Abstract

Changes of molecular weight distribution resulting from vacuum photolysis and photo-oxidation of polystyrene have been determined by gel permeation chromatography. On irradiation at 253.7 nm, crosslinking is predominant in vacuo; in the presence of oxygen, crosslinking and main chain scission occur simultaneously because of light absorption by two or more different chromophores. Main chain scission is more important than crosslinking in the photolysis and photo-oxidation of polystyrene containing cumene hydroperoxide irradiated at 313 nm or containing benzophenone irradiated in the range 320–420 nm. In this last case, main chain scission and crosslinking are both strongly inhibited if the sample contains napthalene which acts as quencher of the excited triplet state of benzophenone. Only moderate inhibition is observed in the presence of 2,6-di- t-butyl-4 methylphenol.

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