Cellulose Science and Technology

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 xvList of Contributors xviiPreface xxiiiAcknowledgements xxv1 Aminocelluloses – Polymers with Fascinating Properties and Application Potential 1Thomas Heinze, Thomas Elschner, and Kristin Ganske1.1 Introduction 11.2 Amino-/ammonium Group Containing Cellulose Esters 21.2.1 (3-Carboxypropyl)trimethylammonium Chloride Esters of Cellulose 21.2.2 Cellulose-4-(N-methylamino)butyrate (CMABC) 71.3 6-Deoxy-6-amino Cellulose Derivatives 91.3.1 Spontaneous Self-assembling of 6-Deoxy-6-amino Cellulose Derivatives 101.3.2 Application Potential of 6-Deoxy-6-amino Cellulose Derivatives 131.4 Amino Cellulose Carbamates 211.4.1 Synthesis 211.4.2 Properties 22Acknowledgment 24References 242 Preparation of Photosensitizer-bound Cellulose Derivatives for Photocurrent Generation System 29Toshiyuki Takano2.1 Introduction 292.2 Porphyrin-bound Cellulose Derivatives 312.3 Phthalocyanine-bound Cellulose Derivatives 342.4 Squaraine-bound Cellulose Derivative 402.5 Ruthenium(II) Complex-bound Cellulose Derivative 422.6 Fullerene-bound Cellulose Derivative 442.7 Porphyrin-bound Chitosan Derivative 452.8 Conclusion 47References 473 Synthesis of Cellulosic Bottlebrushes with Regioselectively Substituted Side Chains and Their Self-assembly 49Keita Sakakibara, Yuji Kinose, and Yoshinobu Tsujii3.1 Introduction 493.2 Strategy for Accomplishing Regioselective Grafting of Cellulose 523.3 Regioselective Introduction of the First Polymer Side Chain 553.3.1 Introduction of Poly(styrene) at O-2,3 Position of 6-O-p-Methoxytritylcellulose (1) 553.3.2 Introduction of Poly(ethylene oxide) at O-2,3 Position of 6-O-p-Methoxytritylcellulose (1) 573.4 Regioselective Introduction of the Second Polymer Side Chain 583.4.1 Introduction of Poly(styrene) at O-6 Position of 2,3-di-O-PEO Cellulose (5) via Grafting-from Approach 583.4.2 Introduction of Poly(styrene) at O-6 Position of 2,3-di-O-PEO Cellulose (5) via Grafting to Approach Combining Click Reaction 583.5 SEC-MALLS Study 613.6 Summary and Outlook 64Acknowledgments 64References 644 Recent Progress on Oxygen Delignification of Softwood Kraft Pulp 67Adriaan R. P. van Heiningen, Yun Ji, and Vahid Jafari4.1 Introduction and State-of-the-Art of Commercial Oxygen Delignification 674.2 Chemistry of Delignification and Cellulose Degradation 704.3 Improving the Reactivity of Residual Lignin 734.4 Improving Delignification/Cellulose Degradation Selectivity DuringOxygen Delignification 794.5 Improving Pulp Yield by Using Oxygen Delignification 904.6 Practical Implementation of High Kappa Oxygen Delignification 92References 935 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 Kajiwara5.1 Introduction 995.2 Cellulose Swelling, Dissolution and Regeneration at the Molecular Level 1025.2.1 The “Viewpoint of Cellulose” 1095.2.2 The “Viewpoint of Cellulose Solvents” 1135.3 Conclusion 118References 1206 Interaction ofWaterMolecules with Carboxyalkyl Cellulose 127HitomiMiyamoto, Keita Sakakibara, IsaoWataoka, Yoshinobu Tsujii, Chihiro Yamane, and Kanji Kajiwara6.1 Introduction 1276.2 Carboxymethyl Cellulose (CMC) and Carboxyethyl Cellulose (CEC) 1286.3 Differential Scanning Calorimetry (DSC) 1316.4 Small-Angle X-ray Scattering (SAXS) 1336.5 Molecular Dynamics 1366.6 Chemical Modification and Biodegradability 138Acknowledgments 140References 1407 Analysis of the Substituent Distribution in Cellulose Ethers – Recent Contributions 143PetraMischnick7.1 Introduction 1437.2 Methyl Cellulose 1467.2.1 Average DS and Methyl Pattern in the Glucosyl Unit 1467.2.2 Distribution Along and Over the Chain 1497.2.3 Summary 1537.3 Hydroxyalkylmethyl Celluloses 1537.3.1 Hydroxyethylmethyl Celluloses 1597.3.2 Hydroxypropylmethyl Celluloses 1607.3.3 Summary 1657.4 Carboxymethyl Cellulose 1667.5 Outlook 166Acknowledgment 167References 1678 AdhesiveMixtures as Sacrificial Substrates in Paper Aging 175Irina Sulaeva, Ute Henniges, Thomas Rosenau, and Antje Potthast8.1 Introduction 1758.2 Materials and Methods 1778.2.1 Chemicals 1778.2.2 Preparation of Adhesive Mixtures and Films from Individual Components 1778.2.3 Preparation of Coated Paper Samples 1778.2.4 Accelerated Heat-Induced Aging 1798.2.5 GPC Analysis 1798.2.6 Contact Angle Measurements 1808.2.7 Analysis of Paper Brightness 1808.3 Results and Discussion 1808.3.1 GPC Analysis of Adhesive Mixtures and Individual Components 1808.3.2 Molar Mass Analysis of Paper Samples 1828.3.3 Contact Angle Analysis 1848.3.4 UV–Vis Measurements of Paper Brightness 1858.4 Conclusion 186Acknowledgments 187References 1879 Solution-state NMR Analysis of Lignocellulosics in Nonderivatizing Solvents 191Ashley J. Holding, AlistairW. T. King, and Ilkka Kilpeläinen9.1 Introduction 1919.2 Solution-state 2D NMR of Lignocellulose andWhole Biomass 1959.3 Solution State 1D and 2D NMR Spectroscopy of Cellulose and Pulp 2039.4 Solution-state NMR Spectroscopy of Modified Nanocrystalline Cellulose 2119.5 Solution State 31P NMR Spectroscopy and Quantification of Hydroxyl Groups 2129.6 Conclusions and Future Prospects 218References 21910 Surface Chemistry and Characterization of Cellulose Nanocrystals 223Samuel Eyley, Christina Schütz, andWimThielemans10.1 Introduction 22310.2 Cellulose Nanocrystals 22510.3 Morphological and Structural Characterization 22810.3.1 Microscopy 22810.3.2 Small Angle Scattering 23010.3.3 Powder X-ray Diffraction 23010.3.4 Solid-State NMR Spectroscopy 23410.4 Chemical Characterization 23710.4.1 Infrared Spectroscopy 23710.4.2 Elemental Analysis 23810.4.3 X-ray Photoelectron Spectroscopy 24010.4.4 Other Methods 24310.5 Conclusion 245Acknowledgments 246References 24611 Some Comments on Chiral Structures fromCellulose 253Derek G. Gray11.1 Chirality and Cellulose Nanocrystals 25311.2 Can CNC Form Nematic or Smectic-ordered Materials? 25511.3 Why Do Some CNC Films Not Display Iridescent Colors? 25611.4 IsThere Any Pattern to the Observed Expressions Of Chirality At Length Scales from the Molecular to the Macroscopic? 257Acknowledgments 259References 25912 Supramolecular Aspects of Native Cellulose: Fringed-fibrillar Model, Leveling-off Degree of Polymerization and Production of Cellulose Nanocrystals 263Eero Kontturi12.1 Introduction 26312.2 Fringed-fibrillarModel: Crystallographic, Spectroscopic, and Microscopic Evidence 26412.3 Leveling-off Degree of Polymerization (LODP) 26712.4 Preparation of Cellulose Nanocrystals (CNCs) 27012.5 Conclusion 271References 27113 Cellulose Nanofibrils: FromHydrogels to Aerogels 277Marco Beaumont, Antje Potthast, and Thomas Rosenau13.1 Introduction 27713.2 Cellulose Nanofibrils 27813.3 Hydrogels 28213.3.1 Cellulose Nanofibrils 28413.3.2 Composites 28813.3.3 Modification 29313.4 Aerogels 29613.4.1 Drying of Solvogels 29713.4.2 Mechanical Properties 30113.4.3 Conductive Aerogels 30513.4.4 Hydrophobic Aerogels and Superabsorbents 30713.4.5 Other Applications 31513.5 Conclusion 317Acknowledgments 318References 31814 High-performance Lignocellulosic Fibers Spun from Ionic Liquid Solution 341Michael Hummel, AnneMichud, YiboMa, Annariikka Roselli, Agnes Stepan, Sanna Hellstén, Shirin Asaadi, and Herbert Sixta14.1 Introduction 34114.2 Materials and Methods 34714.2.1 Pulp Dissolution and Filtration 34814.2.2 Rheological Measurements 34914.2.3 Chemical Composition Analysis 34914.2.4 Molar Mass Distribution Analysis 34914.2.5 Fiber Spinning 35014.2.6 Mechanical Analysis of Fibers 35114.3 Results and Discussion 35114.3.1 Lignocellulosic Solutes 35114.3.2 Rheological Properties 35214.3.3 Fiber Spinning 35414.3.4 Fiber Properties 35514.3.5 Summary of the Influence of Noncellulosic Constituents on the Fiber Properties 36014.4 Conclusion 361References 36215 Bio-based Aerogels: A New Generation of Thermal Superinsulating Materials 371Tatiana Budtova15.1 Introduction 37115.2 Cellulose I Based Aerogels andTheir Composites 37315.3 Cellulose II Based Aerogels and Their Composites 37815.4 Pectin-based Aerogels and Their Composites 38015.5 Starch-based Aerogels 38615.6 Alginate Aerogels 38615.7 Conclusions and Prospects 387References 38816 Nanocelluloses at the Oil–Water Interface: Emulsions Toward Function and Material Development 393Siqi Huan, Mariko Ago, MaryamBorghei, and Orlando J. Rojas16.1 Cellulose Nanocrystal Properties in the Stabilization of O/W Interfaces 39316.2 Surfactant-free Emulsions 39516.3 Emulsions Stabilized with Modified Nanocelluloses 39816.4 Surfactant-assisted Emulsions 40216.5 Emulsions with Polymer Coemulsifiers 40616.6 Double Emulsions 40916.7 Emulsion or Emulsion-precursor Systems with Stimuli-responsive Behavior 41316.8 Closing Remarks 418Acknowledgments 418References 41817 Honeycomb-patterned Cellulose as a Promising Tool to InvestigateWood CellWall Formation and Deformation 423Yasumitsu Uraki, Liang Zhou, Qiang Li, Teuku B. Bardant, and Keiichi Koda17.1 Introduction 42317.2 Theory of Honeycomb Deformation 42517.3 HPRC with Cellulose II Polymorphism andTheir Tensile Strength 42617.4 Validity of Deformation Models 42817.5 Deposition of Wood Cell Wall Components on the Film of HPBC Film 430Acknowledgment 432References 433Index 435