ELECTROCHEMICALLY INDUCED FUNCTIONALIZATION OF FLUOROCONTAINING POLYOLEFINS

Mechanistic aspects of electrochemical transformations of polyvinylide nefluoride (PVDF), polyvinylfluoride (PVF), copolymers of vinylidenefl uoride (VDF) with tetrafluoroethylene (TFE) and hexafluoropropylene (H FP) at a cathodes of different nature in dimethylformamide in the pres ence of 0,1 M (C4H9)4NClO4 have been investigated. It is found that hy drogenfluorocontaining links of the copolymers, PVF and PVDF are able to dehydrofluorination at a cathode in investigated conditions. The ma in reason of this is an attack of macromolecules by negatively charged nucleophilic products that are formed at the dimethylformamide electr ochemical reduction. Perfluorinative TFE and HFP links undergo direct electrochemical reduction through two irreversible stages with subsequ ent fluorine anions elimination and polyconjugated bonds formation. Ba sed on the electrochemical and spectral data two different mechanisms of fluorocontaining carbochain polymers transformation at a cathode we re suggested. On the whole, the obtained data testify to the possibili ty of an employment of polymer electrohemical transformations to reali ze their functionalization.