Abstract
Films of poly( p-propionylstyrene) were exposed to long-wave u.v. radiation ( λ ⩾ 300 nm) under high vacuum at 25°. The volatile products were quantitatively analyzed by mass spectrometry. The principal initial photoreactions are Norrish Type I α-cleavages but some β-cleavage also occurs with the formation of methyl radicals. The resulting free radicals participate in abstraction reactions with the polymer. Cross-linking occurs by the interaction of a variety of macroradicals. The importance of the carbonyl triplet is demonstrated and its lifetime, as determined by time-resolved spectroscopy and laser flash photolysis, is 147 ± 10% nsec. The polymer is less susceptible to photodegradation than poly( p-acetylstyrene).
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