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Revising the mechanism of polymer autooxidation

Gryn'ova, Ganna, Hodgson, Jennifer L., Coote, Michelle L.·2011·Org. Biomol. Chem.
DOI 10.1039/c0ob00596g
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Abstract

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.

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Metadata

Authors
Gryn'ova, G., Hodgson, J. L., & Coote, M. L.
Venue
Org. Biomol. Chem.
Publisher
Royal Society of Chemistry (RSC)
Published
2011
Volume
9
Issue
2
Pages
480-490
ISSN
  • 1477-0520 (ISSN-L)
  • 1477-0539
DOI
10.1039/c0ob00596g
OpenAlex
W2125171327
Cited by
217
References
0
FWCI
1.89
Type
journal article
Language
en
Open access
closed

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Gryn'ova, G., Hodgson, J. L., & Coote, M. L. (2011). Revising the mechanism of polymer autooxidation. Org. Biomol. Chem. https://doi.org/10.1039/c0ob00596g

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