SOLID STATE NMR OF POLYMERS SOLID STATE NMR OF POLYMERS Edited by Lon J. Mathias University of Southern Mississippi Hafflesburg. Mississippi Springer Science+Business Media, LLC Library of Congress Cataloging-in-Publication Data Chemistry Conference of North America on Solid State NMR of Polymers (3rd : 1988 : Toronto, Ont.) Solid state NMR of polymers / edited by Lon J. Mathias, p. cm. "Proceedings of the Third Annual Chemistry Conference of North America on Solid State NMR of Polymers, held June 5-10, 1988, in Toronto, Canada"—T.p. verso. Includes bibliographical references and index. ISBN 978-1-4899-2476-6 1. Polymers—Analysis—Congresses. 2. Nuclear magnetic resonance spectroscopy—Congresses. I. Mathias, Lon J. II. Title. QD139.P6C48 1988 547.7046—dc20 91-23687 CIP Proceedings of the Third Annual Chemistry Conference of North America on Solid State NMR of Polymers, held June 5-10, 1988, in Toronto, Canada ISBN 978-1-4899-2476-6 ISBN 978-1-4899-2474-2 (eBook) DOI 10.1007/978-1-4899-2474-2 © 1991 Springer Science+Business Media New York Originally published by Plenum Press, New York in 1991 Softcover reprint of the hardcover 1st edition 1991 All rights reserved No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher PREFACE The chapters in this collection are from papers which were presented at a symposium on solid-state NMR of polymers. A two-part program on available NMR techniques applicable to solid polymer analysis was presented at the 3rd Chemical Congress of North American held in Toronto, Ontario, June 5-10,1988. The program was sponsored by the Division of Polymer Chemistry with support provided by the Division, its Industrial Sponsors, and the Donors of the Petroleum Research Fund administered by the American Chemical Society. Co-organizers included Professor Colin Fyfe of the University of British Columbia (Vancouver, Canada), Professor Hans Spiess of the Max Planck Institut fur Polymerforschung (Mainz, West Germany), and myself. The full-day tutorial, which was free to registered attendees, covered the range of topics. The purpose of the tutorial was to provide a basic introduction to the field so that newcomers to its present and future applications could develop sufficient understanding to learn effectively from the subsequent symposium. The first talk attempted to give listeners a feel for the way a novice spectroscopist can learn to use the various NMR techniques to explore his own areas of interest. Simple experiments can provide unique information about solid polymers that can be useful in interpreting synthetic results and in relating solid-state conformation, morphology and molecular motion to physical properties. The remaining five talks by internationally recognized experts in their areas covered the most commonly used techniques available today. These range from proven methods such as cross-polarization/magic angle spinning (CP/MAS) to magnetic resonance imaging (MRI) of polymers that is just developing as a useful tool for rigid polymer samples. The former is the frrst and most widely used method, and is "routine" on most instruments available today. It has been applied to nuclei such as UN, 29Si and 31p as well as 13C, and can provide information on chemical composition, molecular motion and relaxation processes, and polymer morphology. Advanced applications such as those employing variable temperature studies and two dimensional NMR pulse programs provide a wealth of information not available with any other single solid-state method. Multipulse NMR of nuclei like IH and 19p is well-suited for evaluating the details of molecular mobility and relaxation in solids. When combined with basic and advanced 2H NMR experiments of specifically labelled polymers, it is possible to probe molecular behavior throughout a polymer sample at relaxation times covering v vi Preface ca. 10 orders of magnitude. Not only is it possible to examine amorphous and crystalline or highly ordered regions of a sample independent of each other, it is now feasible to evaluate the types and rates of motions available to individual segments of polymer backbones and pendent groups. The contents of this talk are summarized in the chapter by Cecil Dybowski. Examples of 2H NMR applications are given in the overview paper by Ron Colletti and myself. One of the most exciting new areas of polymer characterization is a result of the enormous effort successfully devoted to the development of MRI for medical applications and biological research. Compared to CAT scans that are based on X-ray imaging of the hard or X-ray opaque regions of the body, MRI is most sensitive to the soft tissue. Skin, nerves, brain tissue and the circulatory system are examples of body components that can currently be resolved down to the 1 mm level. These methods, especially when coupled with the higher field strengths that can be used on inanimate objects, have been shown to provide 10 to 20 micron resolution images of soft, flexible polymers. New pulse programs and imaging techniques are also beginning to provide information on rigid polymers that are difficult to examine using traditional imaging methodology. This area is summarized by Jack Koenig in Chapter 3. Over 50 talks were given in the four-day symposium that followed the tutorial (see Polym. Preprints, 1988, 29(1), 3-102). These were organized under the same general topics as the tutorial with roughly equal coverage of the five main areas. This provided the 80-100 attendees at each session with a timely and comprehensive survey of current research efforts around the world in solid-state NMR analysis of polymers. In addition to speakers from the US and Canada, there were 7 speakers from West Gennany, 3 from Japan, 2 from Great Britain, and 1 each from France, the Netherlands, and New Zealand. Papers based on many of these talks are included in Chapters 4-25 and are arranged according to general subject areas. This book should provide the polymer community with an extensive introduction to the many aspects of solid-state NMR analysis of polymers. Learn to apply these methods to your own projects and you will find insight and understanding of molecular and microscopic behavior that can open up new vistas of research. I think I speak for all the authors in hoping that you fmd this book informative and useful. Let me also thank all of the contributors for their hard work and excellent contributions, and especially for their patience. Lon 1. Mathias CONTENTS I. Overviews 1. Multi-Pulse IH and I9p Techniques 1 Cecil Dybowski 2. Solid State ~ NMR: Overview with Specific Examples 23 Ronald F. Colletti and Lon 1. Mathias 3. Application of NMR Imaging to Polymers: A Tutorial 61 Jack L. Koenig II. 13C CP/MAS Applications 4. Solid State 13C NMR Studies of the Structures, Conformations, 81 and Dynamics of Semi-Crystalline Polymers A.E. Tonelli, MA. Gomez, Hajime Tanaka, and M.H. Cozine 5. CP/MAS 13C NMR Analysis of Poly(Arylene Methylene)s 107 Michael L. Froehlich and Martin B. Jones 6. Radiation Induced Morphological Changes in a Semi- 117 Crystalline Polymer: A 13C NMR Study A.L. Cholli, F.C. Schilling, and A.E. Tonelli 7. 13C NMR Studies of Poly(Vinylidene Fluoride) Blends 131 R.A. Grinsted and 1.L. Koenig 8. Solid State NMR Detection of Molecular-Level Mixing 145 Phenomena in Strongly Interacting Polymer Blends and Phase-Separated Copolymers Laurence A. Belfiore, Thomas J. Lutz, and Chihmin Cheng 9. CP/MAS NMR Spectra of Poly(N-Vinylcarbazole) and of its 167 Charge Transfer Complexes: Preliminary Investigation Almera Natansohn 10. I3C NMR of Crosslinked Poly(Methacrylic Anhydride) 179 D. Granger vii viii Contents 11. Application of Solid State 13C NMR Spectroscopy to Sulfur 201 Vulcanized Natural Rubber Jack L. Koenig and Mladen Andreis 12. A Solid State 13C NMR Study of Polysiloxane Side Chain 215 Liquid Crystalline Polymers Containing 2-[4-(2S)-Methyl- Butoxy)-Phenyl]-5-(ro-Alkyl)-1,3,2-Dioxaborinane with Alkyl Being Undecanyl and Octyl B.C. Perry and J.L. Koenig 13. VT/MAS NMR as a Probe of Molecular Mobility and Local 233 Composition: Solidified Acrylic Dispersions R. Voelkel III. Deuterium NMR 14. Molecular Motions in Crystalline and Mesomorphous Phases 245 of Large Size Cycloalkanes as a Model for Polyethylene Martin Moller, Gerhard Kogler, Dieter Oelfin, and Hansotto Drotloff 15. Solid State NMR Relaxation Study of Liquid Crystal 261 Polymers Employing a Two-Dimensional Technique A. Schleicher, K. Muller, and G. Kothe 16. Dynamics of Surface Bound Polymers and Coupling Agents 271 Frank D. Blum, Robert B. Funchess, and Wiriya Meesiri 17. Solid-State 2fI and 13C NMR Study of the Structure of 283 Polyanilines S. Kaplan, E.M. Conwell, A.F. Richter, and A.G. MacDiarmid IV. Multinuclear CP/MAS 18. The Solid-State 29Si and 13C NMR of Poly(Di-n-Alkylsilanes) 295 F.A. Bovey and F.C. Schilling 19. 29Si and 13C Magic Angle Sample Spinning Nuclear Magnetic 305 Resonance Spectroscopy of Ceramic Fibers Prepared by Pyrolysis of Organosilicon Polymers Jonathan Lipowitz and Gary L. Turner 20. Variable Temperature Solid-State NMR of Polyphosphazenes 321 James F. Haw and Richard C. Crosby Contents ix 21. Hydrogen Cyanide Polymers: Solid State NMR CSN and J3C) 331 Investigations CN. Matthews and R. Ludicky V. Imaging of Polymers 22. IH NMR Imaging of Solids with Magic Angle Spinning 343 D.G. Cory, A.M. Reichwein, J.C. De Boer, J.WM. van Os, and WS. Veeman 23. NMR Imaging: Application to Elastomeric Materials 363 C.c. Chang and R.A. Komoroski 24. NMR Imaging Investigations of Case II Diffusion in Polymers 377 L.A. Weisenberger and 1L. Koenig 25. Application of One-Dimensional NMR Imaging to Solvent 387 Diffusion Measurements in Polymeric Samples Stephen B. Pickup and Frank D. Blum Contributors 399 Index 403 Chapter 1 MULTIPLE-PULSE IH AND NMR TECHNIQUES 19F CECIL DYBOWSKI 1. Introduction The NMR spectroscopy of solids has developed into a useful tool for chemists in the last decade and a half because the control of the time evolution of the nuclear systems allows one to choose the effects one wishes to emphasize in a particular experiment. This remarkable concept -- that one could analyze only parts of the contributions to the time evolution of a nuclear magnetic system -grew out of an understanding of the physics of radiofrequency excitation of nuclear spins, as developed in several research laboratories in the middle-to-late 1960's [1]. In particular, the early experiments concentrated on the dipole-dipole interactions among protons or fluorines in strongly coupled solid materials. Thus, the ftrst experiments in this class were ones that subverted the dipole-dipole coupling among the abundant spins of a system to reveal subtler interactions such as the chemical shift. Rapid spinning of a solid had been shown, as early as 1958, to overcome the effects of dipole-dipole couplings and the anisotropic contributions to the chemical shift to yield a spectrum that depends only on the isotropic chemical shift - essentially a high-resolution spectrum [2]. Thus, a short time after the introduction of radiofrequency line-narrowing techniques, the coupling of these two technologies permitted a further improvement of the resolution of spectra of abundant spins [3]. We briefly describe the developments in spin dynamics and how they are applied to polymer systems. CECIL DYBOWSKI - Department of Chemistry and Biochemistry, University of Delaware, Newark, Delaware 19716. 1