The Fate of the Peroxyl Radical in Autoxidation: How Does Polymer Degradation Really Occur?

Accounts of Chemical Research
Leesa M SmithMichelle L Coote

Abstract

Bolland and Gee's basic autoxidation scheme (BAS) for lipids and rubbers has long been accepted as a general scheme for the autoxidation of all polymers. This scheme describes a chain process of initiation, propagation, and termination to describe the degradation of polymers in the presence of O2. Central to this scheme is the conjecture that propagation of damage to the next polymer chain occurs via hydrogen atom transfer with a peroxyl radical. However, this reaction is strongly thermodynamically disfavored for all but unsaturated polymers, where the product allylic radical is resonance-stabilized. Paradoxically, there is no denying that the autocatalytic degradation and oxidation of saturated polymers still occurs. Critical analysis of the literature, described herein, has begun to unravel this mystery. One possibility is that the BAS still holds for saturated polymers but only at unsaturated defect sites, where H transfer is thermodynamically favorable. Another is that peroxyl termination rather than H transfer is dominant. If this were the case, tertiary peroxyl radicals (formed at quaternary centers or quaternary branching defects) may terminate to form alkoxy radicals, which can much more readily undergo chain transfer. ...Continue Reading

References

Nov 13, 2010·Organic & Biomolecular Chemistry·Ganna Gryn'ovaMichelle L Coote
Aug 25, 2011·Chemical Reviews·Huiyong YinNed A Porter
Aug 22, 2012·Chemical Society Reviews·Daniel StoneDwayne E Heard
Aug 21, 2013·Physical Chemistry Chemical Physics : PCCP·Richmond Lee, Michelle L Coote
Aug 23, 2016·Physical Chemistry Chemical Physics : PCCP·Richmond Lee, Michelle L Coote
Jul 7, 2008·Science and Technology of Advanced Materials·Hisayuki NakataniMinoru Terano

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Citations

Feb 8, 2020·Macromolecular Rapid Communications·Efthymia VakalopoulouChristian Slugovc
Aug 19, 2020·Biomaterials Science·Junfei HuYiwen Li
Feb 13, 2021·The Journal of Organic Chemistry·Olga V KushchAlexander N Shendrik
Jul 31, 2021·Chemosphere·Wei-Hong LinShang-Lien Lo
Aug 14, 2021·Environmental Pollution·Carmen SorasanRoberto Rosal
Oct 7, 2021·Chemical Reviews·Liang ChangZhiwei Zuo

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