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Mechanisms of Antioxidant Action of Phosphite and Phosphonite Esters

  • Chapter
Mechanisms of Polymer Degradation and Stabilisation

Abstract

Phosphite and phosphonite esters are used on a large scale for the stabilisation of polymers against degradation during processing and long-term applications. They function as antioxidants by various mechanisms depending on their structure, the nature of the substrate to be stabilised and the reaction conditions.

All phosphites and phosphonites are hydroperoxide-decomposing secondary antioxidants. Their reactivity in hydroperoxide reduction decreases with increasing electron-acceptor ability and bulk of the groups bound to phosphorus in the order phosphonites > alkyl phosphites > aryl phosphites > hindered aryl phosphites.

Five-membered cyclic phosphites are capable of decomposing hydro-peroxides catalytically due to the formation of acidic hydrogen phosphates by hydrolysis and peroxidolysis in the course of reaction. The o-hydroxyphenyl phosphates formed in this way from o-phenylene phosphites are excellent chain breaking antioxidants.

Aryl phosphites, particularly these derived from sterically hindered phenols, can act as chain-breaking primary antioxidants by reduction of peroxyl radicals to alkoxyl radicals. The latter react further with the phosphites by substitution, releasing aroxyl radicals which terminate the radical chain oxidation. The chain-breaking antioxidant activity of aryl phosphites is lower than that of hindered phenols, because the rate constants of their reaction with peroxyl radicals and their stoichiometric inhibition factors are lower than those of phenols. The stoichiometric inhibition factors decrease from one to zero with decreasing concentration of the phosphite and increasing oxidisability of the substrate. Therefore, phosphites themselves are active chain-breakers only at rather high concentrations, predominantly in substrates of low oxidisability at lower temperatures.

In oxidising media at higher temperatures, however, hydrolysis of phosphites and phosphonites takes place in addition to oxidation. The phenols so formed synergised by the parent phosphorus compounds and their hydrolysis products, are responsible for the high antioxidative activity of aryl phosphites and phosphonites, especially the hindered compounds, in oxidations at higher temperatures.

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Authors and Affiliations

  1. Dresden University of Technology, Dresden, Germany

    Klaus Schwetlick

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  1. Klaus Schwetlick
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  1. Aston University, Birmingham, UK

    Gerald Scott (Professor of Polymer Science) (Professor of Polymer Science)

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Schwetlick, K. (1990). Mechanisms of Antioxidant Action of Phosphite and Phosphonite Esters. In: Scott, G. (eds) Mechanisms of Polymer Degradation and Stabilisation. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-3838-3_2

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  • DOI: https://doi.org/10.1007/978-94-011-3838-3_2

  • Publisher Name: Springer, Dordrecht

  • Print ISBN: 978-1-85166-505-1

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