in DMC and in halogenated solvent, respectively. The resulting poly-(VDF-co-MAF) random copolymers were condensed with aminophenyl boronic acid pinacol ester (APBAPE) in the presence or absence of a HCl trap to obtain new fluoroboronated copolymer materials. Their ¹H, ¹¹B, ¹³C, and ¹⁹F NMR and ATR IR characterizations confirmed the successful addition of APBAPE onto the fluorinated copolymer. The thermal properties of all these original copolymers were determined. As expected, the thermal stability of poly-(VDF-co-MAF.APBAPE) copolymers displayed better behavior due to the decarboxylation of acid functions in MAF units as noted in their precursors. Such novel fluoropolymers bearing boron-containing groups may have potential applications in various areas as electronics and coatings.