Mechanism research of copper(II)-catalyzed polymerization of 2,4,6-trichlorophenols

The copper(II)-catalyzed polymerization of 2,4,6-trichlorophenol and 2,4,6-trichloro-3-methylphenol were studied. Their polymer structures were confirmed by elemental analysis, infrared (IR), and nuclear magnetic resonance (NMR). The 2,4,6-trichlorophenoxo–copper(II) complex and 2,4,6-trichloro-3-methylphenoxo–copper(II) complex intermediates were isolated. The elemental analysis and electron spin resonance (ESR) measurement of the phenoxo–copper(II) complexes were discussed in relation to their structures. Decomposition of the phenoxo–copper(II) complex in refluxing benzene yielded poly(dichlorophenylene oxide). ESR measurements on the phenoxo–copper(II) complex in the solid state at 120°C indicated that the phenoxy radical was generated during the period of decomposition and the intensity of the ESR spectra based on the copper(II) ion decreased with the measurement time. A single-electron transfer reaction mechanism was proposed for the phenoxo–copper(II) complex intermediate. © 1996 John Wiley & Sons, Inc.