The photo‐oxidation of solid polymers at ambient temperatures is shown to be greatly affected by the low mobility of radicals in the solid state. When a radical pair, produced by photo‐initiation, escapes the initial polymer cage, the probability of its recombination remains high even after several propagation steps. This phenomenon, known as secondary cage recombination, has a pronounced effect on the kinetics of oxidation and on the mechanism of photostabilisation by radical scavengers. The occurrence of secondary cage recombination is demonstrated for polypropylene photo‐oxidation and a kinetic analysis is developed to predict the consequences of this effect.
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Garton et al. (1980) studied this question.
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