Interaction of Polymers with Polluted Atmospheres

279 Pages·2009·12.562 MB·English

by  Gennady Zaikov

Interaction of Polymers
with Polluted Atmosphere
Authors:
Gennady Zaikov
Evgenii Davydov
Georgii Pariiskii
Irina Gapanova
Tat'yana Pokholok
Interaction of Polymers
with Polluted Atmosphere
Nitrogen Oxides
Authors:
Gennady Zaikov, Evgenii Davydov
Georgii Pariiskii, Irina Gapanova
Tat’yana Pokholok
iSmithers – A Smithers Group Company
Shawbury, Shrewsbury, Shropshire, SY4 4NR, United Kingdom
Telephone: [phone] Fax: [phone]
http://www.rapra.net
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First Published in 2009 by
i
Smithers
Shawbury, Shrewsbury, Shropshire, SY4 4NR, UK
©2009, Smithers Rapra
All rights reserved. Except as permitted under current legislation no part
of this publication may be photocopied, reproduced or distributed in any
form or by any means or stored in a database or retrieval system, without
the prior permission from the copyright holder.
A catalogue record for this book is available from the British Library.
Every effort has been made to contact copyright holders of any material reproduced
within the text and the authors and publishers apologise if any have been overlooked.
Every effort has been made to contact copyright holders of any material
reproduced within the text and the authors and publishers apologise if
any have been overlooked.
ISBN: 9781847353795 (hardback)
9781847353771 (softback)
Typeset by Argil Services
Printed and bound by Lightning Source Inc.
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P
reface
‘A man who dares to waste one hour of time has not discovered the value of life’
Charles Robert Darwin (12 February 1809 to 19 April 1882) English biologist,
naturalist, evolutionist
‘Simplicity is the ultimate Sophistication’ Leonardo da Vinci (15 April 1452
to 2 May 1519) Italian polymath: scientist, mathematician, engineer, inventor,
anatomist, sculptor, painter, architect, musician and writer
If one was to estimate the world production of polymers and metals not in units
of weight (tons), but in units of volume (cubic meters), then humans produce as
much polymers, polymeric blends and composites as pig iron, steel, rolled metal and
nonferrous metals taken together. The dynamics of the manufacturing process are
also important: the growth of polymer production has surpassed that of metals by
15–20% each year in the past 20–25 years.
Humans lived in the Stone age, then in the Bronze age, Iron age, and have already
entered into the ‘Polymeric age’. Progress appears to involve replacement of one
problem by another. When there were no polymers, there were no problems with
their application. However, history and progress do not stop, and we should solve
new problems connected with using polymers in engineering, life, agriculture, and
medicine.
The important problems are the stability of polymeric materials, prolongation of
their reliable operating time, predicting the service life of polymeric materials, and
the recycling and utilization of polymers. To solve these problems, it is necessary to
study the processes of polymer degradation, namely, thermal degradation, oxidation,
ozonolysis, photo-ageing, radiolysis, hydrolysis, biodegradation, and mechanical
degradation.
Mention should be made of the outstanding scientists working in this area: Alexandr S.
Kuz’minskii (Rubber Research Institute, Moscow, Russia), Norman Grassie (Glasgow
University, Scotland, UK), Ian McNeill (Glasgow University, Scotland, UK), Georges
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Interaction of Polymers with Polluted Atmosphere Nitrogen Oxides
Geuskens (Universite de Libre de brusel, Belgium), Rainer Wolf (Sandoz Company,
Hunige, Elsas, France), Paul Edwin Stott (Uniroyal Chemical Company, Middlebury,
CT, USA), Gerald Scott (Aston University, Birmingham, UK), Moisei B. Neiman
(Institute of Chemical Physics, Moscow, Russia), Nikolai M. Emanuel (Institute of
Chemical Physics, Moscow, Russia), Frank Mayo (Stanford Research Institute, Palo
Alto, CA, USA), Glenn Russel (Iowa State University, Amis, IO, USA), Keith Ingold
(National Research Council of Canada, Ottawa, Ontario, Canada), Eli M. Pearce
(Brooklyn Polytechnic University, Brooklyn, NY, USA), Herman Mark (Brooklyn
Polytechnic University, Brooklyn, NY, USA), Herbert Morawets (Brooklyn Polytechnic
University, Brooklyn, NY, USA), Tsutomo Kagya (Kyoto University, Kyoto, Japan)
and Ferenz Tüdos (Institute of Chemistry, Budapest, Hungary).
One of the major problems is ascertainment of the mechanism of interaction of
polymers with air pollutants, for example, with nitrogen oxides. This monograph is
devoted to this matter. The results obtained in studies of the interaction of polymers
of different classes with nitrogen oxides are presented. Special attention is given to
investigations carried out by electron spin resonance (ESR) spectroscopy, permitting
us to draw conclusions from the structure of nitrogen-containing macroradicals on
the mechanism of the free-radical stages of the polymer degradation process involving
nitrogen oxides. The use of reactions of nitrogen oxides with polymers for obtaining
spin-labelled macromolecules is also noteworthy. The stable nitrogen-containing
radicals generated in this way can be used for investigations of the molecular
dynamics of macromolecules. The capability of nitrogen trioxide for cross-linking of
polyvinylpyrrolidone in photo processes provoked our intention to write this book.
It is quite possible that hydrogels obtained in this way can serve as specific sorbents
for medical use. The interaction of polymers with nitrogen oxides is therefore not
only degradation, but sometimes a purposeful modification of polymers.
This monograph has seven chapters. The first chapter is devoted to consideration of the
properties of stable aminoxyl radicals, their application in the polymer chemistry, and
for investigations of molecular dynamics and the physical structure of polymers. In the
second chapter, the classification of polymers differing in stability toward aggressive
gases including nitrogen dioxide based on performed chemical and physical-chemical
researches. In Chapters 3–6, the effect of nitric oxide, nitrogen dioxide and nitrogen
trioxide on various polymers and model low-molecular compounds are discussed.
These gases are most important for reactions with polymers because they form eight
known nitrogen oxides thought to be air pollutants. The final chapter is concerned
with features of the oxidative ion-radical mechanism of interaction of polymers with
diamagnetic nitrogen dioxide dimers in the form of nitrosyl nitrate.
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Preface
The monograph will be useful to scientists, engineers, students and postgraduate
students working in the field of chemistry and physics of polymers.
E. Ya. Davydov
I. S. Gaponova
G. B. Pariiskii
T. V. Pokholok
G. E. Zaikov
v
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Interaction of Polymers with Polluted Atmosphere Nitrogen Oxides
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C
ontents
Introduction ....................................................................................................1
1 Classification of Polymers with respect to Reactivity toward Nitro-
gen Oxides ...........................................................................................3
1.1 Interaction of Carbon-chain Polymers with NO ................4
2
1.2 Interaction of Rubbers with NO ........................................7
2
1.3 Interaction of NO with Aliphatic Polyamides and
2
Polyurethanes ...................................................................10
2 Properties and Applications of Aminoxyl Radicals in Polymer
Chemistry ...........................................................................................15
2.1 Structure and Physical Properties of Stable Radicals .........15
2.2 ESR Spectroscopy of ARs .................................................17
2.3 Chemical Properties of ARs ..............................................20
2.4 Applications of ARs ..........................................................26
2.5 Generation of ARs in Reactions of Spin Trapping .............28
2.6 Synthesis of Polymers Containing Stable ARs ...................33
3 Interaction of Polymers with Nitric Oxide .......................................55
3.1 Interaction of NO with Organic Compounds ...................56
3.2 Reactions of NO with Macroradicals Generated by
the Photolysis and Radiolysis of Polymers ........................70
3.2.1 Synthesis of Spin-Labelled Fluorinated Polymers by
Free-Radical Reaction in the Presence of NO ...............70
3.2.2 Photolysis of Polymethylmethacrylate and
Acetyl Cellulose in NO .................................................80
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Interaction of Polymers with Polluted Atmosphere Nitrogen Oxides
3.2.3 Radiolysis of Acetyl Cellulose and
Polymethylmethacrylate in NO ....................................82
3.3 Interaction of Polymeric Hydroperoxides with NO ..........82
4 Free-Radical Conversions of Polymers Initiated by
Nitrogen Trioxide ...............................................................................93
4.1 Methods of Generation of NO ........................................93
3
4.2 Photochemistry of NO ....................................................98
3
4.3 Interaction of NO with Organic Compounds ..................99
3
4.4 Cross-linking of Macromolecules via the Photoreactions
of NO ............................................................................110
3
5 Reactions of Nitrogen Dioxide with Organic Compounds ...........125
5.1 Reactions of NO with Alkanes ......................................125
2
5.2 Reactions of NO with Aromatic Compounds ................132
2
5.3 Reactions of NO with Phenols ......................................150
2
5.4 Interaction of NO with Alkenes, Dienes and Polyenes ...161
2
5.5 Radical Conversions of p-benzoquinones in Reactions
with NO ........................................................................171
2
6 Nitrogen Dioxide Monoradicals in Reactions of Modification
and Degradation of Macromolecules .............................................185
6.1 Formation of Spin-Labelled Polymers in Reactions of
NO with the Double Bonds of Macromolecules ............185
2
6.2 ESR Imaging in Studies of the Spatial Distribution of
the Reaction Front of NO in Polymers ..........................191
2
6.3 Polymer Degradation in Reactions of
Peroxide Macroradicals with NO ..................................193
2
7 Role of Nitrogen Dioxide Dimers in Reactions with Polymers .....199
7.1 Formation of Nitrosonium Complexes from
Organic Compounds and NO .......................................199
2
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Contents
7.2 Direct Experimental Detection of Primary Radical
Cations and Products of Their Decomposition in
the Reactions of Nitrosyl Nitrate ....................................206
7.3 Oxidative Generation of Stable Nitrogen-Containing
Radicals in Aliphatic Polyamides and
Polyvinylpyrrolidone ......................................................216
7.4 Ion-Radical Conversions of Aromatic Polyamides in
the Presence of NO ........................................................219
2
7.5 Oxidative Radical Generation via NO Dimer
2
Conversions Induced by the Amide Groups of
Macromolecules .............................................................229
7.6 Interaction of Aromatic Polyimides with NO ................234
2
Abbreviations .............................................................................................249
Index .........................................................................................................253
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