Atom Transfer Rearrangement Radical Polymerization of Diamminebis( 2,4,6-trihalophenolato)copper(II) Complexes in the Solid State

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The synthesis of the poly(dichloro- or dibromophenylene oxide)s was achieved by the thermal decomposition of diammine-bis(2,4,6-trihalophenolato)copper(II) complexes in the solid state by atom transfer rearrangement radical polymerization. The thermal decomposition was performed either at different temperature ranges, 110 - 250 °C, for 3 h, or at the maximum conversion temperature for different time intervals, 3 - 48 h. Maximum yields of polymers were obtained at 190 °C and 3 h. The polymers were characterized by FTIR, 1H and 13C NMR spectroscopy, SEM, TGA and molecular weight determination by viscometrical methods. All the polymers were rigid, having high Tg values between 178 and 189 °C. Only small amounts of Cu were detected by AAS.