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Biobased Adhesives. Sources, Characteristics, and Applications. Edition No. 1. Adhesion and Adhesives: Fundamental and Applied Aspects

  • Book

  • 768 Pages
  • May 2023
  • John Wiley and Sons Ltd
  • ID: 5836926
Biobased Adhesives

Unique and comprehensive book edited by acknowledged leaders on biobased adhesives that will replace petroleum-based adhesives.

This book contains 23 chapters covering the various ramifications of biobased adhesives. The chapters are written by world-class scientists and technologists actively involved in the arena of biobased adhesives. The book is divided into three parts: Part 1: Fundamental Aspects; Part 2: Classes of Biobased Adhesives; and Part 3: Applications of Biobased Adhesives. Topics covered include: an introduction to biobased adhesives; adhesion theories and adhesion and surface issues with biobased adhesives; chemistry of adhesives; biorefinery products as biobased raw materials for adhesives; naturally aldehyde-based thermosetting resins; natural crosslinkers; curing and adhesive bond strength development in biobased adhesives; mimicking nature; bio-inspired adhesives; protein adhesives; carbohydrates as adhesives; natural polymer-based adhesives; epoxy adhesives from natural materials; biobased polyurethane adhesives; nanocellulose-modified adhesives; debondable, recyclable, and biodegradable biobased adhesives; 5-Hydroxymethylfurfural-based adhesives; adhesive precursors from tree-derived naval stores; and applications in various diverse arenas such as wood bonding, controlled drug delivery, and wearable bioelectronics.

Audience

This book will interest materials scientists, adhesionists, polymer chemists, marine biologists, food and agriculture scientists, and environmentalists. R&D personnel in a slew of wide-ranging industries such as aviation, shipbuilding, railway, automotive, packaging, construction, wood bonding, and composites should find this book a repository of current and much-needed information.

Table of Contents

Preface xvii

Part 1: Fundamental Aspects 1

1 Introduction to Naturally-Based (Bio-) Adhesives 3
Manfred Dunky

1.1 Introduction 3

1.2 Overview and Challenges For Adhesives Based on Natural Resources 6

1.2.1 Combined Use of Synthetic and Naturally-Based Adhesives 8

1.2.2 Overview on Adhesives Based on Natural Resources 9

1.2.3 Requirements, Limitations, and Opportunities for Wood Adhesives Based on Natural Resources 11

1.3 Biorefinery and Platform Chemicals 11

1.4 Lignin as Raw Material for Platform Chemicals 20

1.5 5-Hydroxymethylfurfural (5-HMF) as Platform Chemical 23

1.6 Mimicking Nature 27

1.7 Special Topics and Latest Developments 29

1.8 Prospects 30

1.9 Summary 30

General Literature on Biobased Adhesives 30

List of Abbreviations 34

References 35

2 Adhesion Theories in Naturally-Based Bonding: Adhesion and Surface Issues with Naturally-Based Adhesives 45
Douglas J. Gardner, Geeta Pokhrel and Alexander Collins

2.1 Introduction 45

2.2 Adhesion Theories 46

2.2.1 Mechanical Interlocking 47

2.2.2 Electrostatic Mechanism 48

2.2.3 Adsorption (Thermodynamic) or Wetting Mechanism 49

2.2.4 Diffusion Mechanism 50

2.2.5 Chemical (Covalent) Bonding Mechanism 50

2.2.5.1 Hydrogen Bonding 51

2.2.6 Acid-Base Theory 51

2.2.7 Weak Boundary Layers 52

2.2.8 Stickiness or Tackiness 53

2.3 Protein Adhesives 54

2.3.1 Animal-Sourced Proteins 55

2.3.2 Plant Proteins 57

2.4 Carbohydrate-Based Adhesives 59

2.5 Plant or Wood-Based Extractives 60

2.5.1 Rubber 60

2.5.2 Resins 61

2.5.2.1 Rosin 62

2.5.2.2 Terpene Resins 63

2.5.2.3 Tannins 64

2.5.2.4 Gums 65

2.6 Fats or Oils 66

2.6.1 Tung Oil 67

2.6.2 Linseed Oil 68

2.6.3 Soybean Oil 69

2.6.4 Castor Oil 70

2.6.5 Miscellaneous Oils 71

2.7 Summary 72

Acknowledgements 72

List of Abbreviations 72

References 74

3 The Chemistry of Bioadhesives 85
A. Pizzi

3.1 Introduction 85

3.2 Carbohydrate Bioadhesives 86

3.3 Protein Bioadhesives 91

3.4 Lignin-Based Bioadhesives 93

3.5 Tannin-Based Bioadhesives 95

3.5.1 Hydrolysable Tannins 96

3.5.1.1 Gallo-Tannins 96

3.5.1.2 Ellagi-Tannins 96

3.5.2 Condensed Polyflavonoid Tannins 96

3.5.3 Reactions of Condensed Flavonoid Tannins 99

3.6 Other Bio-Adhesives for Wood Composites 106

3.7 Summary 108

List of Abbreviations 109

References 110

4 Biorefinery Products as Naturally-Based Key Raw Materials for Adhesives 119
Johannes Karl Fink

4.1 Biorefinery Systems 119

4.1.1 History of Biomaterials 119

4.1.2 Classification of Biorefinery Systems 120

4.1.3 Biorefinery Processes 123

4.1.3.1 Hydrothermal Processes 123

4.1.3.2 Thermochemical Processes 123

4.1.3.3 Chemical Processes 124

4.1.3.4 Biochemical Processes 124

4.1.3.5 Bacterial Processes 124

4.1.4 Renewable Materials for Biorefinery 126

4.1.4.1 Carbohydrates 126

4.1.4.2 Lignin 126

4.1.4.3 Triglycerides 127

4.1.4.4 Mixed Organic Residues 127

4.2 Biobased Materials 128

4.2.1 Biobased Monomers 128

4.2.2 Synthesis Methods 129

4.2.2.1 L-3,4-Dihydroxyphenylalanine 135

4.2.2.2 2-Pyrone-4,6-dicarboxylic acid 136

4.3 Biobased Materials Suitable for Adhesives 137

4.3.1 Additives 137

4.3.2 Wood Adhesives 138

4.3.3 Lignin-Based Adhesives 139

4.3.4 Biorefinery Process of Kash 139

4.3.5 Lignin-Phenol Adhesives 140

4.3.5.1 Enzymatic Hydrolysis of Lignin 141

4.3.5.2 Biorefinery Residues 142

4.3.5.3 Phenol Replacement by Lignins 142

4.3.6 Lignin-Epoxy Adhesives 143

4.3.7 Lignosulfonates 145

4.3.8 Tannins 145

4.3.9 Protein-Based Adhesives 146

4.4 Synthesis Methods for Biobased Adhesives 147

4.4.1 Methylolated Wood-Derived Bio-Oil 147

4.4.2 Biosynthesis of Lignin 148

4.4.3 Soy-Based Adhesives 149

4.4.4 Bisphenol A-Glycidyl Methacrylate Replacement 149

4.5 Modification of Lignin for Better Performance 150

4.5.1 Functionalization with Aromatic Compounds 152

4.5.1.1 Functionalization of Lignin 153

4.5.1.2 Phenolation of Lignin 154

4.5.2 Organosolv Lignin-Based Materials 155

4.6 Pressure-Sensitive Adhesives 155

4.6.1 Lignin as Filler 156

4.6.2 Biobased Acrylic Compounds 156

4.6.3 UV-Tunable Pressure-Sensitive Adhesives 157

4.7 Summary 158

References 158

5 Natural Aldehyde-Based Thermosetting Resins 167
Manfred Dunky

5.1 Introduction 167

5.2 Aliphatic Aldehydes 168

5.2.1 Acetaldehyde 168

5.2.2 Glyoxal 169

5.2.2.1 Glyoxalation of Lignin 171

5.2.2.2 Glyoxylic Acid and Glyoxal 176

5.2.2.3 Glyoxal and Glutaraldehyde 176

5.2.2.4 Glyoxal and 5-Hydroxymethylfurfural (5-HMF) 177

5.2.3 Dimethoxy-Ethanal (Dimethoxy-Acetaldehyde, DME) 177

5.2.4 Propanal (Propionaldehyde) 178

5.2.5 Butyraldehyde 178

5.2.6 Isobutyraldehyde (Isobutanal) 179

5.2.7 Succinaldehyde (Butandial) 179

5.2.8 Glutar(di)aldehyde (GA) (Pentandial) 180

5.3 Aldehydes Based on Cyclic Structures 180

5.3.1 Furfural (Furfurylaldehyde) 180

5.3.2 Furfuryl Alcohol (FA) 184

5.3.3 5-Hydroxymethylfurfural (5-HMF) (see also Chapters 1 and 17) 185

5.3.4 2,5-Diformylfuran (2,5-Furan-Dicarbaldehyde) 192

5.3.5 Aromatic Aldehyde Precursors 193

5.3.6 Polymers with Pendent Aldehyde Groups 194

5.4 Summary 195

List of Abbreviations 195

References 198

6 Natural Crosslinkers for Naturally-Based Adhesives 207
Manfred Dunky

6.1 Introduction 207

6.2 Crosslinking Reactions 208

6.2.1 Proteins 208

6.2.2 Tannins 211

6.2.3 Carbohydrates 214

6.2.4 Lignins 217

6.3 Aliphatic Aldehydes as Crosslinkers 219

6.3.1 Formaldehyde 219

6.3.2 Higher Aldehydes 221

6.3.3 Glyoxal 221

6.3.4 Glutaraldehyde 223

6.3.5 Higher Aliphatic Aldehydes 226

6.4 Cyclic and Aromatic Aldehydes as Crosslinkers 226

6.4.1 Furfural 226

6.4.2 5-Hydroxymethylfurfural (5-HMF) 228

6.4.3 Non-Volatile Aldehydes from Carbohydrates 230

6.5 Crosslinkers Prepared from Biomass 231

6.5.1 Furfuryl Alcohol 231

6.5.2 Extracts as Crosslinkers 234

6.5.3 Glycerol Diglycidyl Ether (GDE), Glycerol Polyglycidyl Ether (GPE), and Ethylene Glycol Diglycidyl Ether (EGDE) 234

6.5.4 Triglycidylamine (TGA) 236

6.5.5 Diethylene-Triamine (DETA) 237

6.5.6 Citric Acid 237

6.6 Synthetic Crosslinkers 240

6.6.1 Polyamidoamine-Epichlorohydrin (PAE) Resins 240

6.6.2 Epoxy Resins 241

6.6.3 Polyethylenimine (PEI) 242

6.6.4 Polyamidoamine (PADA) 243

List of Abbreviations 243

References 245

7 Curing and Adhesive Bond Strength Development in Naturally-Based Adhesives 255
Milan Šernek and Jure Žigon

7.1 Introduction 255

7.2 Curing Monitoring Techniques 256

7.2.1 Gel Time Test 256

7.2.2 Differential Scanning Calorimetry (DSC) 257

7.2.3 Thermogravimetric Analysis (TGA) 258

7.2.4 Dielectric Analysis (DEA) 259

7.3 Bond Strength Development Monitoring Techniques 260

7.3.1 Dynamic Mechanical Analysis (DMA) 260

7.3.2 Thermomechanical Analysis (TMA) 261

7.3.3 Automated Bonding Evaluation System (ABES) 262

7.3.4 Tensile-Shear Strength 263

7.4 Curing Mechanisms in Naturally-Based Adhesives 263

7.4.1 Tannin-Based Adhesives 263

7.4.2 Lignin-Based Adhesives 265

7.4.3 Soy-Based Adhesives 267

7.4.4 Sucrose-Based Adhesives 269

7.4.5 Starch-Based Adhesives 270

7.4.6 Liquefied Wood (LW)-Based Adhesives 271

7.5 Summary 272

Acknowledgements 273

List of Abbreviations 273

References 274

8 Mimicking Nature: Bio-Inspired Adhesives 279
Manfred Dunky

8.1 Introduction 279

8.2 Improvement of Adhesive Performance 282

8.3 Underwater Adhesives (Wet Application Adhesives) 286

8.4 Detechable Bonding and Self-Healing Polymers 289

8.5 Medical Applications 292

8.6 Summary 294

List of Abbreviations 294

References 295

Part 2: Classes of Biobased Adhesives 305

9 Protein Adhesives - Composition, Structure and Performance 307
Charles R. Frihart

9.1 Introduction 307

9.2 Composition of Proteins 308

9.3 Types, Sources, Processing, and Properties of Proteins 309

9.3.1 Collagen (Animal) 309

9.3.2 Globular (Plant) 311

9.3.3 Globular (Milk) 315

9.3.4 Globular (Egg) 316

9.3.5 Globular (Blood) 317

9.3.6 Other Protein Sources 317

9.4 Conclusion (Future of Protein Adhesives) and Summary 317

List of Abbreviations 318

References 319

10 Carbohydrates (Polysaccharides) as Adhesives 325
Lee Seng Hua and Lum Wei Chen

10.1 Introduction 325

10.2 Cellulose Derivatives 326

10.3 Starch-Based Adhesives 330

10.4 Dextrin 331

10.5 Natural Gums 333

10.6 Chitosan 335

10.7 Summary and Prospects 339

Acknowledgements 340

List of Abbreviations 340

References 341

11 Natural Polymer-Based Adhesives 345
A.A. Shybi, Siby Varghese, Hanna J. Maria and Sabu Thomas

11.1 Introduction 345

11.2 Natural Rubber (NR)-Based Adhesives 346

11.2.1 Introduction to NR-Based Adhesives 346

11.2.2 NR-Based Wood Adhesives 350

11.2.3 NR-Based Pressure-Sensitive Adhesives 352

11.2.4 NR-Based Adhesives in Leather, Rubber, Textile and Metal Bonding Applications 353

11.3 Poly(lactic acid) (PLA)-Based Wood Adhesives 354

11.3.1 Introduction to PLA-Based Adhesives 354

11.3.2 PLA-Based Wood Adhesives 355

11.3.3 PLA-Based Hot-Melt Adhesives 356

11.3.4 PLA-Based Adhesives for Metal Bonding 357

11.4 Chitosan-Based Adhesives 357

11.4.1 Introduction to Chitosan-Based Adhesives 357

11.4.2 Chitosan-Based Wood Adhesives 358

11.5 Summary 359

List of Abbreviations 360

References 361

12 Epoxy Adhesives from Natural Materials 367
Charles R. Frihart

12.1 Introduction and Morphology 367

12.2 Basic Properties of Epoxies 369

12.3 Epoxy Synthesis 370

12.4 Epoxy Curing 373

12.4.1 One-Component Epoxies 375

12.4.2 Two-Component Epoxies 376

12.5 Aromatic Epoxies 376

12.5.1 Aromatic Bis-Phenol Epoxies 376

12.5.2 Aromatic Novolac Epoxies 377

12.5.3 Biobased Aromatic Epoxies from Polyphenols, Tannins, Cardanol, and Lignin 378

12.5.4 Aromatic Epoxies from Lignin and Woody Biomass 378

12.6 Aliphatic Epoxies 379

12.6.1 Aliphatic Epoxies from Vegetable Oils 380

12.6.2 Aliphatic Epoxies from Sugars 381

12.6.3 Aliphatic Epoxies from Terpenoids 382

12.6.4 Other Aliphatic Epoxies 382

12.7 Hardeners 383

12.7.1 Amines 383

12.7.1.1 Aliphatic Amines 383

12.7.1.2 Biobased Aliphatic Amines 384

12.7.1.3 Aromatic Amines 385

12.7.2 Anhydrides of Organic Acids 386

12.8 Other Curing Mechanisms 386

12.9 Other Additives 386

12.9.1 Tougheners 386

12.9.2 Modifiers 387

12.10 Status of Biobased Epoxy Adhesives 387

12.11 Summary 388

List of Abbreviations 389

References 389

13 Naturally-Based Polyurethane Bioadhesives 395
A. Pizzi

13.1 Introduction 395

13.2 Biopolyols-Isocyanate Polyurethanes 396

13.3 Non-Isocyanate Polyurethanes (NIPUs) 399

13.4 NIPUs as Adhesives 402

13.5 Summary 408

References 408

14 Nanocellulose-Modified Wood Adhesives 415
Stefan Veigel, Stefan Pinkl and Wolfgang Gindl-Altmutter

14.1 Introduction 415

14.2 Nanocellulose as Additive for Conventional and Biobased Wood Adhesives 416

14.3 Nanocellulose-Derived Wood Adhesives 420

14.4 Prospects 421

14.5 Summary 421

Note 422

List of Abbreviations 422

References 423

15 Debondable, Recyclable and/or Biodegradable Naturally-Based Adhesives 427
Natanel Jarach and Hanna Dodiuk

15.1 Introduction 427

15.2 Debondable Adhesives 428

15.2.1 Types of Debonding Adhesives 428

15.2.2 Reversible Covalent Bonds Containing Adhesives 429

15.3 Biobased Debondable and Recyclable Adhesives 431

15.3.1 Biodegradable Adhesives 431

15.3.2 Biobased Reversible Covalent Bonds Containing Adhesives 438

15.4 Summary 453

List of Abbreviations 453

References 454

16 Fungal Mycelia as Bioadhesives 463
Wenjing Sun, Mehdi Tajvidi and Christopher G. Hunt

16.1 Introduction 463

16.2 Basics of Fungal Mycelia 464

16.2.1 Fungal Species 464

16.2.2 Fungal Cell Wall 464

16.2.3 Effects of Fungal Mycelia on Lignocellulosic Substrates 465

16.3 Production Procedure 465

16.4 Adhesive Performance 467

16.4.1 As-Grown Foams 467

16.4.2 Hot-Pressed Panels 470

16.4.3 Engineered Living Materials 470

16.5 Improvement Strategies 470

16.5.1 Incorporating Natural Fibers 471

16.5.2 Infusing Bio-Resin 471

16.5.3 Incorporating Natural Reinforcement Particles 471

16.6 Prospects 471

16.7 Summary 471

Acknowledgements 472

List of Abbreviations 472

References 472

17 5-Hydroxymethylfurfural-Based Adhesives: Challenges and Opportunities 477
Wilfried Sailer-Kronlachner, Catherine Rosenfeld, Johannes Konnerth and Hendrikus van Herwijnen

17.1 Introduction 477

17.2 5-Hydroxymethylfurfural as Biobased Platform Chemical 479

17.2.1 Potential as Chemical Building Block 479

17.2.2 Challenges in the Implementation of an Industrial 5-HMF Production 480

17.3 5-HMF-Based Adhesive Systems 483

17.3.1 Wood Adhesives 484

17.3.2 Non-Wood Applications of 5-HMF-Based Adhesives 487

17.3.3 Examples of Adhesives Produced from 5-HMF Derivatives 488

17.4 Prospects 490

17.5 Summary 491

Acknowledgements 491

List of Abbreviations 492

References 492

18 Adhesive Precursors from Tree-Derived Naval Stores 499
Charles R. Frihart

18.1 Introduction 499

18.2 Sources and Structures 500

18.2.1 Rosins 500

18.2.2 Fatty Acids 502

18.2.3 Terpenes 503

18.3 Pressure-Sensitive Adhesives 503

18.4 Chemistry and Products 505

18.4.1 Rosins 505

18.4.2 Modification of the Carboxylic Acid 506

18.4.3 Modification of the Olefinic Portion 508

18.4.4 Ink Pigment Binders 509

18.4.5 Tall Oil Fatty Acids 510

18.4.6 Terpenes 512

18.5 Summary 513

List of Abbreviations 513

References 513

Part 3: Applications of Biobased Adhesives 517

19 Naturally-Based Adhesives for Wood and Wood-Based Panels 519
Manfred Dunky

19.1 Introduction 519

19.2 Protein-Based Wood Adhesives 521

19.2.1 Wood Bonding with Proteins 522

19.2.2 Plant-Based Proteins (for Soy Proteins see Section 19.2.3) 524

19.2.3 Soy Proteins 525

19.2.4 Animal-Based Proteins 528

19.2.5 Denaturation and Modification of Proteins 531

19.2.6 Crosslinking of Proteins 534

19.3 Wood Adhesives Based on Carbohydrates 535

19.3.1 Types and Sources of Carbohydrates for Use as Wood Adhesives 535

19.3.2 Modification of Starch for Possible Use as Wood Adhesive 537

19.3.3 Combination and Crosslinking of Carbohydrates with Natural and Synthetic Components 539

19.3.4 Degradation and Repolymerization of Carbohydrates 539

19.4 Tannin-Based Wood Adhesives 539

19.4.1 Types and Chemistry of Condensed Tannins 540

19.4.2 Hardening and Crosslinking of Tannins 542

19.4.3 Combination of Tannins with Other Components 546

19.5 Wood Adhesives Based on Lignin 547

19.5.1 Chemistry and Structure of Lignin 547

19.5.2 Modification of Lignin 548

19.5.3 Lignin as Adhesive 552

19.5.4 Lignin as Sole Adhesive 554

19.5.5 Reactions of Lignin with Various Aldehydes and Other Naturally-Based Components 557

19.6 Summary 558

List of Abbreviations 558

References 559

20 Activation of Wood Surfaces and “Binderless” Wood Composites 579
Manfred Dunky

20.1 Introduction 579

20.2 Self-Adhesion and “Binderless” Boards 584

20.2.1 Wood and Non-Wood Components for “Binderless” Boards 586

20.2.2 Thermal and Physical Pretreatments of Wood Material and the Wood Surface 589

20.2.3 Chemical Treatments of the Wood Surface 591

20.2.4 Enzymatic Pretreatment of the Wood Surface 595

20.2.5 Degradation and Re-Polymerization of Carbohydrates 598

20.2.6 Citric Acid 601

20.2.6.1 Sugars and Starch in Combination with Citric Acid 601

20.2.6.2 Wood in Combination with Citric Acid 602

20.2.7 Hardboards (Wet Fiber Process) 605

20.2.8 Wood Welding 607

20.3 Summary 611

List of Abbreviations 611

References 612

21 Bonding of Solid Wood-Based Materials for Timber Construction 621
Peter Niemz and Manfred Dunky

21.1 Introduction 621

21.2 Brief Overview of Solid Wood-Based Materials 622

21.3 Adhesives Used for Materials in Structural Timber Engineering 625

21.3.1 Adhesives for the Production of Glued-Laminated Timber (Surface Bonding) 625

21.3.2 Casein Adhesives 628

21.4 Factors Influencing the Quality of Adhesively-Bonded Wood 631

21.4.1 Short Overview 631

21.4.2 Influence of the Wood Substrate (Structure and Wood Species) 631

21.4.3 Influence of Adhesives 636

21.4.4 Influence of Wood Machining 643

21.4.5 Quality Control of Bonded Wood Joints 644

21.4.6 Influence of Service Conditions 644

21.4.7 Aging of Bonded Wood 646

21.5 Trends in the Use of Biobased Adhesives 649

21.6 Summary 650

List of Abbreviations 651

References 652

22 Applications and Industrial Implementations of Naturally-Based Adhesives 659
Manfred Dunky

22.1 Introduction 659

22.2 Wood-Based Panels 660

22.3 Shoe Fabrication (Footwear Industry) 664

22.4 Bonding of Metals 666

22.5 Composites in Automotive, Aircraft, and Aeronautical Industries 667

22.6 Natural Composites with Matrices Based on Natural Resources 673

22.7 Mineral Wool 679

22.8 Packaging and Other Applications 679

22.9 Biomedical Applications 680

22.10 Biodegradability and Recycling 681

22.11 Life Cycle Analysis (LCA) 683

22.12 Summary 686

List of Abbreviations 686

References 688

23 Bioadhesives for the Advancement of Controlled Drug Delivery and Wearable Bioelectronics 705
Monalisha Ghosh Dastidar, Sharmili Roy and Sudarsan Neogi

23.1 Introduction 705

23.1.1 History of Bioadhesives and their Evolution 706

23.1.2 Classification of Bioadhesives 706

23.1.2.1 Natural Bioadhesives 707

23.1.2.2 Biological and Biocompatible Bioadhesives 707

23.1.2.3 Biomimetic and Bioinspired Bioadhesives 707

23.1.3 Mechanism of Bioadhesives 708

23.2 Bioadhesives in Controlled Drug Delivery 708

23.3 Bioadhesives in Bioelectronics 710

23.4 Limitations of Bioadhesives for Biomedical Applications 717

23.5 Summary and Future Prospects 718

List of Abbreviations 719

References 720

Index 727

Authors

Manfred Dunky K. L. Mittal Maria Curie-Skodowska University, Lublin, Poland.