| Abstract: | “Radical‐controlled” oxidative polymerization of phenol (p‐1) by (1,4,7‐triisopropyl‐1,4,7‐triazacyclononane)copper(II) catalyst was performed and compared with that of 4‐phenoxyphenol (p‐2) in detail. Although the coupling selectivity for p‐1 seemed to be controlled by the catalyst, the C? C coupling, which was excluded completely for p‐2, occurred to some extent. The initial reaction rate of p‐1 was much smaller than that of p‐2, leading to the difference of polymerization behavior between p‐1 and p‐2. The rate‐determining step would be the coupling of controlled radicals species from the ESR measurement of the reaction mixture. The polymer resulting from p‐1 consisted mainly of phenylene oxide units, but had no crystallinity in contrast to the crystalline polymer from p‐2. However, the present polymer showed the highest thermal stability in the polymers obtained by oxidative polymerization of p‐1. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 1955–1962, 2005 |
