1 Introduction ................................................. 1
General Literature ........................................... 5
2 History of Cellulose Research ................................ 7
2.1 The Concept of Cellulose ................................ 7
2.2 Concepts in Structural Research of Cellulose ............ 8
2.3 Arrangements of the Cellulose Molecules in the Solid
State .................................................. 16
2.4 Chemical Constitution of Cellulose as
a Macromolecule ........................................ 21
2.4.1 Linkage of Cellulose - the Chain Structure
of Cellulose (Freudenberg, Haworth) ............. 22
2.4.2 Macromolecule Formation - Size of the Chains
(Staudinger) .................................... 24
2.5 Historical Development of X-ray Models for Native
Cellulose .............................................. 27
References .................................................. 46
3 Background .................................................. 53
3.1 Diffraction ............................................ 53
3.2 Model Building ......................................... 60
3.3 Spectroscopy ........................................... 64
3.3.1 Optical Spectroscopy ............................ 65
3.3.2 NMR Spectroscopy ................................ 68
3.4 Convention for the Description of Cellulosic (Chiral)
Structures ............................................. 72
References .................................................. 74
4 Model Compounds ............................................. 77
4.1 Conformation and Packing Analysis ...................... 77
4.2 Monomers and Dimers .................................... 78
4.3 Trimers and Tetramers .................................. 83
4.3.1 Conformations ................................... 83
4.3.2 Packing Arrangements ............................ 87
4.4 Acetyl Derivatives ..................................... 94
References .................................................. 98
5 Cellulose .................................................. 101
5.1 Cellulose Polymorphy .................................. 101
5.2 Characterization ...................................... 103
5.2.1 X-ray Characterization ......................... 103
5.2.2 Spectroscopic Characterization ................. 105
5.3 Molecular and Crystal Structure ....................... 112
5.3.1 Cellulose 1B ................................... 113
5.3.2 Cellulose la ................................... 122
5.3.3 Cellulose II ................................... 129
5.3.4 Cellulose III .................................. 138
5.3.5 Cellulose IV ................................... 143
5.4 Cellulose Solvent Complexes ........................... 151
5.4.1 Cellulose II-Hydrazine Complex ................. 151
5.4.2 Cellulose II Hydrate ........................... 152
5.4.3 Cellulose I-Ammonia I Complex .................. 156
5.4.4 Cellulose I-Ethylenediamine Complex ............ 160
5.5 Sodium Cellulose ...................................... 164
5.5.1 Sodium Cellulose I ............................. 165
5.5.2 Sodium Cellulose IV ............................ 169
References ................................................. 171
6 Cellulose Derivatives ...................................... 175
6.1 Characterization ...................................... 175
6.1.1 Cellulose Triacetate ........................... 175
6.1.2 Experimental Data for Cellulose Tripropionate
and Cellulose Acetate Dipropionate and
Further Cellulose Esters ....................... 179
6.2 Conformation and Packing Arrangement of СТА I,
СТА II and CTA-N ...................................... 185
6.3 Conformation and Packing Arrangement of CDAP .......... 197
6.4 Conformation and Packing Arrangement of Cellulose
Tribenzoate ........................................... 199
6.5 Trimethyl Cellulose and 6-O-Acetyl-2,3-di-O-methyl
Cellulose ............................................. 200
References ................................................. 204
7 Morphology ................................................. 207
7.1 Crystalline Domain Sizes .............................. 207
7.2 Microfibrils .......................................... 207
7.3 Microfibrils and Fibrils .............................. 212
7.4 Parallel and Antiparallel Packing Arrangements of
Microfibils ........................................... 216
References .................................................... 220
Appendix ...................................................... 223
Index ......................................................... 281
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