Crystalline Cellulose and Cellulose Derivatives - Characterization and Sructures PDF

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Springer Series in Wood Science Series Editors T. E. Timell State University of New York College of Environmental Science and Forestry Syracuse, NY 13210, USA Professor Dr. Rupert Wimmer Bio-based Fibre Materials Department of Material Sciences and Process Engineering University of Natural Resources...

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Crystalline Cellulose and Cellulose Derivatives - Characterization and Sructures Emil Amam

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Springer Series in Wood Science

Series Editors T. E. Timell State University of New York College of Environmental Science and Forestry Syracuse, NY 13210, USA Professor Dr. Rupert Wimmer Bio-based Fibre Materials Department of Material Sciences and Process Engineering University of Natural Resources and Applied Life Sciences BOKU-Vienna Peter-Jordan-Strasse 82 1190 Vienna, Austria

Springer Series in Wood Science Editors: T.E. Timell, R. Wimmer L.W. Roberts/P.B. Gahan/R. Aloni Vascular Differentiation and Plant Growth Regulators (1988) C. Skaar Wood-Water Relations (1988) J.M. Harris Spital Grain and Wave Phenomena in Wood Formation (1989) B.J. Zobel/J.P. van Buijtenen Wood Variation (1989) P. Hakkila Utilization of Residual Forest Biomass (1989) J.W. Rowe (Ed.) Natural Products of Wood Plants (1989) K.-E.L. Eriksson/R.A. Blanchette/P. Ander Microbial and Enzymatic Degradation of Wood and Wood Components (1990) R.A. Blanchette/A.R. Biggs (Eds.) Defense Mechanisms of Woody Plants Againts Fungi (1992) S.Y. Lin/C.W. Dence (Eds.) Methods in Lignin Chemistry (1992) G. Torgovnikov Dielectric Properties of Wood and Wood-Based Materials (1993) F.H. Schweingruber Trees and Wood in Dendrochronology (1993) P.R. Larson The Vascular Camblum: Development and Structure (1994) M.-S. Ilvessalo-Pfaffli Fiber Atlac Identification of Papermaking Fibers (1995) B.J. Zobel/J.B. Jett Genetics of Wood Production (1995) C. Matteck/H. Kabier Wood - The Internal Optimization of Wood (1997) T. Higuchi Biochemistry and Molecular Biology of Trees (1997) B.J. Zobel/J.R. Sprague Juvenile Wood in Forest Trees (1998) E. Sjostrom/R. Alén (Eds.) Analytical Methods in Wood Chemistry, Pulping, and Papermaking (1999) R.B. Kery/T.A.G. Langrish/J.C.F. Walker Kiln-Drying of Lumber (2000) S. Carlquist Comparative Wood Anatomy, 2nd ed. (2001) M.T. Tyree/M.H. Zimmermann Xylem Structure and the Ascent of Sap. 2nd ed. (2002) T. Koshijima/T. Watanabe Association Between Lignin and Carbohydrates in Wood and Other Plant Tissues (2003) V. Bucur Nondestructive Characterisation and Imaging of Wood (2003) V. Bucur Acoustics of Wood (2006) F.H. Schweingruber Wood Structure and Environment (2007) P. Zugenmaier Crystalline Cellulose and Derivatives

Peter Zugenmaier

Crystalline Cellulose and Derivatives Characterization and Structures

Professor Peter Zugenmaier Institute of Physical Chemistry TU Clausthal Arnold-Sommerfeld-Str. 4 D-38678 Clausthal-Zellerfeld Germany

Cover: Transverse section of Pinus lambertiana wood. Courtesy of Dr. Carl de Zeeuw, SUNY College of Environmental Science and Forestry, Syracuse, New York.

ISBN 978-3-540-73933-3

e-ISBN 978-3-540-73934-0

Springer Series in Wood Science ISSN 1431-8563 Library of Congress Control Number: 2007933158 © 2008 Springer-Verlag Berlin Heidelberg This work is subject to copyright. All rights are reserved, whether the whole or part of the material is concerned, specifically the rights of translation, reprinting, reuse of illustrations, recitation, broadcasting, reproduction on microfilm or in any other way, and storage in data banks. Duplication of this publication or parts thereof is permitted only under the provisions of the German Copyright Law of September 9, 1965, in its current version, and permission for use must always be obtained from Springer. Violations are liable to prosecution under the German Copyright Law. The use of general descriptive names, registered names, trademarks, etc. in this publication does not imply, even in the absence of a specific statement, that such names are exempt from the relevant protective laws and regulations and therefore free for general use. Cover design: WMXDesign GmbH, Heidelberg, Germany Printed on acid-free paper springer.com

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Preface

“On making many books there is no end” but we trust that no excuse is needed for the present work. The subject of cellulose chemistry is among the simplest of studies, but the important advances of recent years have clarified it to such an extent that we feel the time is ripe for publishing a relatively simple book which may act as a guide to younger chemists who are entering those branches of our great industries which are concerned with cellulose. J.T. Marsh and F.C. Wood (1939) An Introduction to the Chemistry of Cellulose

Recent progress in crystalline polysaccharide structure determination and the publication of numerous models of cellulose and cellulose derivatives by improved methods made a critical and up-to-date survey of structures and characterization of cellulose possible and necessary. Structural evaluations by refined experimental and computer-aided modeling represent the prerequisite for many research and testing areas of cellulosic materials, e.g., for establishing structure–property relationships (tensile strength, sorption, solubility, etc.), chemical reactivity and derivatization as well as the composition of cell wall materials and the orientation of microfibrils in cellulose fibers. Modern materials science needs tailored materials, linked to the structure for improvements and for new developments. The active species for enantiomeric separation in gel permeation chromatography columns are, e.g., microcrystalline cellulose derivative beads of a particular structure, which produce optimal results. Composites with soft materials and cellulose or cellulose derivatives exhibit enhanced properties strongly dependent on the stiff cellulosic backbone and can be improved by optimizing the interaction parameters. This book is concerned with the crystalline structure and characterization of cellulose, cellulose complexes and cellulose derivatives. The principles of structure determination of polymers rely on fiber diffraction combined with computer-aided modeling and also on spectroscopy. The various now-available results are evaluated and compared with oligomeric structures from which invariants are derived and used as standards. Suitable models were chosen and the geometric data are compared and best models according to standards shown in graphs and the coordinates are collected in an v

vi

Preface

Appendix. Representative X-ray, solid-state 13C NMR and IR patterns are provided for characterizing cellulosic structures. Research on cellulose started as soon as appropriate methods were available at the beginning of the twentieth century. The history of polymer science is closely linked to the development of the structure of native cellulose and in the beginning this was controversially discussed as aggregates of small molecular units or as macromolecules on one side. The macromolecular concept grew out of these controversies. On the other side the crystal packing arrangement was proposed to occur by parallel chains with all the nonreducing cellulose ends on one tip of the native microcrystals or by antiparallel arrangements with adjacent nonreducing ends on opposite tips. It was not until improved crystalline fibers and finer detection methods were available that conclusive computer-aided conformation and packing analysis led to a decisive proposal for the parallel packing of the native structure of cellulose. This development is critically overviewed in a chapter devoted to the history of cellulose research. However, antiparallel arrangements are observed for soft treated mercerized native cellulose and most derivatives. A conversion mechanism is needed and is presented to describe the conversion from native to mercerized cellulose by preserving the orientation of chains in fibers during this conversion. This book is a valuable, concise and up-to-date guide for the materials and life science community involved with cellulose and related materials. A rigorous description of the refinement procedures for structure determination is not presented here but may be found in the original publications. This book represents a collection of critically selected structures and is directed towards students, scientists and researchers in materials quality control who are interested in or depend on knowledge of crystalline cellulosic structures and who need reference data for characterizing materials. This book was initiated by Tore E. Timell, Syracuse, NY, USA, late editor of Springer Series in Wood Science. Without his enthusiastic encouragement and support this book would never have been finished. Cellulose as an abundant renewable material has stimulated basic and applied research throughout the years, as addressed in the historical review, and has inspired significant progress in polymer science. In recent years cellulose has gained renewed significance as a raw material and still possesses high potential for future applications. Academia and industry may equally profit from this comprehensive survey. Peter Zugenmaier

Acknowledgement for Copyrights

I wish to acknowledge permission from the following publishers to reproduce the copyrighted material indicated. Acknowledgments to the original sources are given in the figure captions: American Chemical Society Washington DC: ACS Symposium Series: Cellulose derivatives (1998): Figure 7.2 J Amer Chem Soc: Figures 5.9, 5.14 Macromolecules: Scheme 5.1, Figures 5.4, 5.6, 5.8, 5.13, 5.16, 5.25, 5.26, 5.40, 5.47, 5.51, 6.8, 6.19 a,b, A2 Biomacromolecules: Figures 5.20, 5.33-36 Elsevier Elsevier Publishing Company, Inc. New York-Amsterdam-London-Brussels: Physics and chemistry of cellulose fibres (1949): Figures 2.14, 5.19 Academic Press, London-New York: Polymer and fibre diffraction (1972): Figure 3.6 Advances in Carbohydrate Chemistry and Biochemistry: Figure 3.4 J Struct Biol: Figures 2.20, 5.7, 5.17 J Mol Struct: Figure 3.11, A1 Prog Polym Sci: Figures 3.14, 4.4, 4.4 Polymer: Table 5.11, Figure 5.24 Polymer Comm: Figure 6.5 Solid State Nucl Magn Reson: Figure 5.21 Carbohydr Res: Table 7.2 John Wiley & Sons Ltd, New York Ellis Horwood Ltd, Chichester, Cellulose: Structural and functional aspects (1989): Figures 6.6, 6.12, 6.13 Wiley Interscience, New York: The use of X-ray diffraction study of protein and nucleic structures (1966): Figures 3.3, 3.4 John Wiley, New York: Cellulose and wood – chemistry and technology (1989): Figures A7, A8 Ber Deutsch Chem Ges: Figure: 2.8 vii

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Acknowledgement for Copyrights

Bioploymers: Figures 5.38, 5.43 Helv Chim Acta: Figures 2.10, 2.17 J Appl Polym Sci: Figures 7.7, 7.8 J Polym Sci: Figures 2.19, A3-A6 J Polym Sci B: Figures 5.9, 5.37 J Polym Sci A: Figures 6.1, 6.2, 6.21 J Polym Sci Phys Ed: Figure 6.19c Makromol Chem: Figure 7.1 Verlag Chemie: Figure 2.7 Springer Verlag Berlin-Heidelberg: Cellulose: Table 5.10, Figures 5.18, 5.20, 5.28, 6.10, 6.24 Polym Bull: Table 3.2, Figure 3.13 Colloid & Polym Sci (Kolloid Z, Kolloid Z u Z Polymere):Table 2.2, Figures 6.3, 6.4, 6.21 J Materials Sci: Figure 7.4 Plenum Press, New York: Cellulose and other natural polymer systems (1982): Figure 7.5, Structural electron crystallography.(1995): Figure 6.20 Das Papier, Darmstadt: Figure 7.3 Francis and Taylor, London: J Carbohydr Chem. Figure 3.12 Hanser Publishers, Munich: Cellulosic polymers (1994): Table 5.2, Figures 5.1, 5.3 International Union of Pure and Applied Chemistry: Pure Appl Chem: Figure 3.4 Oldenbourg Wissenschaftsverlag, München:: Z Phys Chem: Figures 2.5b, 2.9, 2.18 The Society of Biotechnology, Osaka: J Biosci Bioeng: Table 5.20, Figure 5.44 The Society of Polymer Science, Tokyo: Polymer J: Figure 5.5 The drawings of the models were produced with software from Keller E (1992) Schakal 92: A computer program for graphic representation of molecules and crystallographic models. Freiburg

Contents

1

2

Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1

General Literature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

5

History of Cellulose Research . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

7

2.1 2.2 2.3 2.4

3

4

The Concept of Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Concepts in Structural Research of Cellulose. . . . . . . . . . . . . . . . . . . Arrangements of the Cellulose Molecules in the Solid State . . . . . . . Chemical Constitution of Cellulose as a Macromolecule. . . . . . . . . . 2.4.1 Linkage of Cellulose – the Chain Structure of Cellulose (Freudenberg, Haworth) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.4.2 Macromolecule Formation – Size of the Chains (Staudinger) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2.5 Historical Development of X-ray Models for Native Cellulose . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

7 8 16 21

Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

53

3.1 3.2 3.3

Diffraction. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Model Building . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3.1 Optical Spectroscopy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.3.2 NMR Spectroscopy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3.4 Convention for the Description of Cellulosic (Chiral) Structures . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

53 60 64 65 68 72 74

Model Compounds . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

77

4.1 4.2 4.3

77 78 83 83 87 94 98

Conformation and Packing Analysis . . . . . . . . . . . . . . . . . . . . . . . . . Monomers and Dimers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Trimers and Tetramers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3.1 Conformations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.3.2 Packing Arrangements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4.4 Acetyl Derivatives. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ix

22 24 27 46

x

Contents

5

Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101 5.1 5.2

Cellulose Polymorphy. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.1 X-ray Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.2.2 Spectroscopic Characterization . . . . . . . . . . . . . . . . . . . . . . . 5.3 Molecular and Crystal Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3.1 Cellulose Iβ. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3.2 Cellulose Iα . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3.3 Cellulose II . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3.4 Cellulose III . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.3.5 Cellulose IV . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.4 Cellulose Solvent Complexes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.4.1 Cellulose II–Hydrazine Complex . . . . . . . . . . . . . . . . . . . . . . 5.4.2 Cellulose II Hydrate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.4.3 Cellulose I–Ammonia I Complex . . . . . . . . . . . . . . . . . . . . . . 5.4.4 Cellulose I–Ethylenediamine Complex . . . . . . . . . . . . . . . . . 5.5 Sodium Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.5.1 Sodium Cellulose I . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5.5.2 Sodium Cellulose IV. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

Cellulose Derivatives . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175 6.1

Characterization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1.1 Cellulose Triacetate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.1.2 Experimental Data for Cellulose Tripropionate and Cellulose Acetate Dipropionate and Further Cellulose Esters . . . . . . . . 6.2 Conformation and Packing Arrangement of CTA I, CTA II and CTA-N . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.3 Conformation and Packing Arrangement of CDAP . . . . . . . . . . . . . . 6.4 Conformation and Packing Arrangement of Cellulose Tribenzoate . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6.5 Trimethyl Cellulose and 6-O-Acetyl-2,3-di-O-methyl Cellulose . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

101 103 103 105 112 113 122 129 138 143 151 151 152 156 160 164 165 169 171

175 175 179 185 197 199 200 204

Morphology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207 7.1 Crystalline Domain Sizes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.2 Microfibrils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.3 Microfibrils and Fibrils . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.4 Parallel and Antiparallel Packing Arrangements of Microfibils. . . . . References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

207 207 212 216 220

Appendix . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 223 Index . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 281

Chapter 1

Introduction

Cellulose represents a naturally occurring linear macromolecular chain of 1–4-linked b-d-glucopyranose and exhibits great chemical variability and potential in applications. The cell walls of all plants contain fibers of cellulose. Cellulose has long been harvested as commercial fibers from the seed hairs of cotton (over 94% cellulose), as bast fibers (60–80% cellulose) from flax, hemp, sisal, jute and ramie or as wood (40–55% cellulose), which is a common building material or is used as a source for purified cellulose. The chemical compositions of some known species are collected in Table 1.1, which, when purified, serve as cellulose sources. Wood represents a composite material with cellulose as a major part combined in excellent form with lignin and hemicelluloses, creating a unique high-strength and durable material, and recently c...