Molecular weight distribution changes during the thermal breakdown of poly‐α‐methylstyrene

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Abstract
The changes in the molecular weight distribution accompanying the thermal depolymerization of poly‐α‐methylstyrene have been investigated. The original polymer, produced by anionic catalysis, had a narrow distribution of molecular weights, which facilitated measurement of the changes. The depolymerization when carried out in a thin polymer film at 226 and 236° caused extensive randomization of molecular weights at low conversions. In contrast, a similar depolymerization carried out in Decalin solution at 232° produced polymer maintaining the original sharp distribution. It is concluded that the kinetic chain length of the depolymerization reaction is much smaller than the molecular chain length in solid film reactions, but much greater than the molecular chain length in solution, under the experimental conditions used.

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