Table Of ContentNMR
Basic Principles and Progress
Grundlagen und Fortschritte
Volume 4
Editors: P. Diehl E. Fluck R. Kosfeld
With 202 Figures
Springer-Verlag Berlin · Heidelberg· New York 1971
Lectures presented at the Seventh Colloquium on
NMR Spectroscopy
Natural and Synthetic
High Polymers
Held in the Institut flir Physikalische Chemie, April 13 -17, 1970 as part of the
100 th anniversary celebrations of the Rheinisch-Westfalische Technische Hoch
schule Aachen, Western Germany
Conference Chairman: Dr. R. KOSFELD
1870 1970
RWTH
AACHEN
Professor Dr. P. DIEHL
Physikalisches Institut der Universitat Basel
Professor Dr. E. FLUCK
Institut fUr Anorganische Chemie der Universitat Stuttgart
Dozent Dr. R. KOSFELD
Institut fUr Physikalische Chemie
der Rhein.-Westf. Technischen Hochschule Aachen
ISBN-13: 978-3-642-65091-8 e-ISBN-13: 978-3-642-65089-5
DOl: 10.1007/978-3-642-65089-5
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Verlag Berlin· Heidelberg 1971. Library of Congress Catalog Card Number 70-94160.
Softcover reprint of the hardcover 1s t edition 1971
Preface
Nuclear magnetic resonance spectroscopy, which has evolved only within
the last 20 years, has become one of the very important tools in chemistry and
physics. The literature on its theory and application has grown immensely and
a comprehensive and adequate treatment of all branches by one author, or even
by several, becomes increasingly difficult.
This series is planned to present articles written by experts working in various
fields of nuclear magnetic resonance spectroscopy, and will contain review
articles as well as progress reports and original work. Its main aim, however,
is to fill a gap, existing in literature, by publishing articles written by specialists,
which take the reader from the introductory stage to the latest development in
the field.
The editors are grateful to the authors for the time and effort spent in writing
the articles, and for their invaluable cooperation.
The papers presented here are condensed versions of the main contributions
to the 7th Colloquium on Nuclear Magnetic Resonance Spectroscopy, which
was made possible by the generous support of the Freunde der Aachener Hoch
schule (FAHO). The RWTH is indebted to the FAHO and to all the participants
who contributed to the success of the Colloquium.
The Editors
Table of Contents
High Resolution NMR Spectroscopy of Polymers. F. A. BOVEY . . . . . . . . . 1
NMR-Untersuchungen an Poly-a-Methylstyrol und dessen Copolymeren
mit Butadien. H.-J. CANTOW, K. F. ELGERT, E. SEILER und H. FRIEBOLIN 21
Complete Triad Assignment of Methylmethacrylate-Methacrylic Acid Co-
polymers. E. KLESPER, W. GRONSKI and A. JOHNSEN............ . .. 47
Problems of Aromatic Copolymer 'Structure. H. J. HARWOOD ........... 71
Research of Homopolymers and Copolymers of Propylene. A. ZAMBELLI 101
Penultimate Effects in Radical Copolymerization 1-Kinetical Study.
J. GUILLOT ................................................... 109
The Cotacticity of (Acrylonitrile-Methyl-Methacrylate) Copolymer by
NMR Spectroscopy. PHAM Q. T. ................................ 119
New Concepts in Copolymer Statistics. C. TOSI . .. . . . . . . . . . . . . . . . . . . . . 129
Nuclear Magnetic Resonance Wide Line Studies of Water Sorption and
Hydrogen Bonding in Cellulose. E. FORSLIND. . . . . . . . . . . . . .. . . . . . . . 145
The Proton Magnetic Resonance Spectroscopy of Proteins. H. A. O. HILL 167
Linienbreiten- und Relaxationsphanomene bei der NMR-Festkorperspek-
troskopie. R. KOSFELD und U. v. MYLIUS ......................... 181
NMR Studies of Solid Polymers. W. P. SLICHTER ..................... 209
Untersuchung von Beweglichkeiten in Polymeren durch NMR. K. BERG-
MANN........................................................ 233
Magnetic Relaxation in Polymers. The Rotating Frame Method. T. M.
CONNOR...................................................... 247
Some Aspects of the Dielectric Relaxation of Amorphous Polymers In
cluding the Effects of a Hydrostatic Pressure. G. WILLIAMS and D. C.
WATTS....................................................... 271
Conformations of Polymer Chains as Revealed by Infrared Spectroscopy.
T. SHIMANOUCHI. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 287
ESR-Untersuchungen an Hochpolymeren. H. FISCHER. . . . . . . . . . . . . . . . . 301
List of Contributors
BERGMANN, K., Dr., MeB- und PrUflaboratorium der Badischen Anilin- & Soda
Fabrik, Ludwigshafen, BRD
BOVEY, F. A., Dr., Bell Telephone Laboratories, Mountain Avenue, Murray Hill,
New Jersey, USA
CANTOW, H.-J., Prof., Dr., Institut fUr Makromolekulare Chemie, Freiburg, BRD
CONNOR, T. M., Dr., Ministry of Technology, National Physical Laboratory,
Teddington, Middlesex, England
ELGERT, K. F., Dr., Institut fUr Makromolekulare Chemie, Freiburg, BRD
FISCHER, H., Prof., Dr., Physikalisch-chemisches Institut der Universitat, ZUrich,
Switzerland
FORSLlND, E., Prof., Dr., Division of Physical Chemistry, The Royal Institute
of Technology, Stockholm, Sweden
FRIEBOLlN, H., Dr., Institut fUr Makromolekulare Chemie, Freiburg, BRD
GRONSKI, W., Dr., Institut fUr Makromolekulare Chemie, Freiburg, BRD
GUILLOT, J., Dr., Institut de Recherches sur la Catalyse, 39, Boulevard du
11 Novembre 1918, Villeurbanne, France
HARWOOD, H. J., Prof., Institute of Polymer Science, The University of Akron,
Ohio, USA
HILL, H. A. 0., Dr., Inorganic Chemistry Laboratory, Oxford, England
JOHNSEN, A., Dr., Institut fUr Makromolekulare Chemie, Freiburg, BRD
KLESPER, E., Dr., Institut fUr Makromolekulare Chemie, Freiburg, BRD
KOSFELD, R., Doz., Dr., Institut fUr Physikalische Chemie der Rhein.-West-
falischen Technischen Hochschule, Aachen, BRD
v. MYLIUS, u., Dipl.-Phys., Institut fUr Physikalische Chemie der Rhein.~West
falischen Technischen Hochschule, Aachen, BRD
PHAM, Q. T., Dr., Institut de Recherches sur la Catalyse, 39, Boulevard du
11 Novembre 1918, Villeurbanne, France
SEILER, E., Dr., Institut fUr Makromolekulare Chemie, Freiburg, BRD
SHIMANOUCHI, T., Prof., Dr., Department of Chemistry, Faculty of Science,
University of Tokyo, Hongo, Tokyo, Japan
x List of Contributors
SLICHTER, W. P., Prof., Dr., Bell Telephone Laboratories, Mountain Avenue,
Murray Hill, New Jersey, USA
TOSI, c., Dr., Centro Ricerche di Milano, Montecatini Edison S.p.A., Via G.
Colombo 81, Milano, Italia
WATTS, D. C., Dr., The University College of Wales, Edward Davies Chemical
Laboratory, Aberystwyth, England
WILLIAMS, G., Dr., The University College of Wales, Edward Davies Chemical
Laboratory, Aberystwyth, England
ZAMBELLI, A., Prof., Dr., Conciglio Nazionale delle Ricerche, Centro Nazionale
di Chimica delle Macromol-Sezione 1, Piazza Leonardo da Vinci 32, Milano,
Italia
High Resolution NMR Spectroscopy of Polymers
F. A. BOVEY
Bell Telephone Laboratories, Incorporated, Murray Hill, New Jersey, USA
Contents
1. Introduction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
2. Polypropylene . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
3. Polyvinyl Chloride ............................................. 12
4. C-13 Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
5. References. . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1. Introduction
The application of high resolution nuclear magnetic resonance spectroscopy
to the study of polymer structure is a field which is now about ten years old and
has recently grown very rapidly. This technique is employed in nearly every
center of polymer research throughout the world and can claim a place as a major
tool of macromolecular science. The literature alone can attest to this fact. In
preparing recent reviews, I found it necessary to refer to nearly 600 substantial
papers, and there are many additional ones of more marginal interest.
Today, I would like to discuss some recent work in our laboratory dealing
with the configuration and conformation of vinyl polymers. Of the several vinyl
polymers that might be discussed, I have chosen two: polypropylene and poly
vinyl chloride. These polymers are not only of major technological importance,
but they also present quite challenging problems of analysis and interpretation.
It may be said at the outset that use of the 220 MHz superconducting spectrometer
and of computer simulation of the spectra are essential in order to be able to draw
unambiguous conclusions.
I would like also to discuss briefly some aspects of future developments in
the high resolution NMR of polymers, in particular, C-13 spectroscopy.
2. Polypropylene
Polypropylene has been the subject of a large number of NMR investigations.
Its spectrum is complicated not only by vicinal coupling of the a. and f3 protons
but also by coupling of the a. and a.-methyl protons. The increased spectral
simplicity attained in high magnetic fields is shown by comparing the 60 MHz
spectra [1J of the isotactic (Fig. 1 a) and syndiotactic (Fig. 1 b) polymers with
2 F. A. BOVEY
the spectra of these same polymers at 220 MHz (Fig.2) [2-4]. The 60 MHz
spectra show extensive peak overlap and broadening, the latter arising in large
2.0 1.5 1.0 0.5
(5 ppm
Fig. 1. 60 MHz spectra of polypropylene (in o-dichlorobenzene at 150C);
(a) isotactic; (b) syndiotactic (ref. 1)
part from the multiplicity of transitions in this strongly coupled system. The
220 MHz spectra, by contrast, are nearly first order (Fig. 2). The (X-CH resonance
near 1.6 <5 is rather insensitive to configuration, but the remainder of the spectrum
is strikingly different for the two polymers. This means that even very low levels
of configurational impurity can be detected and identified, as we shall see. The f3
protons, which appear as the expected single multiplet in the spectrum of the syn
diotactic polymer, are very widely spaced in chemical shift in the isotactic
polymer's spectrum. Some difference in chemical shift is of course expected,
since from first principles these protons must be nonequivalent in the isotactic
polymer, as is now well known. The large magnitude of the difference is, however,
a mystery at present, for calculations by Dr. HEATLEY in our laboratoty, based on
current ideas of C - C and C - H bond anisotropies, predict a difference which
is smaller by an order of magnitude and of the wrong sign. FLORY and FUJIWARA
have recently discussed this question [5].
High Resolution NMR Spectroscopy of Polymers 3
(a)
(b)
1.75 1.25 1.00 0.75 ppm
Fig. 2. 220 MHz spectra of polypropylene (in a-dichlorobenzene at 165°);
(a) isotactic; (b) syndiotactic (refs. 2 and 3)
The parameters of these spectra are calculated on a six-spin "dimer model",
and are as follows for the polymers in o-dichlorobenzene at 110°.
For the isotactic polymer [4, 6] the following parameters are obtained:
CH3HB CH3
I I I
Hx HA Hx
HA (anti, or threo in P-d polymers): 1.26 D JAB: -13.5 Hz
1 1
HB (syn, or erythro): 0.869 D JAX: 6.0 Hz
: 0.85 D J 7.0 Hz
6 BX:
Hx: 1.66 D 6.5 Hz.
0 JCH,-HX:
