The degradation of vinyl polymers

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Abstract
The degradation of a high polymer is the process of breakdown by various agencies of the long chain molecules. In the case of vinyl polymers, (the degradation reaction, though not so important commercially as the polymerization process,) may be utilized in various ways; for instance, (a) polymers such as rubber may be more easily processed if first degraded and the degree of polymerization stabilized at some lower level.(b) monomer may be regenerated from scrap polymer, (c) compounds which cannot easily be synthesized can be produced by chemical reaction with the polymer and subsequent depolymerization, (d) the process may elucidate polymer structure.The degradation of three representative polymers, namely, those of styrene, methyl methacrylate and x‐methylstyrene, (I, II, III), is discussed here Low polymers of α‐methylstyrene have a cyclic structure, but longer chains may contain branches due to activation of the methyl group.In general, degradation increases with reaction temperature, and structures containing quaternary carbon (or hetero) atoms are most readily and perfectly degraded. The destructive distillation polymethyl methncrylate and poly α‐methylstyrene yields more than 90% monomer, but only 60‐65% is obtained from polystyrene.Degradation, whether in bulk pyrolytic or in solution, exhibits the same fundamental principles.

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