Abstract
Electrochemically generated radical anions have been investigated as possible initiators of the anionic polymerization of vinyl monomers in anhydrous DMF. While such radicals are not reactive towards methylmethacrylate and styrene, they decay in the presence of acrylonitrile initiating its anionic polymerization with production of oligomers of average molecular weight about 1200. Kinetic results obtained amperometrically or by EPR spectrometry show that the initiation process is a proton transfer from the monomer to the radical anion. This mechanism is confirmed by the results of substituent effects on the specific rate constants.
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