Cationic polymerization of styrene with electrochemically generated perchloric acid—II

The electroinitiated polymerization of styrene in LiClO₄-PC solutions has a living character due to the absence of termination. Marked side reactions were observed, limiting the yields. These reactions are mainly due to monomer oxidation by HClO₄ and polymer degradation at the anode. They can be minimized by increasing the monomer concentration. Conversion vs time curves show an induction period, an ascending linear portion and a descending portion. Kinetic treatment limited to the ascending portions shows that the polymerization is first-order with respect to monomer and HClO₄ concentrations. K_p values are considerably lower than those found in HClO₄C₂H₄Cl₂ and in HClO₄CH₂Cl₂, thus confirming that the influence of the solvent in these processes is not merely electrostatic.