Abstract
The rate constant of hydrogen abstraction by the n, π* triplet state of poly(4-vinylbenzophenone) (PVBP) from tetrahydrofuran was compared with that of benzophenone (BP) in benzene solution at 25°C, the former being about twice as large as the latter. The electronic behavior of the triplet BP group in the polymer was investigated by T—T absorption and phosphorescence, being the same as that of BP. A well-resolved ESR spectrum of the diphenylamino radical was detected upon UV irradiation of a benzene solution of PVBP and diphenylamine (DPA) and its concentration was compared with that of the poly(vinylbenzophenone-co-methyl methacrylate)—DPA or BP—DPA system. The concentration decreased in the order: PVBP>copolymer>BP. The polymer effect on the rate constant and the radical formation was explained in terms of the increase in the reaction efficiency on account of energy migration along the side chain of the polymer.
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