When attempting to find the mechanisms involved in the thermal degradation of polymers, a problem arises when oligomers are observed as the principal products of thermal decomposition. In this case, one or more of at least three different general mechanisms may be responsible: (i) a high degree of random scission, (ii) intramolecular transfer during unzip, and/or (iii) secondary reactions of the primary products. This paper illustrates how these mechanisms can be differentiated by: (i) appropriate statistical plots of the yields of the products, (ii) quantitative measurements of rate constants for the evolution of the volatiles, and (iii) measurements of product yields and ratios as a function of sample size. Examples of the deduction of oligomer formation mechanisms are chosen from results for the following polymers: BIOPOL, polyisobutylene, polymethylacrylate, natural rubber, and polystyrene. © 1996 Elsevier Science Limited.
Lehrle, R. S., Atkinson, D. J., Bate, D. M., Gardner, P. A., Grimbley, M. R., Groves, S. A., … Williams, R. J. (1996). Diagnosing mechanisms of oligomer formation in the thermal degradation of polymers. Polymer Degradation and Stability, 52(2), 183–196. https://doi.org/10.1016/0141-3910(96)00014-6