Interaction of polymers with polluted atmosphere nitrogen oxides

Classification of Polymers with respect to Reactivity toward Nitrogen Oxides ...........................................................................................3 1.1 Interaction of Carbon-chain Polymers with NO2 ................4 1.2 Interaction of Rubbers with NO2 ........................................7 1.3 Interaction of NO2 with Aliphatic Polyamides and 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 viii 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 NO3 ........................................93 4.2 Photochemistry of NO3 ....................................................98 4.3 Interaction of NO3 with Organic Compounds ..................99 4.4 Cross-linking of Macromolecules via the Photoreactions of NO3 ............................................................................110 5 Reactions of Nitrogen Dioxide with Organic Compounds ...........125 5.1 Reactions of NO2 with Alkanes ......................................125 5.2 Reactions of NO2 with Aromatic Compounds ................132 5.3 Reactions of NO2 with Phenols ......................................150 5.4 Interaction of NO2 with Alkenes, Dienes and Polyenes ...161 5.5 Radical Conversions of p-benzoquinones in Reactions with NO2 ........................................................................171 6 Nitrogen Dioxide Monoradicals in Reactions of Modification and Degradation of Macromolecules .............................................185 6.1 Formation of Spin-Labelled Polymers in Reactions of NO2 with the Double Bonds of Macromolecules ............185 6.2 ESR Imaging in Studies of the Spatial Distribution of the Reaction Front of NO2 in Polymers ..........................191 6.3 Polymer Degradation in Reactions of Peroxide Macroradicals with NO2 ..................................193 7 Role of Nitrogen Dioxide Dimers in Reactions with Polymers .....199 7.1 Formation of Nitrosonium Complexes from Organic Compounds and NO2 .......................................199 Contents ix 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 NO2 ........................................................219 7.5 Oxidative Radical Generation via NO2 Dimer Conversions Induced by the Amide Groups of Macromolecules .............................................................229 7.6 Interaction of Aromatic Polyimides with NO2 ................234 Abbreviations .............................................................................................249