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Thomas Rosenau, PhD, is a professor at BOKU University Vienna, holding the Chair of Wood, Pulp and Fiber Chemistry and heading both the Division of Chemistry of Renewable Resources and the Austrian Biorefinery Center Tulln.
Antje Potthast, PhD, is a professor in the Department of Chemistry and is the deputy head of both the Division of Chemistry of Renewable Resources and the Austrian Biorefinery Center Tulln.
Johannes Hell, PhD, is a technical manager at a Viennese chocolate factory.
Author Biography xv
List of Contributors xvii
Preface xxiii
Acknowledgements xxv
1 Aminocelluloses - Polymers with Fascinating Properties and Application Potential 1Thomas Heinze, Thomas Elschner, and Kristin Ganske
1.1 Introduction 1
1.2 Amino-/ammonium Group Containing Cellulose Esters 2
1.2.1 (3-Carboxypropyl)trimethylammonium Chloride Esters of Cellulose 2
1.2.2 Cellulose-4-(N-methylamino)butyrate (CMABC) 7
1.3 6-Deoxy-6-amino Cellulose Derivatives 9
1.3.1 Spontaneous Self-assembling of 6-Deoxy-6-amino Cellulose Derivatives 10
1.3.2 Application Potential of 6-Deoxy-6-amino Cellulose Derivatives 13
1.4 Amino Cellulose Carbamates 21
1.4.1 Synthesis 21
1.4.2 Properties 22
Acknowledgment 24
References 24
2 Preparation of Photosensitizer-bound Cellulose Derivatives for Photocurrent Generation System 29Toshiyuki Takano
2.1 Introduction 29
2.2 Porphyrin-bound Cellulose Derivatives 31
2.3 Phthalocyanine-bound Cellulose Derivatives 34
2.4 Squaraine-bound Cellulose Derivative 40
2.5 Ruthenium(II) Complex-bound Cellulose Derivative 42
2.6 Fullerene-bound Cellulose Derivative 44
2.7 Porphyrin-bound Chitosan Derivative 45
2.8 Conclusion 47
References 47
3 Synthesis of Cellulosic Bottlebrushes with Regioselectively Substituted Side Chains and Their Self-assembly 49Keita Sakakibara, Yuji Kinose, and Yoshinobu Tsujii
3.1 Introduction 49
3.2 Strategy for Accomplishing Regioselective Grafting of Cellulose 52
3.3 Regioselective Introduction of the First Polymer Side Chain 55
3.3.1 Introduction of Poly(styrene) at O-2,3 Position of 6-O-p-Methoxytritylcellulose (1) 55
3.3.2 Introduction of Poly(ethylene oxide) at O-2,3 Position of 6-O-p-Methoxytritylcellulose (1) 57
3.4 Regioselective Introduction of the Second Polymer Side Chain 58
3.4.1 Introduction of Poly(styrene) at O-6 Position of 2,3-di-O-PEO Cellulose (5) via Grafting-from Approach 58
3.4.2 Introduction of Poly(styrene) at O-6 Position of 2,3-di-O-PEO Cellulose (5) via Grafting to Approach Combining Click Reaction 58
3.5 SEC-MALLS Study 61
3.6 Summary and Outlook 64
Acknowledgments 64
References 64
4 Recent Progress on Oxygen Delignification of Softwood Kraft Pulp 67Adriaan R. P. van Heiningen, Yun Ji, and Vahid Jafari
4.1 Introduction and State-of-the-Art of Commercial Oxygen Delignification 67
4.2 Chemistry of Delignification and Cellulose Degradation 70
4.3 Improving the Reactivity of Residual Lignin 73
4.4 Improving Delignification/Cellulose Degradation Selectivity During
Oxygen Delignification 79
4.5 Improving Pulp Yield by Using Oxygen Delignification 90
4.6 Practical Implementation of High Kappa Oxygen Delignification 92
References 93
5 Toward a Better Understanding of Cellulose Swelling, Dissolution, and Regeneration on theMolecular Level 99Thomas Rosenau, Antje Potthast, Andreas Hofinger,Markus Bacher, Yuko Yoneda, KurtMereiter, Fumiaki Nakatsubo, Christian Jäger, Alfred D. French, and Kanji Kajiwara
5.1 Introduction 99
5.2 Cellulose Swelling, Dissolution and Regeneration at the Molecular Level 102
5.2.1 The "Viewpoint of Cellulose" 109
5.2.2 The "Viewpoint of Cellulose Solvents" 113
5.3 Conclusion 118
References 120
6 Interaction ofWaterMolecules with Carboxyalkyl Cellulose 127HitomiMiyamoto, Keita Sakakibara, IsaoWataoka, Yoshinobu Tsujii, Chihiro Yamane, and Kanji Kajiwara
6.1 Introduction 127
6.2 Carboxymethyl Cellulose (CMC) and Carboxyethyl Cellulose (CEC) 128
6.3 Differential Scanning Calorimetry (DSC) 131
6.4 Small-Angle X-ray Scattering (SAXS) 133
6.5 Molecular Dynamics 136
6.6 Chemical Modification and Biodegradability 138
Acknowledgments 140
References 140
7 Analysis of the Substituent Distribution in Cellulose Ethers - Recent Contributions 143PetraMischnick
7.1 Introduction 143
7.2 Methyl Cellulose 146
7.2.1 Average DS and Methyl Pattern in the Glucosyl Unit 146
7.2.2 Distribution Along and Over the Chain 149
7.2.3 Summary 153
7.3 Hydroxyalkylmethyl Celluloses 153
7.3.1 Hydroxyethylmethyl Celluloses 159
7.3.2 Hydroxypropylmethyl Celluloses 160
7.3.3 Summary 165
7.4 Carboxymethyl Cellulose 166
7.5 Outlook 166
Acknowledgment 167
References 167
8 AdhesiveMixtures as Sacrificial Substrates in Paper Aging 175Irina Sulaeva, Ute Henniges, Thomas Rosenau, and Antje Potthast
8.1 Introduction 175
8.2 Materials and Methods 177
8.2.1 Chemicals 177
8.2.2 Preparation of Adhesive Mixtures and Films from Individual Components 177
8.2.3 Preparation of Coated Paper Samples 177
8.2.4 Accelerated Heat-Induced Aging 179
8.2.5 GPC Analysis 179
8.2.6 Contact Angle Measurements 180
8.2.7 Analysis of Paper Brightness 180
8.3 Results and Discussion 180
8.3.1 GPC Analysis of Adhesive Mixtures and Individual Components 180
8.3.2 Molar Mass Analysis of Paper Samples 182
8.3.3 Contact Angle Analysis 184
8.3.4 UV-Vis Measurements of Paper Brightness 185
8.4 Conclusion 186
Acknowledgments 187
References 187
9 Solution-state NMR Analysis of Lignocellulosics in Nonderivatizing Solvents 191Ashley J. Holding, AlistairW. T. King, and Ilkka Kilpeläinen
9.1 Introduction 191
9.2 Solution-state 2D NMR of Lignocellulose andWhole Biomass 195
9.3 Solution State 1D and 2D NMR Spectroscopy of Cellulose and Pulp 203
9.4 Solution-state NMR Spectroscopy of Modified Nanocrystalline Cellulose 211
9.5 Solution State 31P NMR Spectroscopy and Quantification of Hydroxyl Groups 212
9.6 Conclusions and Future Prospects 218
References 219
10 Surface Chemistry and Characterization of Cellulose Nanocrystals 223Samuel Eyley, Christina Schütz, andWimThielemans
10.1 Introduction 223
10.2 Cellulose Nanocrystals 225
10.3 Morphological and Structural Characterization 228
10.3.1 Microscopy 228
10.3.2 Small Angle Scattering 230
10.3.3 Powder X-ray Diffraction 230
10.3.4 Solid-State NMR Spectroscopy 234
10.4 Chemical Characterization 237
10.4.1 Infrared Spectroscopy 237
10.4.2 Elemental Analysis 238
10.4.3 X-ray Photoelectron Spectroscopy 240
10.4.4 Other Methods 243
10.5 Conclusion 245
Acknowledgments 246
References 246
11 Some Comments on Chiral Structures fromCellulose 253Derek G. Gray
11.1 Chirality and Cellulose Nanocrystals 253
11.2 Can CNC Form Nematic or Smectic-ordered Materials? 255
11.3 Why Do Some CNC Films Not Display Iridescent Colors? 256
11.4 IsThere Any Pattern to the Observed Expressions Of Chirality At Length Scales from the Molecular to the Macroscopic? 257
Acknowledgments 259
References 259
12 Supramolecular Aspects of Native Cellulose: Fringed-fibrillar Model, Leveling-off Degree of Polymerization and Production of Cellulose Nanocrystals 263Eero Kontturi
12.1 Introduction 263
12.2 Fringed-fibrillarModel: Crystallographic, Spectroscopic, and Microscopic Evidence 264
12.3 Leveling-off Degree of Polymerization (LODP) 267
12.4 Preparation of Cellulose Nanocrystals (CNCs) 270
12.5 Conclusion 271
References 271
13 Cellulose Nanofibrils: FromHydrogels to Aerogels 277Marco Beaumont, Antje Potthast, and Thomas Rosenau
13.1 Introduction 277
13.2 Cellulose Nanofibrils 278
13.3 Hydrogels 282
13.3.1 Cellulose Nanofibrils 284
13.3.2 Composites 288
13.3.3 Modification 293
13.4 Aerogels 296
13.4.1 Drying of Solvogels 297
13.4.2 Mechanical Properties 301
13.4.3 Conductive Aerogels 305
13.4.4 Hydrophobic Aerogels and Superabsorbents 307
13.4.5 Other Applications 315
13.5 Conclusion 317
Acknowledgments 318
References 318
14 High-performance Lignocellulosic Fibers Spun from Ionic Liquid Solution 341Michael Hummel, AnneMichud, YiboMa, Annariikka Roselli, Agnes Stepan, Sanna Hellstén, Shirin Asaadi, and Herbert Sixta
14.1 Introduction 341
14.2 Materials and Methods 347
14.2.1 Pulp Dissolution and Filtration 348
14.2.2 Rheological Measurements 349
14.2.3 Chemical Composition Analysis 349
14.2.4 Molar Mass Distribution Analysis 349
14.2.5 Fiber Spinning 350
14.2.6 Mechanical Analysis of Fibers 351
14.3 Results and Discussion 351
14.3.1 Lignocellulosic Solutes 351
14.3.2 Rheological Properties 352
14.3.3 Fiber Spinning 354
14.3.4 Fiber Properties 355
14.3.5 Summary of the Influence of Noncellulosic Constituents on the Fiber Properties 360
14.4 Conclusion 361
References 362
15 Bio-based Aerogels: A New Generation of Thermal Superinsulating Materials 371Tatiana Budtova
15.1 Introduction 371
15.2 Cellulose I Based Aerogels andTheir Composites 373
15.3 Cellulose II Based Aerogels and Their Composites 378
15.4 Pectin-based Aerogels and Their Composites 380
15.5 Starch-based Aerogels 386
15.6 Alginate Aerogels 386
15.7 Conclusions and Prospects 387
References 388
16 Nanocelluloses at the Oil-Water Interface: Emulsions Toward Function and Material Development 393Siqi Huan, Mariko Ago, MaryamBorghei, and Orlando J. Rojas
16.1 Cellulose Nanocrystal Properties in the Stabilization of O/W Interfaces 393
16.2 Surfactant-free Emulsions 395
16.3 Emulsions Stabilized with Modified Nanocelluloses 398
16.4 Surfactant-assisted Emulsions 402
16.5 Emulsions with Polymer Coemulsifiers 406
16.6 Double Emulsions 409
16.7 Emulsion or Emulsion-precursor Systems with Stimuli-responsive Behavior 413
16.8 Closing Remarks 418
Acknowledgments 418
References 418
17 Honeycomb-patterned Cellulose as a Promising Tool to InvestigateWood CellWall Formation and Deformation 423Yasumitsu Uraki, Liang Zhou, Qiang Li, Teuku B. Bardant, and Keiichi Koda
17.1 Introduction 423
17.2 Theory of Honeycomb Deformation 425
17.3 HPRC with Cellulose II Polymorphism andTheir Tensile Strength 426
17.4 Validity of Deformation Models 428
17.5 Deposition of Wood Cell Wall Components on the Film of HPBC Film 430
Acknowledgment 432
References 433
Index 435
Thomas Heinze Thomas Elschner and Kristin Ganske
Centre of Excellence for Polysaccharide Research, Institute of Organic Chemistry and Macromolecular Chemistry, Friedrich Schiller University of Jena, Humboldtstraße 10, D-07743 Jena, Germany
Cellulose is a linear D-glucan containing ß-1? 4 linkages and is the world's most abundant natural polymer with an estimated annual global production of about 1.5?×?1012?tons and, hence, a very important renewable and sustainable resource [1]. Although unmodified cellulose is used largely as paper, board, and fibers, there is huge space to design novel and advanced products based on cellulose by its chemical modification. In particular, esters and ethers of cellulose are most important [1, 2].
Due to their low-cost production, biodegradability, and low-toxicity cationized polysaccharides are promising in fields of effluent treatment, papermaking, and food, cosmetic, pharmaceutical, petroleum, and textile industries, as well as in analytical chemistry and molecular biology [3]. In particular, cationic cellulose derivatives gain increasing interest in different scientific and industrial fields, e.g. as flocculation agents [4], being an alternative to toxic polyacrylamide. In Germany, the disposal of sludge treated with polyacrylamides has been forbidden in areas under cultivation since 2014 [5].
Considering the recent literature, the huge amount of publications was summarized in reviews about cationic synthetic polyelectrolytes [6] as well as cationized polysaccharides (amino and ammonium hydroxypropyl ethers) [3]. However, in this chapter, the authors will not review the cationic ethers; the overview refers to cationic esters, 6-deoxy-6-amino cellulose derivatives, and amino carbamates of cellulose. In spite of the industrial applications that are usually associated with cationic polymers, a variety of advanced polymer coatings providing sophisticated features, e.g. biosensors or immuno assays, will be presented.
An efficient approach to cationic cellulose derivatives is the esterification of the hydroxyl groups with cationic carboxylic acids. Activated carboxylic acids such as acyl chlorides or acid anhydrides are not appropriate due to their limited solubility, availability, and the formation of acidic by-products. However, the esterification applying imidazolides obtained from the corresponding carboxylic acid and N,N-carbonyldiimidazole () is a mild and efficient synthesis strategy [2].
To synthesize cationic cellulose esters (3-carboxypropyl)trimethylammonium chloride was activated with CDI in dimethylsulfoxide () separately and allowed to react with cellulose dissolved in N,N-dimethylacetamide ()/LiCl [7]. Thus, a product with a degree of substitution () of 0.75 was accessible that could be characterized by 13C NMR spectroscopy (Figure 1.1).
Figure 1.1 13C NMR spectrum of cellulose (3-carboxypropyl)trimethylammonium chloride ester in DMSO-d6.
Source: Vega et al. 2013 [7]. Reproduced with permission of American Chemical Society.
Cellulose (3-carboxypropyl)trimethylammonium chloride esters adsorbed on cellulose films may trigger the protein adsorption, which is a key parameter in the design of advanced materials for a variety of technological fields [8]. The protein affinity to the surface can be controlled by the charge density and solubility, adjusted by the pH value, the concentration of protein and the DS of the tailored cationic cellulose derivative. To understand the influence of the cationic cellulose ester on the protein affinity, the interaction capacity with fluorescence-labeled bovine serum albumin () at different concentrations and pH values was carried out (Figure 1.2). The adsorbed material was quantified applying (quartz crystal microbalance with dissipation monitoring, wet mass) and (multi-parameter surface plasmon resonance, dry mass). Thus, the amount of coupled water in the layer could be evaluated by a combination of QCM-D and surface plasmon resonance () data. According to these studies the interaction decreases in order of pH 5?>?pH 6?>?pH 7 and DShigh?>?DSlow, respectively. The adsorption of BSA may be adjusted over a range from 0.6 to 3.9?mg?m-2 (dry mass). This approach is suitable to utilize BSA as blocking agent on the surface and achieve selective functionalization of cellulosic surfaces by functional proteins (e.g. antibodies).
Figure 1.2 Cyclic olefin polymer slides equipped with cellulose and cellulose (3-carboxypropyl)trimethylammonium chloride ester incubated with different concentrations of labeled BSA (1000, 500, 100, 10, 1, 0.1, 0.01, and 0.001 µg mL-1) at different pH values. A) low DS; B) high DS [8]. (See insert for color representation of this figure.)
Reproduced with permission of American Chemical Society.
Another application of (3-carboxypropyl)trimethylammonium chloride esters of cellulose is the surface modification of pulp fibers in order to preserve the inherent bulk properties (e.g. low density, mechanical strength) and to improve the properties of the fiber surface (e.g. wetting behavior, bacteriostatic activity) [7]. In recent studies, polyelectrolyte complexes (s) were prepared applying the cationic cellulose ester and anionic xylan derivatives, which were subsequently adsorbed to wood fibers. The adsorption process was studied using polyelectrolyte titration and elemental analysis. The fiber surfaces modified were characterized by X-ray spectroscopy () and time-of-flight secondary ion mass spectrometry (). The measurements evidence the interaction between the pulp fibers and the PECs and provide useful information about the adsorption process.
In addition to monofunctional cationic cellulose (3-carboxypropyl)trimethylammonium chloride esters, multifunctional photoactive derivatives provide advanced features in context with the design of smart materials. However, sufficient DS values are required to give a pronounced photochemical response and water solubility. Therefore, different cellulose 2-[(4-methyl-2-oxo-2H-chromen-7-yl)oxy]acetates were prepared applying CDI and the corresponding carboxylic acid in DMA/LiCl [9]. Subsequently, (3-carboxypropyl)trimethylammonium chloride activated with CDI forming the corresponding imidazolide was allowed to react with the photoactive cellulose derivative to obtain a water-soluble product (Figure 1.3). The partial DS values could be determined by a combination of UV-Vis spectroscopy and elemental analysis. The DS is in the range from 0.05 to 0.37 for the photoactive moiety and from 0.19 to 0.34 for the cationic group.
Figure 1.3 Synthesis scheme of cellulose 2-[(4-methyl-2-oxo-2H-chromen-7-yl)oxy]acetates and cellulose 2-[(4-methyl-2-oxo-2H-chromen-7-yl)oxy]acetate [4-(N,N,N-trimethylamonium) chloride] butyrates by in situ activation of 2-[(4-methyl-2-oxo-2H-chromen-7-yl)oxy]acetic acid and (3-carboxypropyl)trimethylammonium chloride with N,N-carbonyldiimidazole (CDI) in N,N-dimethylacetamide/LiCl (DMA/LiCl).
Source: Wondraczek et al. 2012 [9]. Reproduced with permission of Springer Nature.
Multifunctional, i.e. photoactive and cationic, cellulose esters were used for the coating of pulp fibers to yield new fiber-based materials, whose properties could be triggered by an external stimulus [10]. The adsorption of the polymer onto the fiber was studied by UV-Vis spectroscopy and SPR. It turned out that electrostatic interaction is the main driving force of the adsorption. However, there is a contribution of hydrophobic interactions between the fibers and the cellulose derivatives and between the polymer chains themselves. Considering the adsorption behavior, UV-Vis measurements of the solutions applied for coating led to a mechanism according to the Freundlich model. ToF-SIMS imaging revealed evenly distributed derivatives on the fiber surfaces independent of the dosage and DS of the photoactive group. Moreover, UV irradiation of the modified fibers results in crosslinking by [2+2] cycloaddition of the photoactive moieties and both light adsorption and fluorescence behavior change (Figure 1.4). Moreover, there is an enhancement of the tensile strength and Z-directional tensile strength of the pulp fibers by 81% and 84% compared to the unmodified fiber network [11]....
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