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Polymer Spectroscopy Edited by ALLAN H. FAWCETT The Queens University of Belfast, Belfast, Northern Ireland, UK JOHN WILEY & SONS Chichester • New York • Brisbane • Toronto • Singapore Copyright © 1996 by John Wiley & Sons Ltd, Baffins Lane, Chichester, West Sussex PO19 IUD, England National 01243779777 International (+44) 1243 779777 All rights reserved. No part of this book may be reproduced by any means, or transmitted, or translated into a machine language without the written permission of the publisher. Other Wiley Editorial Offices John Wiley & Sons, Inc., 605 Third Avenue, New York, NY 10158-0012, USA Jacaranda Wiley Ltd, 33 Park Road, Milton, Queensland 4064, Australia John Wiley & Sons (Canada) Ltd, 22 Worcester Road, Rexdale, Ontario M9W ILl, Canada John Wiley & Sons (SEA) Pte Ltd, 37 Jalan Pemimpin #05-04, Block B, Union Industrial Building, Singapore 2057 British Library Cataloguing in Publication Data A catalogue record for this book is available from the British Library ISBNO 471960292 Typeset in 10/12pt Times by Thomson Press (India) Ltd, New Delhi Printed and bound by Antony Rowe Ltd, Eastbourne This book is printed on acid-free paper responsibly manufactured from sustainable forestation, for which at least two trees are planted for each one used for paper production. LIST OF CONTRIBUTORS Gordon G. Cameron Department of Chemistry, University of Aberdeen, Meeston Walk, Old Aberdeen AB92UE, Scotland, UK Michelle Carey Department of Chemistry, Imperial College of Science, Technology and Medicine, South Kensington, London SWl'2AY, UK Trudy G. Carswell Chemistry Department, University of Queensland, Brisbane, QLD 4072, Australia Francesco Ciardelli Dipartimento di Chimica e Chimica Industriale, Universita of Pisa, Via Risorgimento 35, 56126 Pisa, Italy Iain G. Davidson Department of Chemistry, University of Aberdeen, Meeston Walk, Old Aberdeen AB9 2UE, Scotland, UK Christine Duch Chemistry Department, University of Wales, Swansea, Singleton Park, Swansea SA2 8PP, Wales, UK Allan H. Fawcett School of Chemistry, The Queen's University of Belfast, Belfast BT95AG, North- ern Ireland, UK Adriano Fissi, CNR Institute of Biophysics, University of Pisa, Via Risorgimento 35,56126 Pisa, Italy Jerome Fournier Chemistry Department, University of Wales, Swansea, Singleton Park, Swansea SA2 8PP, Wales, UK R. Wayne Garrett Chemistry Department, University of Queensland, Brisbane, QLD 4072, Australia J. G. Hamilton School of Chemistry, The Queens University of Belfast, Belfast BT95AG, Northern Ireland, UK Robin K. Harris Department of Chemistry, University of Durham, Science Laboratories, South Road, Durham DHl 3LE, UK James R. Hayden Chemistry Department, University of Wales, Swansea, Singleton Park, Swansea SA28PP,Wales,UK Patrick J. Hendra Department of Chemistry, University of Southampton, Highfield, Southampton SO95NH, UK Ian R. Herbert Department of Chemistry, University of Durham, Science Laboratories, South Road, Durham DHl 3LE, UK David J. T. Hill Chemistry Department, University of Queensland, Brisbane, QLD 4072, Australia Oliver W. Howarth Centre for Nuclear Magnetic Resonance, Department of Chemistry, University of Warwick, Coventry CV4IAL, UK Roger N. Ibbett Department of Chemistry, University of Durham, Science Laboratories, South Road, Durham DHl 3LE, UK Jack L. Koenig Department of Macromolecular Science, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, OH 44106-7202, USA W.F.Maddams, Department of Chemistry, University of Southampton, Highfield, Southampton SO95NH,UK James H. O'Donnell Chemistry Department, University of Queensland, Brisbane, QLD 4072, Australia (Deceased) David Phillips Department of Chemistry, Imperial College of Science, Technology and Medicine, South Kensington, London SW72AY, UK Osvaldo Pieroni Dipartimento di Chimica e Chimica Industriale, and CNR, Institute of Biophysics, Universita di Pisa, Via Risorgimemto 35, 56126 Pisa, Italy Peter J. Pomery Chemistry Department, University of Queensland, Brisbane, QLD 4072, Australia Adrian R. Rennie Polymers and Colloids Group, Cavendish Laboratory, University of Cambridge, Madingley Road, Cambridge CB3 OHE, UK R. W. Richards Department of Chemistry, University of Durham, Durham DHl 3LE, UK J. J. Rooney School of Chemistry, The Queen's University of Belfast, Belfast BT9 5AG, Northern Ireland, UK H.W.Spiess Max-Planck-Institute fur Polymerforschung, Postfach 3148, D-55021 Mainz, Germany Alan E. Tonelli Fiber and Polymer Science Program, College of Textiles, North Carolina State University, PO Box 8301, Raleigh, NC 27695-8301, USA Graham Williams Chemistry Department, University of Wales, Swansea, Singleton Park, Swansea SA2 8PP, Wales, UK Mark A. Whiskens Department of Chemistry, University of Durham, Science Laboratories, South Road, Durham DHl 3LE, UK Catherine L. Winzor Chemistry of Department University of Queensland, Brisbane, QLD 4072, Australia Robert J. Young Manchester Materials Science Centre, University of Manchester, Grosvenor Street, Manchester Ml 7HS, UK v This page has been reformatted by Knovel to provide easier navigation. Contents List of Contributors ............................................................. xiii Introduction to Polymer Spectroscopy .......................... 1 1. NMR Characterisation of Macromolecules in Solution ....................................................................... 7 1.1 Introduction ................................................................... 7 1.2 Branched Molecules: Polyethylene and a Polyester System .......................................................... 9 1.3 The Microstructure of Linear Chains ............................ 15 1.4 The Participation of a Charge-Transfer Complex in a Free Radical Polymerization Reaction ...................... 22 1.5 The Polymerization of Dienes ...................................... 25 1.6 Ring-Opening-Metathesis Polymerizations .................. 30 1.6.1 Stereoselectivity in ROMP ......................... 32 1.6.2 Distribution of trans Double Bonds in High cis Poly(Norbornene) ......................... 36 1.6.3 Regioselectivity in ROMP .......................... 41 1.6.4 Direct Observation of Tacticity ................... 45 1.7 References ................................................................... 52 2. Conformation: the Connection between the NMR Spectra and the Microstructures of Polymers ......... 55 2.1 Introduction ................................................................... 55 2.2 Substituent Effects on 13C Chemical Shifts .................. 56 vi Contents This page has been reformatted by Knovel to provide easier navigation. 2.3 γ-Gauche Effect Method of Predicting NMR Chemical Shifts ............................................................. 60 2.4 Applications of γ-Gauche Effect Analysis of Polymer Microstructures ............................................... 64 2.4.1 Polypropylene (PP) .................................... 64 2.4.2 Propylene-Vinyl Chloride Copolymers (P-VC) ........................................................ 67 2.4.3 Poly(Propylene Oxide) (PPO) .................... 68 2.4.4 Poly(Vinylidene Fluoride) (PVF2) ................ 81 2.5 NMR Spectroscopy as a Means to Probe Polymer Conformations .............................................................. 84 2.5.1 Styrene-Methyl Methacrylate Copolymers (S-MM) ................................... 84 2.5.2 Ethylene-Vinyl Acetate (E-VAc) Copolymers ................................................ 88 2.6 NMR Observation of Rigid Polymer Conformations .............................................................. 92 2.7 References ................................................................... 93 3. ‘Model-Free’ RIS Statistical Weight Parameters from 13C NMR Data ..................................................... 97 3.1 Introduction ................................................................... 97 3.2 Methods ........................................................................ 100 3.3 Some Calculation Details ............................................. 101 3.4 Individual Polymers ...................................................... 102 3.5 The Calculated RIS Parameters .................................. 109 3.6 β-Gauche Effects .......................................................... 111 3.7 Coupling Constants ...................................................... 111 3.8 Characteristic Ratios .................................................... 113 3.9 Conclusions .................................................................. 114 Contents vii This page has been reformatted by Knovel to provide easier navigation. 3.10 Acknowledgement ........................................................ 115 3.11 References ................................................................... 115 4. NMR Studies of Solid Polymers ................................ 117 4.1 Introduction ................................................................... 117 4.2 The Techniques ............................................................ 118 4.3 High-Resolution Carbon-13 NMR of Polymers ............ 121 4.4 Proton Spin Relaxation ................................................. 125 4.5 Discrimination in Carbon-13 Spectra ........................... 128 4.6 Spectra of Abundant Spins ........................................... 131 4.7 Conclusion .................................................................... 132 4.8 Acknowledgements ...................................................... 132 4.9 References ................................................................... 133 5. Multidimensional Solid-State NMR of Polymers ...... 135 5.1 Introduction ................................................................... 135 5.2 Multidimensional Solid-State NMR Spectra ................. 137 5.3 Examples ...................................................................... 138 5.3.1 Increase of Spectral Resolution ................. 138 5.3.2 Separated Local Field NMR ....................... 140 5.3.3 Wideline Separation Experiments .............. 141 5.3.4 2D and 3D Exchange NMR ........................ 142 5.3.5 Chain Alignment from 2D and 3D NMR ...... 144 5.3.6 Domain Sizes from Spin Diffusion Experiments ............................................... 146 5.3.7 Spatially Resolved Solid State NMR .......... 146 5.4 Conclusion .................................................................... 148 5.5 Acknowledgements ...................................................... 149 5.6 References ................................................................... 149 viii Contents This page has been reformatted by Knovel to provide easier navigation. 6. NMR Imaging of Polymers ......................................... 151 6.1 Introduction ................................................................... 151 6.1.1 Basis of NMR Imaging ............................... 151 6.1.2 Relaxation Parameters in NMR Imaging .... 153 6.1.3 Resolution in NMR Imaging ....................... 155 6.1.4 Utility of NMRI ............................................ 155 6.1.5 Image Processing ...................................... 156 6.2 Advanced Imaging Techniques .................................... 156 6.2.1 Chemical Shift Imaging .............................. 156 6.3 Applications of NMRI to Polymers ................................ 159 6.3.1 Detection of Voids in Composites .............. 159 6.3.2 Detection of Nonuniform Dispersion of Filler ........................................................... 161 6.3.3 NMRI of Physical Aging ............................. 161 6.3.4 NMRI Studies of Diffusion in Polymers ...... 162 6.3.5 Desorption of Liquids from Polymers ......... 165 6.3.6 Multicomponent Diffusion as Studied by NMRI ......................................................... 167 6.3.7 Absorption-Desorption Cycling of Liquids in Polymers .................................... 169 6.4 Acknowledgements ...................................................... 171 6.5 References ................................................................... 171 7. Fourier Transform Infrared and Raman Spectroscopies in the Study of Polymer Orientation .................................................................. 173 7.1 Introduction ................................................................... 173 7.1.1 The Basis of Orientation Measurements by Infrared Spectroscopy ........................... 174 Contents ix This page has been reformatted by Knovel to provide easier navigation. 7.1.2 The Basis of Orientation Measurements by Raman Spectroscopy ............................ 176 7.2 ........................................................................................ 177 7.2.1 Experimental Techniques on Static Samples ..................................................... 177 7.2.2 Infrared Spectroscopic Studies on Oriented Polymers ..................................... 180 7.2.3 Raman Spectroscopic Studies on Oriented Polymers ..................................... 182 7.3 Time Resolved Measurements .................................... 185 7.3.1 The Response of a Viscoelastic System to Sinusoidal Stress ................................... 185 7.3.2 Experimental .............................................. 187 7.3.3 Some Examples of Dynamic Linear Dichroic Infrared Studies ............................ 192 7.4 Elastomers Under Stress ............................................. 198 7.5 Conclusion .................................................................... 200 7.6 References ................................................................... 201 8. Deformation Studies of Polymers using Raman Spectroscopy ............................................................. 203 8.1 Introduction ................................................................... 203 8.1.1 Polydiacetylene Single Crystals ................. 204 8.1.2 Extension of the Technique to Other Materials .................................................... 206 8.2 High-Performance Polymer Fibres ............................... 206 8.2.1 Aromatic Polyamide Fibres ........................ 206 8.2.2 Polyethylene Fibres ................................... 210 8.3 Isotropic Polymers ........................................................ 214 8.3.1 Urethane-Diacetylene Copolymers ............ 214 x Contents This page has been reformatted by Knovel to provide easier navigation. 8.3.2 Deformation Studies .................................. 217 8.4 Composites ................................................................... 221 8.4.1 Single-Fibre Composites ............................ 221 8.4.2 Interfacial Micromechanics ......................... 224 8.5 Conclusions .................................................................. 227 8.6 Acknowledgements ...................................................... 228 8.7 References ................................................................... 228 9. Spin-Label Studies of Heterogeneous Polymer Systems ...................................................................... 231 9.1 Introduction ................................................................... 231 9.1.1 Synthesis of Spin Labels ............................ 232 9.2 Theoretical Background ............................................... 235 9.2.1 Correlation Times ...................................... 235 9.2.1.1 Fast Motion ................................... 239 9.2.1.2 Slow Motion ................................... 240 9.2.2 The Glass Transition and T50G ................... 240 9.3 Heterogeneous Systems .............................................. 242 9.4 Polymer Blends ............................................................. 245 9.5 References ................................................................... 251 10. The Use of ESR Spectroscopy for Studying Polymerization and Polymer Degradation Reactions .................................................................... 253 10.1 Introduction ................................................................... 253 10.2 Experimental ................................................................. 254 10.3 Results and Discussion ................................................ 255 10.3.1 Free Radical Polymerization ...................... 255 10.3.1.1 Identification of the Radicals in the ESR Spectrum ........................ 255 Contents xi This page has been reformatted by Knovel to provide easier navigation. 10.3.1.2 Measurement of Radical Concentration ................................ 256 10.3.1.3 Monomer Concentration during Polymerization ............................... 256 10.3.1.4 Radical Concentration during Polymerization ............................... 257 10.3.1.5 Correction for Changing Sensitivity of the Spectrometer ..... 259 10.3.1.6 Kinetic Analysis ............................. 260 10.3.1.7 Crosslinking Methacrylate Monomers ..................................... 261 10.3.2 Polymer Degradation by High-Energy Radiation ................................................... 263 10.3.2.1 Poly(Methyl Methacrylate) ............. 263 10.3.2.2 Polystyrene ................................... 267 10.3.2.3 Random Copolymers of Methyl Methacrylate and Styrene ............. 268 10.3.2.4 ESR and the Mechanism of Radiolysis ...................................... 269 10.4 Conclusions .................................................................. 273 10.5 Acknowledgements ...................................................... 273 10.6 References ................................................................... 273 11. Dynamics of Bulk Polymers and Polymerizing Systems as Studied Using Dielectric Relaxation Spectroscopy ............................................................. 275 11.1 Introduction ................................................................... 275 11.2 Amorphous Polymers: Phenomenological and Molecular Aspects ........................................................ 276 11.3 Crystalline Polymers ..................................................... 280 xii Contents This page has been reformatted by Knovel to provide easier navigation. 11.4 Liquid Crystalline (LC) Polymers .................................. 282 11.5 Real-Time Studies of Chemical and Physical Changes ....................................................................... 288 11.6 Conclusions and Future Prospects .............................. 293 11.7 Acknowledgements ...................................................... 294 11.8 References ................................................................... 294 12. Light Scattering from Polymer Systems .................. 297 12.1 Introduction ................................................................... 297 12.2 Small Angle Light Scattering (SALS) ........................... 298 12.2.1 Semi-Crystalline Polymers ......................... 298 12.2.2 Phase-Separating Polymer Mixtures .......... 305 12.3 Quasi-Elastic Light Scattering (QELS) ......................... 309 12.3.1 Dilute Polymer Solutions ............................ 309 12.3.2 Gels ........................................................... 311 12.3.3 Semi-Dilute Solutions and Trapped Chains ....................................................... 313