Pud A. Electrochemical reductive degradation of polymers.

The dissertation contains results of system investigations and analysis of electrochemical destructive and polymeranalogous transformations of polymers at a cathode, which were defined in total as electrochemical reductive degradation (ECRD). In the work this phenomenon was characterized from unified positions for the first time. There were established its causes and regularities for polymers of different classes. Systematization of ECRD processes was performed and their classification was suggested. The classification is based on dividing the processes on direct transformations of polymers (accumulative and dissociative types) realizing under the effect of polymer direct electrochemical reactions, and on indirect ones (three types) running in the result of interaction of pristine or electrochemically reduced polymers with other components of electrochemical system or with products of electrochemical transformations of these components. For the first the electrochemical activity of some aromatic polyesters (polycarbonates, poly(ethylene terephthalate) and aromatic fluorinated polyamides was established and investigated. Their ECRD regularities were determined and mechanism of this process was suggested. In the case of perfluorinated polymers (PTFE) and perfluorinated units of fluorinated polymers as well as of ethylene-vinyl acetate copolymers a dissociative mechanism of direct ECRD was found and investigated. Mechanism of splitting of C-F bonds when electrochemical reduction of perfluorinated links of polymers was suggested and studied for the first time. The principal change of direct mechanism of electrochemical transformations to indirect one was found and investigated when transition from perhalogenated polymers to incompletely halogenated polymers.