NMR and Macromolecules, Copyright, ACS Symposium Series

Downloaded by 80.82.77.83 on January 4, 2018 | http://pubs.acs.org Publication Date: March 28, 1984 | doi: 10.1021/bk-1984-0247.fw001

NMR and Macromolecules

Randall; NMR and Macromolecules ACS Symposium Series; American Chemical Society: Washington, DC, 1984.



ACS SYMPOSIUM SERIES

247

NMR and Macromolecules


Sequence, Dynamic, and Domain Structure James C. Randall, E D I T O R Phillips Petroleum Company

Based on a symposium sponsored by the Division of Organic Coatings and Plastics Chemistry at the 185th Meeting of the American Chemical Society, Seattle, Washington, March 20-25, 1983

American Chemical Society, Washington, D.C. 1984


Library of Congress Cataloging in Publication Data


N M R and macromolecules. ( A C S symposium series, I S S N 0097-6156; 247) "Based on a symposium sponsored by the Division of Organic Coatings and Plastics Chemistry at the 185th Meeting of the American Chemical Society, Seattle, Washington, March 20-25, 1983." Includes bibliographies and index. 1. Macromolecules—Analysis—Congresses. 2. Nuclear magnetic resonance spectroscopy— Congresses. I. Randall, James C . II. American Chemical Society. Division of Organic Coatings and Plastics Chemistry. III. Title: N.M.R. and macromolecules. IV. Series. QD380.N57 1984 I S B N 0-8412-0829-8

547.7'046

84-366

Copyright © 1984 American Chemical Society A l l Rights Reserved. The appearance of the code at the bottom of the first page of each chapter in this volume indicates the copyright owner's consent that reprographic copies of the chapter may be made for personal or internal use or for the personal or internal use of specific clients. This consent is given on the condition, however, that the copier pay the stated per copy fee through the Copyright Clearance Center, Inc., 21 Congress Street, Salem, M A 01970, for copying beyond that permitted by Sections 107 or 108 of the U . S . Copyright Law. This consent does not extend to copying or transmission by any means—graphic or electronic—for any other purpose, such as for general distribution, for advertising or promotional purposes, for creating a new collective work, for resale, or for information storage and retrieval systems. The copying fee for each chapter is indicated in the code at the bottom of the first page of the chapter. The citation of trade names and/or names of manufacturers in this publication is not to be construed as an endorsement or as approval by A C S of the commercial products or services referenced herein; nor should the mere reference herein to any drawing, specification, chemical process, or other data be regarded as a license or as a conveyance of any right or permission, to the holder, reader, or any other person or corporation, to manufacture, reproduce, use, or sell any patented invention or copyrighted work that may in any way be related thereto. Registered names, trademarks, etc., used in this publication, even without specific indication thereof, are not to be considered unprotected by law. PRINTED IN T H E UNITED STATES OF A M E R I C A


ACS Symposium Series Downloaded by 80.82.77.83 on January 4, 2018 | http://pubs.acs.org Publication Date: March 28, 1984 | doi: 10.1021/bk-1984-0247.fw001

M . Joan Comstock, Series Editor

Advisory Board Robert Baker

Geoffrey D. Parfitt

U.S. Geological Survey

Carnegie Mellon University

Martin L. Gorbaty

Theodore Provder

Exxon Research and Engineering Co.

Glidden Coatings and Resins

Herbert D. Kaesz

James C. Randall

University of California- Los Angeles

Phillips Petroleum Company

Rudolph J. Marcus

Charles N . Satterfield

Office of Naval Research

Massachusetts Institute of Technology

Marvin Margoshes

Dennis Schuetzle

Technicon Instruments Corporation

Ford Motor Company Research Laboratory

Donald E. Moreland U S D A , Agricultural Research Service

Davis L . Temple, Jr. Mead Johnson

W. H . Norton J. T. Baker Chemical Company

Charles S. Tuesday General Motors Research Laboratory

Robert Ory U S D A , Southern Regional Research Center

C. Grant Willson I B M Research Department



FOREWORD The A C S SYMPOSIUM SERIES was founded in 1974 to provide a medium for publishing symposia quickly in book form. The format of the Series parallels that of the continuing ADVANCES I N CHEMISTRY SERIES except that in order to save time the papers are not typeset but are reproduced as they are submitted by the authors in camera-ready form. Papers are reviewed under the supervision of the Editors with the assistance of the Series Advisory Board and are selected to maintain the integrity of the symposia; however, verbatim reproductions of previously published papers are not accepted. Both reviews and

reports of research are acceptable since symposia may

embrace both types of presentation.



This book is dedicated to Frank A . Bovey, a pioneer researcher in NMR studies of polymers, on the occasion of his receipt of the American Chemical Society award in Applied Polymer Science, sponsored by the Phillips Petroleum Company, March 22, 1983.





FRANK A . BOVEY's research interests center a r o u n d the application o f N M R spectroscopy to the study o f structure, dynamics, and m o r p h o l o g y o f synthetic polymers and bio poly mers. H e has made major contributions to these fields, p r i m a r i l y through the development of techniques to determine microstructure in h o m o p o l y m e r and c o p o l y m e r chains and in the discovery and characterization of defect structures in v i n y l and related polymers. H e is the head of the P o l y m e r C h e m i s t r y Research Department at Bell L a b o r a t o ries, M u r r a y H i l l , N . J . D r . Bovey was b o r n in M i n n e a p o l i s in 1918. H e received a B . S . degree in chemistry from H a r v a r d in 1940, w o r k e d d u r i n g W o r l d W a r II for the N a t i o n a l Synthetic R u b b e r C o r p o r a t i o n , a 3 M subsidiary, and entered graduate school at the University of M i n n e s o t a as a R u b b e r Reserve F e l l o w in 1945. H i s thesis w o r k , carried out under the direction of I. M . Kolthoff, dealt with the mechanism o f free radical polymerization. D u r i n g this time he w o r k e d out the mechanism of oxygen i n h i b i t i o n and discovered oxygen sty re ne copolymers. After receiving his P h . D . in 1948, D r . Bovey returned to 3 M , now in the C e n t r a l Research Department, where he was made a research associate in 1955. It was at 3 M , d u r i n g the period from 1956 to 1962, that he conducted his pioneering investigations into the characterization o f polymers using N M R techniques. He reported some o f the first high-resolution p r o t o n N M R spectra of polymers in the late 1950s, at a time when it was still generally assumed that the spectra of macromolecules were too c o m p l e x to interpret. E x p l o i t i n g the rich detail in these spectra, he developed N M R techniques that are now used routinely in measuring the microstructure of polymer chains. These N M R methods made possible for the first time the determination and quantification o f the stereochemical configurations of noncrystallizable polymers. In 1962 D r . Bovey joined Bell Laboratories as a member of the technical staff, and was appointed to his present position in 1967. H e continued his detailed studies of polymer structure and c o n f o r m a t i o n at Bell Laboratories, and extended the scope of his w o r k to include investigations o f nuclei other than protons, branch analyses in polyethylene, and determination o f defect structures in v i n y l and related polymers. He continues to have a vigorous research p r o g r a m in the areas of polymer conformations in the solid state, polymer m o r p h o l o g y , and the mechanisms of polymer stabilization and degradation. D r . Bovey has published more than 125 papers o n his e x p l o r a t o r y research o n polymers and has contributed about 20 chapters to b o o k s in the field. He has written or has been coauthor of 10 books, including " M a c r o molecules, an Introduction to P o l y m e r Science" w i t h F. H . W i n s l o w in 1979 and " C h a i n Structure and C o n f o r m a t i o n of M a c r o m o l e c u l e s " in 1982. IX



He has served on an ad hoc panel of the National Academy of Sciences for the study of guayule rubber, and is currently serving on the nominating committee for a National Research Council panel on Polymer Science and Engineering. He has recently served on the Chemistry Panel of the National Research Council Fellowship Office; on the National Research Council Evaluation Panel for the Center for Materials Science of the National Bureau of Standards; on the Study Section for the National Institute of General Medicine (NIH) Shared Instrumentation Program; and both on the organizing committee and as a member of the U.S. delegation to the 1979 China U.S. Bilateral Polymer Symposium (Beijing, October 1979), spon sored by the National Academy of Sciences. He is a member of the award committee for the Baker Award of the National Academy of Sciences. In addition, he serves on the editorial boards of the Journal of Polymer Science—Polymer Chemistry and Polymer Physics Editions—and is an associate editor of Macromolecules. Many awards and honors attest to Dr. Bovey's contributions to poly mer science. He received the Union Carbide Award of the Minnesota Section of the A C S in 1962. In 1969 he received the Witco Award in Polymer Chemistry of the A C S and the Outstanding Achievement Award of the University of Minnesota. In 1974 he was awarded the Ford High Polymer Physics Prize of the American Physical Society. In 1978 he received the Nichols Medal Award of the New York Section of the A C S and delivered the Whitby Memorial Lectures at the University of Akron. His receipt in 1983 of the American Chemical Society Award in Applied Polymer Science, sponsored by Phillips Petroleum Company, was the occasion for the sympo sium in his honor on which this book is based. Dr. Bovey is a member of the American Chemical Society, the Ameri can Physical Society, the American Society of Biological Chemists, the New York Academy of Sciences, Sigma X i , and Phi Lambda Upsilon. He was elected to the National Academy of Sciences in 1975.

L. W. JELINSKY Bell Laboratories Murray Hill, N . J .

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NMR and Macromolecules, Copyright, ACS Symposium Series

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