Electrochemical polymerization of dicarboxylic acids—VI. Mechanism of polymerization

Abstract

The mechanism of the electrochemical polymerization of dicarboxylic acids in various solvents, which also leads to the formation of various side products, is discussed. The formation of hydrocarbons was rationalized through the formation of α,ω-biradicals which suffer coupling or disproportionation reactions. Carboxylic acids are shown to originate from reactions of •(CH 2) k COOH radicals which couple radicals which couple or disproportionate among themselves or other radicals to give saturated and unsaturated acids. Cations formed from anodic oxidation of the radicals are the precursors of lactones and some olefins. The conformations of the dicarboxylate anions at the anode surface are discussed with a view of rationalizing the formation of the various products. Polymer formation was explained as occurring through α,ω-biradicals having a definite conformation. Pyridine affected to a large extent these conformations, and higher concentrations of pyridine led to an increase in the conformations which lead to polymer formation.