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Issue 2, 2011
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Revising the mechanism of polymer autooxidation

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The basic scheme for autooxidation of polymers, originally developed by Bolland, Gee and co-workers for rubbers and lipids, is now widely applied to all types of polymeric materials. According to their scheme, the reaction that makes this process autocatalytic, referred to as the propagation step, is a hydrogen abstraction from the next substrate by the peroxyl radical (ROO˙ + RH → ROOH + R˙). In this study, using advanced quantum-chemical methods, we have shown that this step is actually characterised by largely positive Gibbs free energy (10–65 kJ mol−1) for most regular polymers with saturated chains (polypropylene, polyethylene, polyvinyl chloride, polyvinyl acetate, polyurethane, poly(methyl methacrylate)etc.) and even some polymers with unsaturated fragments (polystyrene, polyethylene terephthalate). Neither elevated temperature, nor solvation makes this process thermodynamically favourable. Only when the formed radical centre is conjugated with adjacent double bonds (as in polybutadiene) or captodatively stabilised by two suitable functional groups (such as a carbonyl and a lone pair donor such as oxygen or nitrogen), is the propagation step exoergic. Instead, we show that it is the presence of structural defects, such as terminal or internal double bonds, formed either during polymerisation or in the degradation process itself, that is responsible for the autooxidation of most polyesters and most polyalkenes. Recognition of the real mechanism of autooxidation in polymers is a key to developing strategies for the prevention of their degradation.

Graphical abstract: Revising the mechanism of polymer autooxidation

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Publication details

The article was received on 18 Aug 2010, accepted on 29 Sep 2010 and first published on 11 Nov 2010

Article type: Paper
DOI: 10.1039/C0OB00596G
Org. Biomol. Chem., 2011,9, 480-490

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    Revising the mechanism of polymer autooxidation

    G. Gryn'ova, J. L. Hodgson and M. L. Coote, Org. Biomol. Chem., 2011, 9, 480
    DOI: 10.1039/C0OB00596G

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