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      Damage of polyesters by the atmospheric free radical oxidant NO 3 : a product study involving model systems

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          Summary

          Manufactured polymer materials are used in increasingly demanding applications, but their lifetime is strongly influenced by environmental conditions. In particular, weathering and ageing leads to dramatic changes in the properties of the polymers, which results in decreased service life and limited usage. Despite the heavy reliance of our society on polymers, the mechanism of their degradation upon exposure to environmental oxidants is barely understood. In this work, model systems of important structural motifs in commercial high-performing polyesters were used to study the reaction with the night-time free radical oxidant NO 3 in the absence and presence of other radical and non-radical oxidants. Identification of the products revealed ‘hot spots’ in polyesters that are particularly vulnerable to attack by NO 3 and insight into the mechanism of oxidative damage by this environmentally important radical. It is suggested that both intermediates as well as products of these reactions are potentially capable of promoting further degradation processes in polyesters under environmental conditions.

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          Most cited references33

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          The nitrate radical: Physics, chemistry, and the atmosphere

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            Radical cascades initiated by intermolecular radical addition to alkynes and related triple bond systems.

            Uta Wille (2013)
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              Kinetics and Mechanisms of the Gas‐Phase Reactions of the NO3 Radical with Organic Compounds

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                Author and article information

                Contributors
                Role: Guest Editor
                Journal
                Beilstein J Org Chem
                Beilstein J Org Chem
                Beilstein Journal of Organic Chemistry
                Beilstein-Institut (Trakehner Str. 7-9, 60487 Frankfurt am Main, Germany )
                1860-5397
                2013
                20 September 2013
                : 9
                : 1907-1916
                Affiliations
                [1 ]ARC Centre of Excellence for Free Radical Chemistry and Biotechnology, School of Chemistry and Bio21 Institute, The University of Melbourne, 30 Flemington Road, Parkville, VIC 3010, Australia
                Article
                10.3762/bjoc.9.225
                3817593
                fd323494-3396-4164-be63-ccbac19f322d
                Copyright © 2013, Goeschen and Wille; licensee Beilstein-Institut.

                This is an Open Access article under the terms of the Creative Commons Attribution License ( http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

                The license is subject to the Beilstein Journal of Organic Chemistry terms and conditions: ( http://www.beilstein-journals.org/bjoc)

                History
                : 12 July 2013
                : 23 August 2013
                Categories
                Full Research Paper
                Chemistry
                Organic Chemistry

                Organic & Biomolecular chemistry
                environmental oxidants,free radicals,nitrate radicals,polyester degradation,product studies,reaction mechanisms

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