Electron Transfer Reactions of Radical Anions with TEMPO: A Versatile Route for Transformation of Living Anionic Polymerization into Stable Radical‐Mediated Polymerization

Summary: The possibility of transforming a living anionic polymerization into a stable radical‐mediated radical polymerization (SFRP) was demonstrated. For this purpose, 2,2,6,6‐tetramethylpiperidine‐ N ‐oxyl (TEMPO) alcoholate, formed by a one‐electron redox reaction between potassium naphthalene and TEMPO, was used to initiate the living anionic polymerization of ethylene oxide (EO). Poly(ethylene oxide) obtained in this way possessed TEMPO terminal units and was subsequently used as an initiator for the SFRP of styrene to give block copolymers. A one‐electron redox reaction gives rise to TEMPO alcoholate, which is able to initiate the living anionic polymerization of ethylene oxide (EO). image A one‐electron redox reaction gives rise to TEMPO alcoholate, which is able to initiate the living anionic polymerization of ethylene oxide (EO).