Reactions and stability of fluorinated poly(vinyl trimethylsilane) in electrochemical systems

Fluorinated poly(vinyl trimethylsilane) (FPVTMS) unlike virgin PVTMS is able to participate in electrochemical reactions and undergoes direct and indirect electrochemical reductive degradation. Specifically, its perfluorinated units are reduced irreversibly at a glass carbon electrode in a 0.05-M (C4H9)4ClO4 solution in dimethylformamide with subsequent splitting of C–F bonds and formation of conjugated double bonds in macromolecules at the polymer surface. On the other hand, the incompletely fluorinated units at the FPVTMS surface interact with the previously electrochemically reduced background solution to be dehydrofluorinated. This is accompanied by the formation of conjugated double bonds and dissolution of the dehydrofluorinated layer also. The data obtained allowed distinguishing the incompletely fluorinated units from the perfluorinated ones in the fluorinated layer of FPVTMS. Moreover, the quantity of the incompletely fluorinated units in FPVTMS can be determined. It was found that the strengthening of fluorination conditions led to an enhancement of the electrochemically induced FPVTMS transformations.