Pyrolysis of Polymers

The nature of their pyrolysis products, monomer, oligomers and carbonaceous residues enables one to group polymers into three classes, those that decompose by net main chain scission; by stripping of the main chain, for example the thermal dehydrochlorination of polyvinyl chloride; and by crosslinking of the main chain followed by some production of volatiles. Highly unsaturated or aromatic chains tend to follow the latter course.

At the present time a theoretical framework exists which permits, provided adequate experiments are performed, the elucidation of the decompositions of the first type. For most of the well-known polymers in this class, this framework of knowledge gives very acceptable mechanistic explanations or interpretations of the decomposition process based on observations of rate of weight loss, of molecular weight changes and composition of volatile products.

Knowledge of the decomposition of the second class of polymers is at an intermediate state development. However, an important practical research objective would be the acquisition of methods for converting the mechanisms of decomposition of class one substances to that for class two type.

For the third class of materials, knowledge of their pyrolysis mechanisms is nonexistent. This is largely due to the fact that methods for quantitatively following solid-phase processes of decomposition are relatively difficult and unsatisfactory.