Phenylacetylene, diphenyldiacetylene and methyl propiolate were polymerized by electrochemical initiation in aprotic, polar solvents (dimethylformamide, dimethylacetamide and acetonitrile) using ammonium, phosphonium, arsonium and stibonium quaternary salts (alkyl‐, aryl‐ and alkyl‐aryl‐substituted) as background electrolytes. The effect of electrolyte nature and concentration, of the solvents and of electrolysis conditions on the product yields were studied as well as some properties of the obtained polymers.
SUMMARY: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.
ZUSAMMENFASSUNG:Es wurde die polarographische Reduktion von Acetylenderivaten vom Typus des Phenylacetylens, des Diphenyldiacetylens und des Methylpropiolats untersucht , sowie auch die von Elektrolyten vom Typus der quaternken Salze (Ammonium, Phosphonium, Arsonium und Stibonium), um festzustellen, ob die elektro-initiierte Polymerisation durch unmittelbare Elektroneniibertragung an das Monomere oder indirekt stattfindet. Es wurden die Halbwellenpotentiale der erwahnten Verbindungen an der Quecksilbertropfelektrode und an einer stationaren Platinelektrode gemessen. Aus den Versuchsergebnissen der obigen Polymerisation von Acetylenmonomeren ergaben sich einige Folgerungen fiir die Kinetik des Polymerisationsvorgangs.
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.
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