Cellulose Derivatives (eBook)

Preface 9
Organization of This Book 10
Acknowledgements 12
Contents 13
Abbreviations and Symbols 16
1 Production and Characteristics of Cellulose from Different Sources 25
1.1 Plant Cellulose 26
1.1.1 Cellulose from Conventional Sources 26
1.1.1.1 Wood 26
1.1.1.2 Cotton Linters 32
1.1.2 Cellulose from Alternative Sources: Sisal and Agriculture Residues 35
1.2 Bacterial Cellulose 38
1.3 Structurally Modified Cellulose 43
1.3.1 Microcrystalline Cellulose 43
1.3.2 Cellulose Whiskers 45
1.3.3 Microfibrillated Cellulose 48
Annex 50
References 55
2 Structure and Properties of Cellulose and Its Derivatives 63
2.1 Molecular and Supramolecular Structure of Cellulose 63
2.2 Molar Mass and Its Distribution 65
2.2.1 Rheology and Viscometry 67
2.2.1.1 Theoretical Background 67
2.2.1.2 Practical Aspects 70
2.2.1.3 Applications of Viscometry in Cellulose Chemistry 72
2.2.2 Size Exclusion Chromatography, SEC 74
2.2.2.1 Theoretical Background 74
2.2.2.2 Practical Aspects 75
2.2.3 Light Scattering (LS) 77
2.2.3.1 Theoretical Background 77
2.2.3.2 Practical Aspects 79
2.2.4 Use of Integrated Analytical Techniques 81
2.3 Structural Information 83
2.3.1 X-ray Diffraction 83
2.3.1.1 Theoretical Aspects 83
2.3.1.2 Probing the Structure and Hydrogen Bonding in Cellulose 84
2.3.2 Infrared and Raman Spectroscopy 96
2.3.2.1 Theoretical Background 96
2.3.2.2 Practical Aspects 96
2.3.3 NMR Spectroscopy 106
2.3.3.1 Solid-State NMR of Cellulose 107
2.3.3.2 Application of Liquid Phase NMR 113
2.3.4 Chromatographic Analysis 145
2.3.4.1 HPLC Analysis of Cellulose After Degradation 147
2.3.4.2 Analysis of Cellulose Derivatives After Degradation 148
2.3.4.3 Chromatographic Techniques Applied After Degradation and Subsequent Derivatization 152
2.3.5 Mass Spectroscopy (MS) 157
2.3.6 Thermal Analysis 167
2.3.6.1 Theoretical Background 167
2.3.6.2 Practical Aspects—Applications of TA to Cellulose and Its Derivatives 173
References 178
3 Cellulose Activation and Dissolution 197
3.1 Activation of Cellulose 197
3.1.1 Introduction 197
3.1.2 Accessibility and Its Methods of Determination 198
3.1.3 Activation by Intercrystalline Swelling 206
3.1.4 Activation by Intracrystalline Swelling 215
3.2 Dissolution of Cellulose 225
3.2.1 Non-derivatizing Solvents 225
3.2.2 Derivatizing Solvents 259
References 263
4 Principles of Cellulose Derivatization 282
4.1 The Heterogeneous Versus the Homogeneous Reaction Path: Advantages and Limitations 284
4.2 Esterification of Cellulose—General Comments 285
4.3 Etherification of Cellulose—Overview 292
4.4 Regioselective Synthesis of Cellulose Derivatives Using Protecting Groups 297
4.4.1 Triphenylmethyl Ethers 300
4.4.2 Trialkylsilyl Ethers 302
4.4.3 3-O-Ethers of Cellulose 304
4.4.4 Thermal Properties in Aqueous Solution 306
4.4.5 Application of Orthogonal Protecting Groups 308
References 310
5 Cellulose Esters 316
5.1 Esters of Carboxylic Acids 316
5.1.1 Industrial Preparation of Cellulose Esters 316
5.1.2 Laboratory Synthesis of Cellulose Carboxylic Esters 318
5.1.2.1 Heterogeneous Procedures 318
5.1.2.2 Synthesis of Cellulose Esters Applying Derivatizing Solvents 322
Cellulose Trifluoroacetate and -Formate 322
Methylol Cellulose 324
Cellulose Nitrite 325
5.1.2.3 Esterification of Cellulose in Nonderivatizing Solvents 326
Electrolytes/Dipolar Aprotic Solvents 326
DMAc/LiCl 327
In Situ Activation of Carboxylic Acids 328
Quaternary Ammonium Fluorides/DMSO 331
Ionic Liquids 333
5.1.2.4 Factors Influencing the DS of the Produced Esters 337
5.1.3 Some Properties and Applications of Cellulose Esters of Carboxylic Acids 342
5.1.3.1 Properties 342
5.1.3.2 Applications 344
5.2 Esters of Sulfonic Acids and Their Use for SN Reactions 346
5.2.1 Introduction 346
5.2.2 Synthesis of Cellulose Sulfonates 348
5.2.3 Modification of the Remaining Hydroxyl Groups of Cellulose Sulfonates 350
5.2.4 Nucleophilic Displacement Reaction with Cellulose Tosylates 350
5.2.5 6-Deoxy-6-Amino Cellulose Derivatives—Synthesis and Properties 355
5.2.5.1 Alkylene Diamine (ADA) Cellulose Derivatives 358
5.2.5.2 Amino Cellulose Derivatives with Oligoamine Residues 358
5.2.5.3 Supramolecular Aggregation of Amino Cellulose 359
5.3 Esters of Inorganic Acids 361
5.3.1 Cellulose Nitrate 364
5.3.1.1 Introduction 364
5.3.1.2 The Chemistry of Cellulose Nitration 365
5.3.1.3 Industrial Production of Cellulose Nitrate 367
5.3.1.4 Properties of Cellulose Nitrate 369
5.3.1.5 Applications of Cellulose Nitrate 371
5.3.2 Cellulose Phosphate and Phosphite 371
5.3.2.1 Introduction 371
5.3.2.2 Synthesis of Cellulose Phosphate Under Heterogeneous Conditions 372
5.3.2.3 Synthesis of Cellulose Phosphate Under Homogeneous Conditions 376
5.3.2.4 Applications of Cellulose Phosphate 378
5.3.3 Esters of Sulfuric Acid 381
5.3.3.1 Introduction 381
5.3.3.2 Direct Sulfation of Cellulose 381
5.3.3.3 Sulfation of Partially Substituted Cellulose Derivatives 385
5.3.3.4 Sulfation of Cellulose Derivatives by Substitution of the Labile Group Present 388
5.3.3.5 Properties of Cellulose Sulfates 390
5.3.3.6 Applications of Cellulose Sulfates 391
Biomedical-Related Applications 391
5.3.3.7 Heterogeneous Catalysts in Organic Synthesis 393
5.3.4 Cellulose Borates and Boronates 394
5.3.5 Cellulose Esters of Carbonic Acid and Its Derivatives 400
5.3.5.1 Cellulose Esters of Carbonic Acid 402
Simple Esters of Carbonic Acid 402
Cellulose Esters of Carbonic Acid 403
Synthesis Under Heterogeneous Conditions 404
Synthesis Under Homogeneous Conditions 405
Properties and Applications of Cellulose Carbonate 408
5.3.5.2 Cellulose Esters of Thiocarbonic Acids 410
Applications of Esters of Thiocarbonic Acids: The Viscose Process and the Rayon Fiber 411
The Pulp 413
The Steeping Step 413
DP Reduction: Pre-aging or Mercerization 413
Xanthation 414
Viscose Aging 414
Spinning 416
Properties and Application of Rayon Fibers [359, 360] 418
5.3.5.3 Esters of Carbamic Acid and Its N-Substituted Derivatives 418
Synthesis of Cellulose Carbamates 419
Heterogeneous Reaction Without Solvent 419
Heterogeneous Carbanilation in the Presence of Solvent 420
Carbanilation Under Homogeneous Reaction Conditions 422
Applications of Cellulose Carbamates 423
The Carbamate Process for Cellulose Fiber Spinning 426
References 432
6 Etherification of Cellulose 451
6.1 Ionic Cellulose Ethers 453
6.1.1 Anionic Cellulose Ethers 453
6.1.2 Cationic Cellulose Ethers 466
6.2 Nonionic Cellulose Ethers 473
6.2.1 Alkyl Ethers 474
6.2.2 Aromatic and Unsaturated Alkyl Ethers 477
6.2.3 Hydroxy Alkyl and Mixed Alkyl/Hydroxy Alkyl Ethers 482
6.3 Silyl Ethers 487
References 494
7 Miscellaneous Cellulose Derivatives and Reactions 500
7.1 Oxidation of Cellulose 500
7.1.1 Introduction 500
7.1.2 Reagents for and Products of the Oxidation of Cellulose 500
7.1.3 Oxidation of the Primary Hydroxyl Groups at Position 6 of the AGU 501
7.1.4 Oxidation of the Secondary Hydroxyl Groups 506
7.2 Click Chemistry with Cellulose 510
7.2.1 Introduction 510
7.2.2 Click Chemistry with Cellulose 510
7.2.2.1 Huisgen Reaction 510
7.2.2.2 Dendronization of Cellulose 518
7.2.2.3 Diels–Alder Reaction 521
7.2.2.4 Thiol-Michael Reaction/Thiol-Ene Reaction 527
7.3 Grafting of Cellulose 531
7.3.1 Introduction 531
7.3.2 Mechanisms of Grafting 537
7.3.2.1 Free Radical Grafting 537
7.3.2.2 Ionic Grafting by Ring Opening Polymerization (ROP) 539
7.3.3 Characterization of Cellulose Graft Copolymers 542
7.3.4 Applications of Cellulose Graft Copolymers 543
References 544