PolymerSpectroscopy

Front Matter......Page 1 List of Contributors......Page 3 Table of Contents......Page 0 Table of Contents......Page 6 1.1 Introduction......Page 16 1.2 Branched Molecules: Polyethylene and a Polyester System......Page 18 1.3 The Microstructure of Linear Chains......Page 24 1.4 The Participation of a Charge-Transfer Complex in a Free Radical Polymerization Reaction......Page 31 1.5 The Polymerization of Dienes......Page 34 1.6 Ring-Opening-Metathesis Polymerizations......Page 39 1.6.1 Stereoselectivity in ROMP......Page 41 1.6.2 Distribution of trans Double Bonds In High cis Poly(Norbornene)......Page 45 1.6.3 Regioselectivity in ROMP......Page 50 1.6.4 Direct Observation of Tacticity......Page 56 1.7 References......Page 61 2.1 Introduction......Page 64 2.2 Substituent Effects on 13C Chemical Shifts......Page 65 2.3 gamma-Gauche Effect Method of Predicting NMR Chemical Shifts......Page 69 2.4.1 Polypropylene (PP)......Page 73 7.3.1 The Response of a Viscoelastic System to Sinusoidal Stress......Page 76 2.4.3 Poly(Propylene Oxide) (PPO)......Page 77 2.4.4 Poly(Vinylidene Fluoride) (PVF2)......Page 90 2.5.1 Styrene-Methyl Methacrylate Copolymers (S-MM)......Page 93 2.5.2 Ethylene-Vinyl Acetate (E-VAc) Copolymers......Page 97 2.6 NMR Observation of Rigid Polymer Conformations......Page 101 2.7 References......Page 102 3.1 Introduction......Page 105 3.2 Methods......Page 108 3.3 Some Calculation Details......Page 109 3.4 Individual Polymers......Page 110 3.5 The Calculated RIS Parameters......Page 117 3.7 Coupling Constants......Page 119 3.8 Characteristic Ratios......Page 121 3.9 Conclusions......Page 122 3.11 References......Page 123 4.1 Introduction......Page 124 4.2 The Techniques......Page 125 4.3 High-Resolution Carbon-13 NMR of Polymers......Page 128 4.4 Proton Spin Relaxation......Page 132 4.5 Discrimination in Carbon-13 Spectra......Page 135 4.6 Spectra of Abundant Spins......Page 138 4.8 Acknowledgements......Page 139 4.9 References......Page 140 5.1 Introduction......Page 141 5.2 Multidimensional Solid-State NMR Spectra......Page 143 5.3.1 Increase of Spectral Resolution......Page 144 5.3.2 Separated Local Field NMR......Page 146 5.3.3 Wideline Separation Experiments......Page 147 5.3.4 2D and 3D Exchange NMR......Page 148 5.3.5 Chain Alignment from 2D and 3D NMR......Page 150 5.3.7 Spatially Resolved Solid State NMR......Page 152 5.4 Conclusion......Page 154 5.6 References......Page 155 6.1.1 Basis of NMR Imaging......Page 157 6.1.2 Relaxation Parameters in NMR Imaging......Page 159 6.1.4 Utility of NMRI......Page 161 6.2.1 Chemical Shift Imaging......Page 162 6.3.1 Detection of Voids in Composites......Page 165 6.3.3 NMRI of Physical Aging......Page 167 6.3.4 NMRI Studies of Diffusion in Polymers......Page 168 6.3.5 Desorption of Liquids from Polymers......Page 171 6.3.6 Multicomponent Diffusion as Studied by NMRI......Page 173 6.3.7 Absorption-Desorption Cycling of Liquids in Polymers......Page 175 6.5 References......Page 177 7.1 Introduction......Page 179 7.1.1 The Basis of Orientation Measurements by Infrared Spectroscopy......Page 180 7.1.2 The Basis of Orientation Measurements by Raman Spectroscopy......Page 182 7.2.1 Experimental Techniques on Static Samples......Page 183 7.2.2 Infrared Spectroscopic Studies on Oriented Polymers......Page 186 7.2.3 Raman Spectroscopic Studies on Oriented Polymers......Page 188 7.3 Time Resolved Measurements......Page 191 7.3.2 Experimental......Page 193 7.3.3 Some Examples of Dynamic Linear Dichroic Infrared Studies......Page 198 7.4 Elastomers Under Stress......Page 204 7.5 Conclusion......Page 206 7.6 References......Page 207 8.1 Introduction......Page 209 8.1.1 Polydiacetylene Single Crystals......Page 210 8.2.1 Aromatic Polyamide Fibres......Page 212 8.2.2 Polyethylene Fibres......Page 216 8.3.1 Urethane-Diacetylene Copolymers......Page 220 8.3.2 Deformation Studies......Page 223 8.4.1 Single-Fibre Composites......Page 227 8.4.2 Interfacial Micromechanics......Page 230 8.5 Conclusions......Page 233 8.7 References......Page 234 9.1 Introduction......Page 237 9.1.1 Synthesis of Spin Labels......Page 238 9.2.1 Correlation Times......Page 241 9.2.1.1 Fast Motion......Page 245 9.2.2 The Glass Transition and T50G......Page 246 9.3 Heterogeneous Systems......Page 248 9.4 Polymer Blends......Page 251 9.5 References......Page 257 10.1 Introduction......Page 259 10.2 Experimental......Page 260 10.3.1.1 Identification of the Radicals in the ESR Spectrum......Page 261 10.3.1.3 Monomer Concentration during Polymerization......Page 262 10.3.1.4 Radical Concentration during Polymerization......Page 263 10.3.1.5 Correction for Changing Sensitivity of the Spectrometer......Page 265 10.3.1.6 Kinetic Analysis......Page 266 10.3.1.7 Crosslinking Methacrylate Monomers......Page 267 10.3.2.1 Poly(Methyl Methacrylate)......Page 269 10.3.2.2 Polystyrene......Page 273 10.3.2.3 Random Copolymers of Methyl Methacrylate and Styrene......Page 274 10.3.2.4 ESR and the Mechanism of Radiolysis......Page 275 10.6 References......Page 279 11.1 Introduction......Page 281 11.2 Amorphous Polymers: Phenomenological and Molecular Aspects......Page 282 11.3 Crystalline Polymers......Page 286 11.4 Liquid Crystalline (LC) Polymers......Page 288 11.5 Real-Time Studies of Chemical and Physical Changes......Page 294 11.6 Conclusions and Future Prospects......Page 299 11.8 References......Page 300 12.1 Introduction......Page 303 12.2.1 Semi-Crystalline Polymers......Page 304 12.2.2 Phase-Separating Polymer Mixtures......Page 311 12.3.1 Dilute Polymer Solutions......Page 315 12.3.2 Gels......Page 317 12.3.3 Semi-Dilute Solutions and Trapped Chains......Page 319 12.3.4 Surface Quasi-Elastic Light Scattering (SQELS)......Page 322 12.5 References......Page 327 13.2 The Principles of Neutron Scattering......Page 330 13.3 Neutron Experiments......Page 334 13.3.1 Studies of Polymer Dimensions: Small Angle Scattering......Page 335 13.3.2 Polymers at Surfaces-Reflection......Page 338 13.3.3 Polymer Dynamics-Quasi-Elastic Scattering......Page 339 13.4.1 Studies of Copolymers......Page 341 13.4.2 Adsorption at Surfaces......Page 344 13.4.3 Kinetics and Polymer Motion......Page 346 13.6 References......Page 347 14.1.1 Origin of Optical Activity in Macromolecules......Page 351 14.1.2 Objective......Page 354 14.2.1.1 Azobenzene-Containing Polypeptides......Page 355 14.2.1.2 Light-Induced Conformational Changes......Page 356 14.2.1.3 Photosimulated Aggregation-Disaggregation Effects......Page 359 14.2.2.1 Spiropyran-Containing Polypeptides......Page 361 14.2.2.2 Photomodulation of Conformation......Page 364 14.2.2.3 Photoinduced Variations of Viscosity......Page 370 14.3 References......Page 371 15.1 Introduction......Page 373 15.2 Probes of Order in Polymers......Page 374 15.4 Photochemistry in Polymers......Page 376 15.5 Excimer-Forming Polymers......Page 378 15.6 Dynamics of Luminescence......Page 380 15.7 Fluorescence Decay in Vinyl Aromatic Polymers......Page 381 15.7.1 Diffusional Models......Page 383 15.7.1.2 Random Water, Random Distribution Chromophores......Page 384 15.7.1.5 Diffusion of Energy and Chromophore......Page 385 15.7.1.6 Fluorescence Anisotrophy Measurements......Page 389 15.8 Conclusion......Page 391 15.10 References......Page 392 B......Page 394 D......Page 395 F......Page 396 K......Page 397 N......Page 398 P......Page 399 S......Page 401 T......Page 402 Z......Page 403