Biodegradable and Biobased Polymers for Environmental and Biomedical Applications

ISBN-13: 9781119117339 / Angielski / Twarda / 2016 / 515 str.

Susheel Kalia; Luc Averous

Opis

This volume incorporates 13 contributions from renowned experts from the relevant research fields that are related biodegradable and biobased polymers and their environmental and biomedical applications. Specifically, the book highlights:

• Developments in polyhydroxyalkanoates applications in agriculture, biodegradable packaging material and biomedical field like drug delivery systems, implants, tissue engineering and scaffolds
• The synthesis and elaboration of cellulose microfibrils from sisal fibres for high performance engineering applications in various sectors such as the automotive and aerospace industries, or for building and construction

• The different classes and chemical modifications of tannins

• Electro-activity and applications of Jatropha latex and seed

• The synthesis, properties and applications of poly(lactic acid)

• The synthesis, processing and properties of poly(butylene succinate), its copolymers, composites and nanocomposites

• The different routes for preparation polymers from vegetable oil and the effects of reinforcement and nano-reinforcement on the physical properties of such biobased polymers

• The different types of modified drug delivery systems together with the concept of the drug delivery matrix for controlled release of drugs and for antitumor drugs

• The use of nanocellulose as sustainable adsorbents for the removal of water pollutants mainly heavy metal ions, organic molecules, dyes, oil and CO₂

• The main extraction techniques, structure, properties and different chemical modifications of lignins

• Proteins and nucleic acids based biopolymers

• The role of tamarind seed polysaccharide-based multiple-unit systems in sustained drug release

Spis treści

Preface xvii

1 Biomedical Applications for Thermoplastic Starch 1
Antonio José Felix de Carvalho and Eliane Trovatti

1.1 Starch as Source of Material in the Polymer Industry 1

1.2 Starch in Plastic Material and Thermoplastic Starch 2

1.3 Uses of Starch and TPS in Biomedical and Pharmaceutical Fields 5

1.3.1 Native Starch (Granule) as Pharmaceutical Excipient 6

1.3.2 Gelatinized and Thermoplastic Starch in Biomedical Application 6

1.3.3 Starch–based Scaffolds 10

1.3.4 Starch–based Biosorbable Materials – Degradation Inside Human Body 12

1.3.5 Cell Response to Starch and Its Degradation Products 15

1.4 Conclusion and Future Perspectives for Starch–based Polymers 16

Acknowledgment 16

References 16

2 Polyhydroxyalkanoates: The Application of Eco–Friendly Materials 25
G.V.N. Rathna, Bhagyashri S. Thorat Gadgil and Naresh Killi

2.1 Introduction 25

2.2 Natural Occurrence 26

2.3 Bio–Synthetic/ Semi–Synthetic Approach 29

2.4 Environmental Aspects 31

2.5 Applications 33

2.6 Biomedical Applications 33

2.6.1 Drug Delivery 34

2.6.2 Implants and Scaffolds 36

2.7 Biodegradable Packaging Material 38

2.8 Agriculture 44

2.9 Other Applications 45

2.10 Scope of PHAs 46

2.11 Conclusions 46

References 47

3 Cellulose Microfibrils from Natural Fiber Reinforced Biocomposites and its Applications 55
Atul P Johari, Smita Mohanty and Sanjay K Nayak

3.1 Introduction 55

3.1.1 Industrial Applications 57

3.2 Natural Fibers: Applications and Limitations 58

3.3 Plant–based Fibers 59

3.4 Chemical Composition, structure and Properties of Sisal Fiber 60

3.4.1 Cellulose Fibers 61

3.4.2 Hemicellulose 61

3.4.3 Lignin 62

3.4.4 Pectin 63

3.4.5 Bio–based and Biodegradable Polymers 63

3.5 Biocomposites 64

3.6 Classification of Biocomposites 65

3.6.1 Green Composites 65

3.6.2 Hybrid Composites 66

3.7 Biocomposites of CMF Reinforced of Poly (lactic acid) 67

3.7.1 Extraction of Cellulose Microfibrils from Sisal Fiber 67

3.7.2 CMF Extraction Process 69

3.7.3 Fabrication of PLA/CMF Biocomposite 72

3.8 Effect of CMF Reinforcement on the Mechanical Properties of PLA 72

3.9 FT–IR Analysis of Untreated Sisal Fiber (UTS), Mercerized Sisal Fiber (MSF) and Cellulose Microfibrils (CMF) 73

3.10 Crystalline Structure of UTS, MSF and CMF 75

3.11 Particle Size Determination: Transmission Electron Microscopy (TEM) 76

3.12 Thermal Properties 77

3.12.1 Differential Scanning Calorimetry of CMF Reinforced PLA biocomposites 77

3.12.2 Thermo Gravimetric Analysis of CMF Reinforced PLA Biocomposites 79

3.12.3 Dynamic Mechanical Analysis (DMA) of CMF Reinforced PLA Biocomposites 82

3.13 Scanning Electron Microscopy 85

3.13.1 Surface Morphology of Sisal Fiber (USF, MSF and CMF) 85

3.13.2 Surface Morphology of CMF Reinforced PLA

References 91

4 Tannins: A Resource to Elaborate Aromatic and Biobased Polymers 97
Alice Arbenz and Luc Avérous

4.1 Introduction 97

4.2 Tannin Chemistry 98

4.2.1 Historical Outline 98

4.2.2 Classification and Chemical Structure of Vascular Plant Tannins 99

4.2.3 Hydrolysable Tannins 99

4.3 Complex Tannins 101

4.4 Condensed Tannins 101

4.5 Non–vascular Plant Tannins 103

4.5.1 Phlorotannins with Ether Bonds 104

4.5.2 Phlorotannins with Phenyl bonds 104

4.5.3 Phlorotannins with Ether and Phenyl bonds 105

4.5.4 Phlorotannins with Ibenzo–p–dioxin Links 106

4.6 Extraction of Tannins 106

4.7 Chemical Modification 108

4.7.1 General Background 108

4.7.2 Heterocycle Reactivity 108

4.8 Heterocyclic Ring Opening with Acid 110

4.9 Sulfonation 112

4.9.1 Reactivity of Nucleophilic Sites 113

4.9.2 Bromination 114

4.9.3 Reactions with Aldehydes 116

4.9.4 Reaction with the Hexamine 117

4.10 Mannich Reaction 119

4.11 Coupling Reaction 119

4.11.1 Michael Reaction 119

4.11.2 Oxa–Pictet–Spengler Reaction 120

4.11.3 Functionalization of the Hydroxyl Groups 121

4.11.4 Acylation 121

4.12 Etherification 124

4.12.1 Substitution by Ammonia 127

4.12.2 Reactions Between Tannin and Epoxy Groups 128

4.13 Alkoxylation 129

4.13.1 Reaction with Isocyanates 130

4.14 Toward Biobased Polymers and Materials 130

4.14.1 Adhesives 130

4.14.2 Phenol–formaldehyde Foam Type 132

4.15 Materials Based on Polyurethane 133

4.15.1 Polyurethanes Foams 133

4.15.2 Non–porous Polyurethane Materials 133

4.16 Materials Based on Polyesters 134

4.16.1 Materials Based on Epoxy Resins 134

4.17 Conclusion 135

Acknowledgments 136

References 136

5 Electroactivity and Applications of Jatropha Latex and Seed 149
S. S. Pradhan and A. Sarkar

5.1 Introduction 149

5.2 Plant Latex 150

5.3 Jatropha Latex 151

5.3.1 Chemistry 151

5.4 Jatropha Seed 151

5.5 Material Preparation 151

5.6 Microscopic Observations 153

5.6.1 X–ray Diffraction 153

5.6.2 Electronic or Vibrational Properties 154

5.7 Electroactivity in Jatropha Latex 157

5.7.1 Ionic Liquid Property 157

5.8 Electroactivity in Jatropha Latex 158

5.8.1 DC Volt–ampere Characteristics 162

5.8.2 Temperature Variation of AC Conductivity 164

5.9 Applications 165

5.10 Conclusion 167

Acknowledgements 168

References 168

6 Characteristics and Applications of PLA 171
Sandra Domenek and Violette Ducruet

6.1 Introduction 171

6.2 Production of PLA 172

6.2.1 Production of Lactic Acid 172

6.2.2 Synthesis of PLA 174

6.3 Physical PLA properties 179

6.4 Microstructure and Thermal properties 181

6.4.1 Amorphous Phase of PLA 181

6.4.2 Crystalline Structure of PLA 183

6.4.3 Crystallization Kinetics of PLA 185

6.4.4 Melting of PLA 187

6.5 Mechanical Properties of PLA 188

6.6 Barrier Properties of PLA 190

6.6.1 Gas Barrier Properties of PLA 190

6.6.2 Water Vapour Permeability of PLA 193

6.6.3 Permeability of Organic Vapours through PLA 194

6.7 Degradation Behaviour of PLA 195

6.7.1 Thermal Degradation 195

6.7.2 Hydrolysis 196

6.7.3 Biodegradation 198

6.8 Processing 200

6.9 Nanocomposites 202

6.10 Applications 204

6.10.1 Biomedical Applications of PLA 204

6.10.2 Packaging Applications Commodity of PLA 205

6.10.3 Textile Applications 208

6.10.4 Automotive Applications of PLA 209

6.10.5 Building Applications 210

6.10.6 Other Applications of PLA 210

6.11 Conclusion 211

References 211

7 PBS Makes Its Entrance into the Family of Biobased Plastics 225
Laura Sisti, Grazia Totaro and Paola Marchese

7.1 Introduction 225

7.2 PBS Market 227

7.3 PBS Production 229

7.3.1 Succinic Acid Production 230

7.3.2 1,4–Butanediol Production 233

7.3.3 Synthesis of PBS 234

7.4 Properties of PBS 237

7.5 Copolymers of PBS 240

7.5.1 Random Copolymers 240

7.5.2 Block Copolymers 247

7.5.3 Chain Branching 250

7.6 PBS Composites and Nanocomposites 253

7.6.1 Inorganic Fillers 253

7.6.2 Natural Fibers 258

7.7 Degradation and Recycling 262

7.7.1 Enzymatic Degradation 262

7.7.2 Non Enzymatic Degradation 266

7.7.3 Natural Weathering Degradation 266

7.7.4 Thermal Degradation 267

7.7.5 Recycling 267

7.8 Processing and Applications of PBS and its Copolymers 269

7.9 Conclusions 273

Abbreviations 273

References 274

8 Development of Biobased Polymers and Their Composites from Vegetable Oils 289
Patit P. Kundu and Rakesh Das

8.1 Introduction 289

8.2 Source and Functional Groups of Vegetable Oil 290

8.3 Direct Cross–Linking of Vegetable Oil for

Polymer Synthesis 292

8.3.1 Cationic Polymerization 292

8.4 Free Radical Polymerization 295

8.5 Chemical Modification of Vegetable Oils for Polymer Synthesis 297

8.5.1 Synthesis of Polymers after Epoxidation of Vegetable Oils 297

8.6 Polymer Synthesis after Esterification of Vegetable Oils 299

8.7 Polyol and Polyurethanes from Vegetable Oils 302

8.8 Polymer Composites and Nanocomposites from Vegetable Oils 306

8.9 Conclusions 311

References 312

9 Polymers as Drug Delivery Systems 323
Magdy W. Sabaa

9.1 Introduction 323

9.2 Types of Modified Drug Delivery Systems 324

9.3 Concept of Drug Delivery Matrix 325

9.4 Polymeric Materials as Carriers for Drug Delivery Systems 326

9.4.1 Polysaccharides and Modified Polysaccharides as Matrices for Drug Delivery Systems 326

9.4.2 pH–sensitive as Drug Delivery Systems 331

9.4.3 Thermo–sensitive as Drug Delivery Systems 335

9.4.4 Light–sensitive as Drug Delivery Systems 338

9.5 Conclusions 340

References 341

10 Nanocellulose as a Millennium Material with Enhancing Adsorption Capacities 351
Norhene Mahfoudhi and Sami Boufi

10.1 Introduction 351

10.2 From Cellulose to Nanocellulose 353

10.3 General Remarks about Adsorption Phenomena 355

10.4 Nanobibrillated Cellulose as a Novel Adsorbent 359

10.5 NFC in Heavy Metal Adsorption 363

10.6 NFC as an Adsorbent for Organic Pollutants 372

10.7 NFC in Oil Adsorption 373

10.8 NFC in Adsorption of Dyes 376

10.9 Nanofibrillar Cellulose as a Flocculent for Waste Water 379

10.10 NFC in CO2 Adsorption 380

10.11 Conclusion 381

References 381

11 Towards Biobased Aromatic Polymers from Lignins 387
Stephanie Laurichesse and Luc Avérous 387

11.1 Introduction 388

11.2 Lignin Chemistry 389

11.2.1 Historical Outline 389

11.2.2 Chemical Structure 390

11.2.3 Physical Properties 391

11.3 Isolation of Lignin from Wood 393

11.3.1 The Biorefinery Concept 393

11.3.2 Extraction Processes and their Resulting Technical Lignins 394

11.4 Chemical Modification 398

11.4.1 General Background 398

11.4.2 Fragmentation of Lignin 399

11.4.3 Pyrolysis 401

11.4.4 Gasification 403

11.4.5 Oxidation 403

11.4.6 Liquefaction 404

11.4.7 Enzymatic Oxidation 406

11.4.8 Outlook 407

11.5 Synthesis of New Chemical Active Sites 407

11.5.1 Alkylation/Dealkylation 407

11.5.2 Hydroxalkylation 409

11.5.3 Amination 410

11.5.4 Nitration 411

11.6 Functionalization of Hydroxyl Groups 412

11.6.1 Esterification 412

11.6.2 Phenolation 415

11.6.3 Etherification and Ring Opening Polymerisations 416

11.6.4 Urethanisation 418

11.7 Toward Lignin Based Polymers and Materials 420

11.7.1 Lignin as a Viable Route for

Polymers Syntheses 420

11.7.2 ATRP – A Useful Method to Develop Lignin–Based Functional Material 422

11.7.3 High Performance Material Made with Lignin: Carbon Fibers 423

11.7.4 Toward Commercialized Lignin–based Polymers   424

11.8 Conclusion 424

Acknowledgments 425

References 425

12 Biopolymers Proteins (Polypeptides) and Nucleic Acids 439
S. Georgiev, Z. Angelova and T. Dekova

12.1 Structure of Protein Molecules 440

12.1.1 Peptide Bonds 441

12.1.2 Secondary Structure of Protein Molecule 441

12.1.3 Tertiary Structure of Proteins 442

12.1.4 Quaternary Structure of Proteins 443

12.2 Abnormal Haemoglobin 444

12.3 Methods for Proteome Analysis 446

12.4 Advantages of the Method 446

12.5 Study of Proteins with Post–Translational Modifications 447

12.6 Biodegradable Polymers 448

12.6.1 DNA The Molecule of Heredity 451

12.6.2 Experiments Designate DNA as the Genetic Material 452

12.6.3 Bacterial Transformation Implicates DNA as the Substance of Genes 452

12.6.4 Identification of RNA as the Genetic Material 454

12.6.5 The Structures of DNA and RNA 455

12.6.6 Left Handed DNA Helices 456

12.6.7 Some DNA Molecules are Circular instead of Linear 456

12.6.8 RNA as the Genetic Material (Structure) 457

12.6.9 Hammerhead Ribozymes HHRs 458

12.7 Regulation Gene Function Through RNA Interfering and MicroRNA Pathways 460

12.7.1 How dsRNA can Switch off Expression of a Gene? 461

12.7.2 MicroRNAs Also Control the Expression of Some Genes 463

12.8 DNA Vaccines 464

12.9 Conclusion 467

References 467

13 Tamarind Seed Polysaccharide–based Multiple–unit Systems for Sustained Drug Release 471
Amit Kumar Nayak 471

13.1 Introduction 471

13.2 Tamarind Seed Polysaccharide 473

13.2.1 Sources and Extraction 473

13.3 Composition 474

13.4 Properties 474

13.5 Use of Tamarind Seed Polysaccharide in Drug Delivery 475

13.6 Tamarind Seed Polysaccharide–based Microparticle/Beads for Sustained Drug Delivery 476

13.7 Extrusion–Spheronization Method 476

13.7.1 Tamarind Seed Polysaccharide Spheroids  Containing Diclofenac Sodium 476

13.8 Ionotropic–Gelation  Method 478

13.8.1 Tamarind Seed Polysaccharide–alginate Beads Containing Diclofenac Sodium 478

13.8.2 Tamarind Seed Polysaccharide–alginate Mucoadhesive Microspheres Containing Gliclazide 480

13.8.3 Tamarind Seed Polysaccharide–alginate Mucoadhesive Beads Containing Metformin HCl 481

13.7.4 Tamarind Seed Polysaccharide–pectinate Mucoadhesive Beads Containing Metformin HCl 481

13.8.5 Tamarind Seed Polysaccharide–gellan Mucoadhesive Beads Containing Metformin HCl 483

13.9 Covalent Crosslinking 485

13.9.1 Chitosan–Tamarind Seed Polysaccharide Interpenetrating Polymeric Network Microparticles Containing Aceclofenac 485

13.10 Combined  Ionotropic–Gelation/Covalent Crosslinking 488

13.10.1 Interpenetrated Polymer Network Microbeads Containing Diltiazem–Indion 254® Complex made of Tamarind Seed Polysaccharide and Sodium Alginate 488

13.11 By Ionotropic Emulsion–gelation 489

13.11.1 Oil–entrapped Tamarind Seed Polysaccharide– Alginate Blend Floating Beads Containing Diclofenac Sodium 489

13.12 Conclusion 490

References 490

Index 493

O autorze

Susheel Kalia?is an associate professor in the Department of Chemistry at Bahra University, Solan, India. He has around 65 research papers in international journals along with 80 publications in national and international conferences and many book chapters. He has edited a number of books including?Biopolymers: Biomedical and Environmental Applications?(Wiley–Scrivener, 2011).

Luc Avérous?is a Group Leader, Head of Polymer Research Department in an institute (ICPEES–UMR CNRS 7515) at University of Strasbourg (France), and former Lab Director. In 2003, he became a Full Professor at ECPM (University of Strasbourg), where he teaches polymer science and engineering. During the last two decades, his major research projects have dealt with biobased and/or biodegradable polymers for environmental & biomedical applications.