Abstract

The reaction of poly(2,6-dimethyl-1,4-phenylene oxide) with hydroxy (HO .) and hydroperoxy (HO 2 .) radicals generated by the UV photolysis of concentrated hydrogen peroxide (H 2O 2) (35wt%) has been studied. The HO ./HO 2 . radicals accelerate the photo-oxidative chain-scission of a polymer, in comparison with photo-oxidative degradation in air or in water. However, both HO . and HO 2 . radicals undergo additional reactions to the aromatic phenyl rings in a polymer. Spectroscopic analyses suggest the presence of phenols and hydroxy-mucondialdehydes among the photo-oxidation products, indicating that HO . and HO 2 . addition occurs at the phenyl groups of the polymer. Rearrangement of hydroxy-phenyl radicals can also produce quinoide structures. Coloration of the polymer can result from formation both of quinone and hydroxy-mucondialdehyde structures in photo-oxidized polymer. The significance of HO . radicals formed from the thermolysis and/or photolysis of hydroperoxides in the polymer is considered.

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