'Radical-controlled' oxidative polymerization of m-cresol catalyzed by μ-η2:η2-peroxo dicopper(II) complex

Described is an oxidative polymerization of m-cresol catalyzed by (1,4,7-triisopropyl-1,4,7-triazacydononane)copper complex, from which a mu-eta(2):eta(2)-peroxo dicopper(II) complex is formed under dioxygen and reacts with m-cresol to give 'controlled' phenoxy radical-copper(I) complex exclusively without formation of 'free' phenoxy radical. The present catalyst showed the highest activity in the metal complex catalysts reported for the polymerization of m-cresol with dioxygen. The resulting polymer consisted of oxyphenylene units and showed high molecular weight and high thermal stability. The high selectivity toward C-O linkage would be due to the coupling from the phenoxy radical species controlled by this catalyst. (C) 2000 Elsevier Science B.V. All rights reserved.