ESR Spectroscopy in Polymer Research

1. Generation of Free Radicals.- 1.1. Free Radicals, Biradicals, and Radical Ions.- 1.2. Basic Properties of Free Radicals.- 1.3. Free Radical Reactions.- 1.4. Interaction of Electromagnetic Radiation with Matter.- 1.4.1. Interaction of Low Energy Photons with Matter.- 1.4.2. Interaction of High Energy Photons with Matter.- 1.5. Interaction of Charged Particles with Matter.- 1.6. Physical Sources of Free Radicals.- 1.6.1. Ionizing Radiation.- 1.6.1.1. Charged Particle Accelerators.- 1.6.1.2. Radioisotope Sources.- 1.6.1.3. Nuclear Reactors.- 1.6.2. Light Irradiation.- 1.6.3. Other Physical Sources for the Production of Free Radicals.- 1.7. Chemical Sources for the Production of Free Radicals.- 2. Principles of ESR Spectroscopy.- 2.1. Introduction.- 2.2. Interaction Between the Electron Spin and Internal Magnetic Field.- 2.3. Spin Relaxation.- 2.4. The Shape of ESR Resonance Lines.- 2.4.1. Line Shape.- 2.4.2. Line Width.- 2.4.3. Intensity.- 2.5. g-Value.- 2.6. Interaction Between the Electron and the Nuclear Spins.- 2.6.1. Hyperfine Structure Spectrum due to a Single Proton.- 2.6.2. Spectra with Hyperfine Structure due to Equivalent Protons.- 2.6.3. Hyperfine Structure Spectra due to Nonequivalent Protons.- 2.6.4. Second Order Splittings of Lines.- 3. Experimental Instrumentation of Electron Spin Resonance.- 3.1. ESR Spectrometers.- 3.2. Field Sweep Calibration.- 3.3. Measurements of Spin Concentration.- 3.4. Measurements of ESR Spectra at Different Temperatures.- 3.5. Computer Application into ESR Spectroscopy.- 3.6. Preparation of Samples for ESR Experiments.- 3.6.1. Gases.- 3.6.2. Liquids.- 3.6.3. Solids.- 3.6.4. Stabilization of Free Radicals.- 3.6.5. Apparatus for High Pressure Annealing of Samples.- 3.6.6. Loading Apparatus for ESR Stretching Experiments.- 3.6.7. Milling Devices for Grinding Samples.- 3.6.8. Preparation of Samples Containing Free Radicals by Sawing Technique.- 3.7. Special Techniques for ESR Spectroscopy.- 4. ESR Study of Polymerization Processes.- 4.1. Homogeneous Chain-growth Polymerization.- 4.2. Ionizing Polymerization.- 4.2.1. Solid-state Polymerization.- 4.2.1.1. Olefin Monomers.- 4.2.1.2. Dienes.- 4.2.1.3. Cyclic Olefines.- 4.2.1.4. Vinyl Monomers.- 4.2.1.4.1. Acrylic and Methacrylic Acide Monomers.- 4.2.1.4.2. Acrylamides.- 4.2.1.4.3. Methyl Methacrylate.- 4.2.1.4.4. Acrylonitrile and Methacrylonitrile.- 4.2.1.4.5. Vinyl Acetate.- 4.2.1.4.6. Styrene.- 4.2.1.4.7. N-Vinylcarbazole.- 4.2.1.4.8. Radical Pairs in ?-Irradiated Vinyl Monomers.- 4.2.1.5. Cyclic Monomers.- 4.2.2. Polymerization in Organic Glass Matrices.- 4.2.2.1. ESR Studies of Ionic Processes in ?-Irradiated Organic Glasses.- 4.2.2.2. ESR Studies of Ionic Polymerization in Organic Glass Matrices.- 4.2.2.2.1. Nitroethylene.- 4.2.2.2.2. Isobutene.- 4.2.2.2.3. 1,3-Butadiene.- 4.2.2.2.4. Vinyl Ethers.- 4.2.2.2.5. Acrylic Acid.- 4.2.2.2.6. Methyl Methacrylate.- 4.2.2.2.7. Acrylonitrile.- 4.2.2.2.8. Styrene and ?-Methylstyrene.- 4.2.3. Ionizing Polymerization — Miscellaneous Problems.- 4.3. Photopolymerization.- 4.3.1. Photosensitized by Hydrogen Peroxide.- 4.3.2. Photosensitized by Hydroperoxides and Peroxides.- 4.3.3. Photosensitized by Diacyl Peroxides and Tert-Butyl Peresters.- 4.3.4. Photosensitized by Dialkyl Peroxydicarbonates.- 4.3.5. Photosensitized by Benzophenone.- 4.3.6. Quinones.- 4.3.7. Photosensitized by Azo-Compounds.- 4.3.8. Photosensitized by Metal Halides.- 4.3.9. Photosensitized by Metal Acetylacetonates.- 4.4. Thermal Polymerization.- 4.4.1. Application of a Polymer Matrix for Studies of Growing Chain Radicals at High Pressure.- 4.4.2. Stabilization of Free Radicals on the Surface of Synthetic Zeolites.- 4.4.3. Popcorn Polymerization.- 4.4.4. Thermal Polymerization — Miscellaneous Problems.- 4.5. Polymerization Initiated by Mechano-radicals.- 4.6. Polymerization Initiated by Various Free Radical Initiation Systems.- 4.6.1. Hydroperoxide-SO2 System.- 4.6.2. Tetraphenylborate-Organic Acid Systems.- 4.6.3. Redox Systems.- 4.6.3.1. Polymerization Initiated by Redox Systems.- 4.6.3.1.1. Acrylic and Methacrylic Acid Monomers.- 4.6.3.1.2. Acrylamides.- 4.6.3.1.3. Acrylonitrile.- 4.6.3.1.4. Vinyl Esters.- 4.6.3.1.5. Copolymerization of Vinyl Acetate and Acrylonitrile with Various Comonomers.- 4.6.3.1.6. Allyl Monomers.- 4.6.3.1.7. Miscellaneous Monomers.- 4.7. Anionic Polymerization.- 4.7.1. Introduction.- 4.7.2. ESR Study of Ion Pairs, Free Ions, and Electron-transfer Reactions.- 4.7.3. Initiation of Polymerization by Electron Transfer.- 4.7.4. Initiation of Polymerization with Stable Alkali Metal Complexes.- 4.7.4.1. Polycyclic Aromatic Complexes.- 4.7.4.2. Ketyl Complexes.- 4.7.4.3. Aromatic Nitrile Complexes.- 4.7.4.4. Pyridyl Complexes.- 4.7.4.5. Organic Sulphur Complexes.- 4.8. Cationic Polymerization.- 4.8.1. Photo-Induced Cationic Polymerization.- 4.8.2. Cationic Polymerization Initiated with Lewis Acids.- 4.9. Heterogenous Chain-Growth Polymerization.- 4.9.1. Ziegler-Natta Catalysts.- 4.9.2. Phillips Catalysts.- 4.9.3. Other Metal Catalysts for Polymerization.- 4.9.4. Polymerization Initiated by Clays.- 4.9.5. Polymerization Initiated by Silica Gel.- 4.9.6. Polymerization Initiated by Molecular Sieves.- 5. ESR Study of Degradation Processes in Polymers.- 5.1. Radiation and Photo-Degradation of Polymers.- 5.1.1. Polyolefines.- 5.1.1.1. n-Alkane Single Crystals.- 5.1.1.2. Polyethylene.- 5.1.1.2.1. Radical Formation Under Ionizing Radiation.- 5.1.1.2.2. Radical Formation Under UV-Irradiation.- 5.1.1.2.2.1. ESR Studies on Photosensitized Degradation of Polyethylene.- 5.1.1.2.3. Conversion of Free Radicals Under Light Irradiation and Warming.- 5.1.1.2.4. Morphological Effects on the Formation and Behavior of Radicals.- 5.1.1.2.5. Decay of Free Radicals.- 5.1.1.2.6. Ethylene Copolymers.- 5.1.1.3. Polypropylene.- 5.1.1.3.1. Radical Formation Under Ionizing Radiation.- 5.1.1.3.2. Radical Formation Under UV-Irradiation.- 5.1.1.4. Molecular Motions in Solid Polyolefmes.- 5.1.1.5. Radical Pairs in ?-Irradiated Polyolefines.- 5.1.1.6. Poly-1-butene.- 5.1.1.7. Polyisobutylene.- 5.1.1.8. Poly-3-methyl-1-butene.- 5.1.1.9. Poly-4-methyl-1-pentene.- 5.1.1.10. Trapped Electrons in Polyolefines.- 5.1.2. Polydienes.- 5.1.2.1. Polybutadiene.- 5.1.2.2. Polyisoprene.- 5.1.2.3. Polypiperylene.- 5.1.2.4. Polychloroprene.- 5.1.3. Poly(methyl acrylate) and Poly(methyl methacrylate).- 5.1.4. Polystyrenes.- 5.1.5. Poly(vinyl chloride) and Poly(vinylidene chloride).- 5.1.6. Fluorinated Polymers.- 5.1.7. Poly(vinyl acetate).- 5.1.8. Polyvinyl alcohol).- 5.1.9. Polynitroethylene.- 5.1.10. Polyvinylpyridines.- 5.1.11. Poly(vinyl pyrrolidone).- 5.1.12. Polyethers.- 5.1.12.1. Polyoxymethylene.- 5.1.12.2. Polyoxyethylene.- 5.1.12.3. Poly-3,3-bis(chloromethyl)oxethane.- 5.1.12.4. Poly(2,6-dimethyl-1,4-phenyleneoxide).- 5.1.12.5. Polyglycols.- 5.1.13. Polycarbonates.- 5.1.14. Polyesters.- 5.1.14.1. Poly(?-propiolactone).- 5.1.14.2. Linear Aliphatic Polyesters.- 5.1.14.3. Poly(ethylene terephthalate).- 5.1.14.4. Poly(ethylene-2,6-naphthalene-dicarboxylate.- 5.1.15. Polyamides.- 5.1.16. Polyurethanes.- 5.1.17. Sulphur-Containing Polymers.- 5.1.18. Polysiloxanes.- 5.1.19. Biopolymers.- 5.1.19.1. Cellulose.- 5.1.19.2. Starch.- 5.1.19.3. Other Polysaccharides.- 5.1.19.4. Lignin.- 5.1.19.5. Wool.- 5.1.19.6. Polynucleotides.- 5.2. Free Radicals Formed in Glow Discharge of Polymers.- 5.3. Anionic Degradation of Vinylaromatic Polymers.- 5.4. Reaction of Polymers with Hydroxy Radicals.- 6. ESR Study of Polymers in Reactive Gases.- 6.1. Molecular Oxygen.- 6.2. Singlet Oxygen.- 6.3. Atomic Oxygen.- 6.4. Atomic Hydrogen.- 6.5. Atomic Nitrogen.- 6.6. Noble Gases.- 6.7. Other Gases.- 7. ESR Studies of the Oxidation of Polymers.- 7.1. Radiation-Induced Oxidation of Polymers.- 7.2. Polyethylene.- 7.3. Polypropylene.- 7.4. Poly(tetrafluoroethylene).- 7.5. ESR Studies of Antioxidants.- 8. ESR Studies of Molecular Fracture in Polymers.- 8.1. Introduction.- 8.2. Generation of Submicrocracks.- 8.3. Generation of Free Radicals in Mechanically Deformed Polyethylene.- 8.4. ESR Study of Free Radicals Formed During Fracture in Rubber.- 8.5. ESR Study of Fatigue Processes in Polymers.- 8.6. ESR Study of Free Radicals Formed During Grinding and Machining of Polymers.- 8.7. Anomalous Behavior of Free Radicals Obtained by Sawing Technique.- 8.8. Mechanical Degradation of Polymers in Frozen Solution Matrix.- 9. ESR Studies of Graft Copolymerization.- 9.1. Graft Copolymerization of Polyethylene.- 9.2. Cellulose Graft Copolymers.- 9.3. Miscellaneous Problems.- 10. ESR Studies of Crosslinking.- 10.1. ESR Study of Enhanced Crosslinking of Polymers.- 10.2. ESR Study of Free Radicals Observed During the Curing of Unsaturated Polyester Resins.- 10.3. ESR Study of the Vulcanization of Rubber.- 10.4. ESR Spectra of Light-Irradiated Poly(vinyl cinnamate).- 11. Application of Stable Free Radicals in Polymer Research.- 11.1. Nitroxide Radicals.- 11.2. Spin-Probe Technique.- 11.3. Spin-Trapping Technique.- 11.4. Spin-Labeling Technique.- 12. ESR Spectroscopy of Stable Polymer Radicals and their Low Molecular Analogues.- 12.1. Poly(triphenylmethyl) Radicals.- 12.2. Poly(?,??-diphenyl-p-xylene) Radicals.- 12.3. Polyphenoxy Radicals.- 12.4. Poly(triphenylhydrazyl) Radicals.- 12.5. Polymers Containing Stable Free Radicals of the Nitroxide Type.- 12.6. Poly(pyridinyl) Radicals.- 12.7. Poly(verdazyl) Radicals.- 12.8. Polymers Containing Stable Free Radicals of the Tetrazine Type.- 12.9. Polyradical Anions.- 12.10. ESR Study of Donor-Acceptor Polymer Complexes.- 12.11. Organic Polymeric Semiconductors.- 12.12. Free Radicals Formed by Pyrolysis of Polymers.- 12.13. Free Radicals in Carbon Black.- 13. ESR Study of Ion-Exchange Resins.- References.