The changes in the molecular composition of purified commercial polystyrene following thermal degradation were analyzed by gel permeation, reverse phase liquid and gas chromatography. Three major low molecular weight compounds were identified: styrene monomer, a dimer, and a trimer. The composition, the molecular weight, and the structure of the two oligomers were determined by elementary analysis, mass spectroscopy, nuclear magnetic resonance, and infrared spectroscopy. A linear structure with an ethylene end group is proposed for the two oligomers. The appearance of these degradation compounds is explained on the basis of an intramolecular mechanism involving chain‐end folding and transfer of a labile tertiary hydrogen.
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Daoust et al. (1981) studied this question.
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