Ls. Shi et Lb. Yuan, MECHANISM RESEARCH OF COPPER(II)-CATALYZED POLYMERIZATION OF 2,4,6-TRICHLOROPHENOLS, Journal of applied polymer science, 61(8), 1996, pp. 1279-1285
The copper(II)-catalyzed polymerization of 2,4,6-trichlorophenol and 2
,4,6-trichloro-3-methylphenol were studied. Their polymer structures w
ere confirmed by elemental analysis, infrared (IR), and nuclear magnet
ic 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) mea
surement of the phenoxo-copper(II) complexes were discussed in relatio
n to their structures. Decem position of the phenoxo-copper(II) comple
x in refluxing benzene yielded poly(dichlorophenylene oxide). ESR meas
urements on the phenoxo-copper(II) complex in the solid state at 120 d
egrees C indicated that the phenoxy radical was generated during the p
eriod of decomposition and the intensity of the ESR spectra based on t
he copper(II) ion decreased with the measurement time. A single-electr
on transfer reaction mechanism was proposed for the phenoxo-copper(II)
complex intermediate. (C) 1996 John Wiley & Sons, Inc.