Abstract
The effect of temperature on the photo-degradation of polystyrene has been investigated using electron spin resonance, Fourier Transform infra-red spectral analysis and gel fraction measurement. Photo-irradiations were carried out with light from a medium pressure mercury lamp at 30°C (< Tg), 100°C (⋍ Tg) and 120°C (> Tg). The initial product of photo-degradation was the polystyryl radical. The concentration of this radical decreased and oxygenated product formation was accelerated by irradiations at higher temperatures, reflecting the segmental motion of the polymer chain. Crosslinking through combination of polystyryl radicals occurred as a result of irradiations both in air and in vacuum, and the maximum crosslinking was obtained in the case of irradiation in the vicinity of Tg. These results are explained on the basis of the segmental motion of polymer chains.
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