Cationic polymerization of styrene with electrochemically generated perchloric acid—II |
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Authors: | G. Pistoia |
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Affiliation: | Istituto di Chimica delle Macromolecole del Consiglio Nazionale delle Ricerche, Istituto Chimico, Università di Roma, Rome, Italy |
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Abstract: | 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. Kp values are considerably lower than those found in HClO4C2H4Cl2 and in HClO4CH2Cl2, thus confirming that the influence of the solvent in these processes is not merely electrostatic. |
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