Electroinitiated polymerization of some acetylenic derivatives, a polarographic study

Abstract

The polarographic reduction of some acetylenic derivatives—phenylacetylene, diphenyldiacetylene and methyl propiolate, as well as of some quarternary salts (ammonium, phosphonium, arsonium and stibonium), was investigated in order to establish whether the electroinitiated polymerization process took place by direct electron transfer to the acetylenic monomer or indirectly. The half‐wave potentials of the compounds mentioned at the dropping mercury cathode and at the stationary platinum electrode were measured. From the experimental data on the polymerization of the above acetylenic monomers, some statements on the kinetics of the polymerization process were made.

Mechanism of electropolymerization of phenylacetylene in propylene carbonate

“…Although most of these polymers can be synthesized chemically using catalysts, the electrochemical method is an easier means of production and control of the polymerization. This method allows one to control the kinetic parameters of the reaction, the polydispersity, the molar mass of the final product and the fact that it leads to materials with special properties which cannot be obtained by conventional methods [3]. The main requirements for electropolymerization via oxidation are that the monomer should have an oxidation potential which should be accessible via a suitable solvent system, producing a radical cation which is able to react more readily with other monomer molecules to form the polymer than with other nucleophiles which could be present in the electrolyte solution [2].…”

Electropolymerization of phenylacetylene in acetonitrile

“…Most of the polymers derived from acetylene are chemically synthesized with metal catalysts. Another method of production is anodic oxidation electropolymerization, which offers the possibility of controlling the kinetic parameters of the reaction, the polydispersity and the molecular weight, and also leads to materials with special properties that cannot be obtained by catalytic methods 1. The main requirement for efficient anodic oxidation is the oxidation potential of the monomer.…”