D. Klemm, B. Philipp, T.

Heinze,
U. Heinze, W Wagenknecht

Comprehensive
Cellulose Chemistry
Volume 1
Fundamentals and Analytical Methods

WILEY-VCH
Weinheim • New York • Chichester • Brisbane • Singapore • Toronto
Contents

Volume 1: Chapters 1 to 3

1 Introduction 1

2 General Considerations on Structure and Reactivity

of Cellulose 9
2.1 Structure and Properties of Cellulose 9
2.1.1 The molecular structure 9
2.1.2 The supramolecular structure 15
2.1.3 The morphological structure 22
2.1.4 Pore structure and inner surface 25
2.1.5 The accessibility of cellulose 29
2.1.6 Alien substances associated with the cellulose matrix 32
2.1.7 Macroscopic properties of cellulose 33
2.1.7.1 General properties and gross morphology 33
2.1.7.2 Mechanical properties of cellulose 35
2.1.7.3 Electrical, optical and thermal properties of cellulose 37
2.1.7.4 Chemical and environmental properties of cellulose 39
2.2 Swelling and Dissolution of Cellulose 43
2.2.1 Limited swelling of cellulose 44
2.2.1.1 Swelling of cellulose in water 45
2.2.1.2 Limited swelling of cellulose in some organic liquids in
comparison with water 51
2.2.1.3 Swelling of cellulose in aqueous solutions of sodium hydroxide
and in related systems 56
2.2.1.4 Interaction of cellulose in media in the transition range between
solvent and swelling agent 58
2.2.2 Dissolution of cellulose 60
2.2.2.1 Some general comments on cellulose dissolution 60
2.2.2.2 Systematic description of important classes of cellulose solvent
systems 62
2.2.2.3 Structure formation of cellulose and cellulose derivatives 73
2.2.3 Concluding remarks 79
VIII Contents

2.3 Degradation of Cellulose 83

2.3.1 Hydrolytic degradation of cellulose : 84
2.3.1.1 Acid hydrolysis of cellulose 85
2.3.1.2 Enzymatic hydrolysis 93
2.3.2 Degradation of cellulose by aqueous alkali 99
2.3.3 Oxidative degradation of cellulose 101
2.3.4 Mechanical degradation of cellulose 104
2.3.5 Thermal degradation of cellulose and cellulose derivatives 107
2.3.6 Radiation degradation of cellulose 118
2.3.7 Consequences of degradation of cellulose on its chemical
processing 124
2.4 Principles of Cellulose Reactions 130
2.4.1 Some principles of polymer reactions 130
2.4.2 Survey of important reaction types of cellulose 135
2.4.2.1 Principles and characteristics of cellulose reactions under
homogeneous conditions 141
2.4.2.2 Principles and characteristics of cellulose reactions under
heterogeneous conditions 145
2.4.2.3 Activation of cellulose 150
2.4.3 Advantages and limitations of cellulose reactions in DMA/LiCl
solution 155

3 Analytical Methods in Cellulose Chemistry 167

3.1 Determination of the Degree of Polymerization of
Cellulose and its Derivatives 168
3.2 Chemical Analysis (Elemental Analysis and Functional Group
Analysis) of Cellulose and Cellulose Derivatives 173
3.3 Application of Instrumental Analysis in Cellulose Chemistry 181
3.4 Techniques of Polymer Fractionation and Chromatographic
Separation in Cellulose Analysis 195
3.5 Summary of Analytical Routes to Total DS and Substituent
Distribution 202
3.6 Characterization of the Structure of Cellulosics in the Solid
State 204
3.7 Characterization of Cellulose-Liquid Interaction on Swelling
and Dissolution 213
3.8 Outlook for the Future Development of Cellulose Analysis 217
 Contents IX

Appendix I Experimental Protocols for the Analysis of Cellulose 223

Fractionation of cellulose nitrate .' 227
Preparation of:
level-off DP cellulose 232
decrystallized cellulose 232
cellulose tricarbanilate 233
Determination of:
DP of cellulose 234
DS of cellulose acetate 235
carbonyl group content of cellulose 236
carboxyl group content 236
water retention value of cellulose 237
DS of cellulose xanthogenate 238
DS of carboxymethylcellulose 240
DS of tritylcellulose 241
Structure analysis of thexyldimethylsilylcelluloses by NMR spectroscopy
andHPLC 241
Alkali resistance of cellulosic materials 243
Alkali solubility of cellulose materials 247

Subject index 253