Ion-Radical Conversions in Main or Side Chains of Nitrogen-Containing Polymers in Nitrogen Dioxide Atmosphere

Mechanism of nitrogen dioxide interaction with polymers containing amide and imide groups in the main or side chains of macromolecules (polycaproamide, polyvinylpyrrolidone, poly- m -phenylene isophthalamide and polypyromellitimide) is considered. The initiators of conversions of polymers of the giv...

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Bibliographic Details
Published in:Journal of polymers and the environment 2011-03, Vol.19 (1), p.312-327
Main Authors: Davydov, Evgeny Ya, Gaponova, Irina S., Pokholok, Tatiana V., Pariiskii, Georgy B.
Format: Article
Language:English
Subjects:
Cations
Chemical bonds
Chemistry
Chemistry and Materials Science
Conversion
Environmental Chemistry
Environmental Engineering/Biotechnology
Free radicals
Industrial Chemistry/Chemical Engineering
Macromolecules
Materials Science
Molecular chemistry
Nitrates
Nitric oxide
Nitrogen
Nitrogen dioxide
Nitrosyls
Original Paper
Polymer Sciences
Polymers
Radicals
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Summary:Mechanism of nitrogen dioxide interaction with polymers containing amide and imide groups in the main or side chains of macromolecules (polycaproamide, polyvinylpyrrolidone, poly- m -phenylene isophthalamide and polypyromellitimide) is considered. The initiators of conversions of polymers of the given classes are not monoradicals of nitrogen dioxide rather than its equilibrium dimers in the form of nitrosyl nitrate. In primary oxidizing reaction of an electron transfer from donor groups of macromolecules to nitrosyl nitrate, radical cations, nitric oxide and nitrate anion are formed, which in the subsequent reactions give products of nitration and nitrosation. These products are precursors of stable acylalkylaminoxyl, acylarylaminoxyl, iminoxyl macroradicals. The specific interactions of nitrogen dioxide dimers with functional groups of macromolecules determine features of the mechanism of ion-radical conversions of the polymers and the composition of radical and molecular products. The direct detection of radical cations has been realized by ESR method for confirmation of the ion-radical initiation concept using model reaction of nitrogen dioxide with triphenylamine.
ISSN:1566-2543
1572-8919
1572-8900
DOI:10.1007/s10924-010-0261-5