Chain transfer, thermal degradation

Mechanisms of thermal degradation of PVC, the structure of PVC and the stabilization of PVC have been the subject of many reviews. Those by Starnes,44 Endo45 and Ivan46 are some of the more recent. Defect structures in PVC arise during the propagation and chain transfer steps. As with PMMA, PVC formed by... 

Richards and Slater (75) used a labelled polystyrene to demonstrate the existence of intermolecular chain transfer in the thermal degradation process. Polystyrene-14C, prepared in the normal way, was mixed with an inactive polystyrene specially prepared with weak links so that it degraded at temperatures where the polystyrene-14C was stable when on its own. Appearance of styrene- C monomer in the volatile degradation products proved the existence of intermolecular chain transfer (Reaction 9). 

The degradation reactions of polymers have been widely reviewed 525). In the absence of air, thermal reactions are the important degradation route. They may involve reactions of functional groups on the chain without chain scission, typified for example by the dehydrochlorination of PVC, or reactions involving chain scission, often followed by depropagation and chain-transfer reactions to yield complex mixtures of products. This latter route would be typical of the degradation of poly(methyl methacrylate), which depolymerizes smoothly to its monomer, and of polystyrene, which produces a wide range of tarry products. 

Instability of the polymer is responsible for the primary step in decomposition and is attributed either to fragments of initiator or to branched chains or to terminal double bonds. The appearance of branching is the result of reactions of chain transfer through the polymer, while that of unsaturated terminal groups results from reaction of disproportionation and chain transfer through the monomer. During thermal and thermo-oxidative dehydrochlorination of PVC, allyl activation of the chlorine atoms next to the double bonds occurs. In this volume, Klemchuk describes the kinetics of PVC degradation based on experiments with allylic chloride as a model substance. He observed that thermal stabilizers replace the allylic chlorine at a faster ratio than the decomposition rate of the allylic chloride. 

Tsuchlya and Suml (6) have thermally degraded polypropylene in the temperature range ShO-AOO C and have made a detailed analysis of all products with 1-12 carbon atoms. On this basis, a decomposition mechanism has been proposed. Initiation occurs by random scission of the main chain. The radicals thus formed undergo transfer reactions most readily at tertiary carbon atoms but the distribution of products indicates that intramolecular transfer to both third and fourth carbon atoms is particularly important. 

The radical mechanism of thermal degradation of pristine PE has been widely discussed in a framework of random scission type reactions [14-22], It is known that PE decomposition products comprise a wide range of alkanes, alkenes and dienes. Branching of PE chains causes enhanced intermolecular hydrogen transfer and results in lowering thermal stability. The polymer matrix transformations, usually observed at lower temperatures and involving... 

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