Application of the random break theory to thermal degradation of polymers

Thermal degradation of high-molecular-weight polyethylene is considered from the standpoint of the random break theory. The quantitative estimations made indicate that the vaporization conditions realized in the experiment exert a decisive effect on the total conversion rate. The heat of vaporization of macromolecular fragments formed by cleavage of C-C bonds amounts to approximately a half of the total thermal effect recorded by thermal analysis. The results obtained make it possible to rationalize some phenomena that were observed experimentally but have not been satisfactorily interpreted previously, and also to predict the influence of experimental conditions on the course of thermal degradation of polymers.