Photobleaching of chemically degraded poly(vinyl chloride)

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Abstract
Dilute (0.23%) tetrahydrofuran solutions of chemically degraded poly(vinyl chloride) were irradiated with monochromatic light (307,320, or 354 nm) after being degassed or saturated with oxygen. The rates of the resulting photobleaching reactions of the polyene sequences present depended in a complex way on the wavelength of the light used and on the presence or absence of oxygen. During 307‐nm irradiation an initial fast decrease in absorbance at 307 nm, which proceeded with a rapidly decreasing quantum yield and which was unaffected by oxygen, was followed by a slower reaction with constant quantum yield that was strongly inhibited by oxygen. The same general trend was observed for solutions irradiated with 320‐ or 354‐nm light but in each case the rates of changes in absorbance at wavelengths other than those irradiated were complex. A mechanism that involves intra‐ and intermolecular reactions of the polyenes is suggested to explain the observed effects.

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