Abstract
The paper deals with the effect of the light wavelength and plasticizers on the formation of polyenes and evolution of HCl, as well as on accumulation of alkyl and polyenyl radicals, during photolysis of poly(vinyl chloride) (PVC). The total number of polyenes and the distribution of their lengths are quantitatively analyzed by numerical modelling of the recorded spectra with the aid of the absorption spectra of model compounds. The dependences of the quantum yield of dehydrochlorination on the wavelength are determined. The correlation between the dehydrochlorination rate and steady-state concentration of radicals, as well as the agreement between the photochemical sensitivity spectra of an intermediate and the absorption spectra of radicals, suggest that radicals are photochemically active intermediate products of the dehydrochlorination. The constants of the individual stages are evaluated on the basis of ideas about the photochain character of the process in rigid PVC.
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