Handbook of Polymer Synthesis, Characterization, and Processing

Covering a broad range of polymer science topics, Handbook of Polymer Synthesis, Characterization, and Processing provides polymer industry professionals and researchers in polymer science and technology with a single, comprehensive handbook summarizing all aspects involved in the polymer production chain. The handbook focuses on industrially important polymers, analytical techniques, and formulation methods, with chapters covering step-growth, radical, and co-polymerization, crosslinking and grafting, reaction engineering, advanced technology applications, including conjugated, dendritic, and nanomaterial polymers and emulsions, and characterization methods, including spectroscopy, light scattering, and microscopy.

Auteur

ENRIQUE SALDÍVAR-GUERRA is Senior Scientist and Head of the Polymerization Processes Department at the Center for Research on Applied Chemistry in Mexico. Formerly the president of the Mexican Polymer Society, he holds five patents and serves as a reviewer for the Journal of Applied Polymer Science, Industrial & Engineering Chemistry Research, and Macromolecular Theory and Simulations, among others.

EDUARDO VIVALDO-LIMA is Professor in the Department of Chemical Engineering of the Faculty of Chemistry at Universidad Nacional Autónoma de México, and External Academic Member of the Institute for Polymer Research of the University of Waterloo in Canada. A former president of the Mexican Polymer Society, Dr. Vivaldo-Lima is a reviewer for quite a number of journals, including Polymer Engineering & Science, Journal of Applied Polymer Science, Macromolecular Theory and Simulations, and Macromolecular Reaction Engineering.

Contenu

Preface xv

Acknowledgments xvii

Contributors xix

Part I Basic Concepts 1

1 Introduction to Polymers and Polymer Types 3
Enrique Saldívar-Guerra and Eduardo Vivaldo-Lima

1.1 Introduction to Polymers 3

1.2 Classification of Polymers 8

1.3 Nomenclature 12

References 13

2 Polymer States and Properties 15
J. Betzabe González-Campos, Gabriel Luna-Bárcenas, Diana G. Zárate-Triviño, Arturo Mendoza-Galván, Evgen Prokhorov, Francisco Villaseñor-Ortega, and Isaac C. Sanchez

2.1 Introduction 15

2.2 Glass Transition Temperature (a-Relaxation) Controversy in Chitin, Chitosan, and PVA 16

2.3 Glass Transition Related to the a-Relaxation 16

2.4 Moisture Content Effects on Polymer's Molecular Relaxations 17

2.5 Dielectric Fundamentals 18

2.6 Chitin, Chitosan, and PVA Films Preparation for Dielectric Measurements 21

2.7 Dielectric Relaxations in Chitin: Evidence for a Glass Transition 22

2.8 Dielectric Relaxations in Neutralized and Nonneutralized Chitosan: The Stronger Water Content Effect on the a-Relaxation and the Glass Transition Phenomenon 30

2.9 PVA Dielectric Relaxations 35

References 38

Part II Polymer Synthesis and Modification 41

3 Step-Growth Polymerization 43
Luis E. Elizalde, Gladys de los Santos-Villarreal, José L. Santiago-García, and Manuel Aguilar-Vega

3.1 Introduction 43

3.2 Polymerization Kinetics 46

3.3 Polyamides 48

3.4 Polyimides 50

3.5 Polyesters 50

3.6 Inorganic Condensation Polymers 53

3.7 Dendrimers 54

3.8 Thermoset Polycondensation Polymers 55

3.9 Controlled Molecular Weight Condensation Polymers 57

References 62

4 Free Radical Polymerization 65
Ramiro Guerrero-Santos, Enrique Saldívar-Guerra, and José Bonilla-Cruz

4.1 Introduction 65

4.2 Basic Mechanism 66

4.3 Other Free Radical Reactions 68

4.4 Kinetics and Polymerization Rate 71

4.5 Molecular Weight and Molecular Weight Distribution 74

4.6 Experimental Determination of Rate Constants 76

4.7 Thermodynamics of Polymerization 77

4.8 Controlled Radical Polymerization 78

References 81

5 Coordination Polymerization 85
João B. P. Soares and Odilia Pérez

5.1 Introduction 85

5.2 Polymer Types 87

5.3 Catalyst Types 87

5.4 Coordination Polymerization Mechanism 93

5.5 Polymerization Kinetics and Mathematical Modeling 93

References 101

6 Copolymerization 105
Marc A. Dubé, Enrique Saldívar-Guerra, and Iván Zapata-González

6.1 Introduction 105

6.2 Types of Copolymers 106

6.3 Copolymer Composition and Microstructure 107

6.4 Reaction Conditions: Considerations 118

References 121

7 Anionic Polymerization 127
Roderic Quirk

7.1 Introduction 127

7.2 Living Anionic Polymerization 127

7.3 General Considerations 129

7.4 Kinetics and Mechanism of Polymerization 134

7.5 Stereochemistry 144

7.6 Copolymerization of Styrenes and Dienes 148

7.7 Synthetic Applications of Living Anionic Polymerization 150

References 157

8 Cationic Polymerizations 163
Filip E. Du Prez, Eric J. Goethals, and Richard Hoogenboom

8.1 Introduction 163

8.2 Carbocationic Polymerization 163

8.3 Cationic Ring-Opening Polymerization 172

8.4 Summary and Prospects 181

Acknowledgment 181

References 181

9 Crosslinking 187
Julio César Hernández-Ortiz and Eduardo Vivaldo-Lima

9.1 Introduction 187

9.2 Background on Polymer Networks 187

9.3 Main Chemical Routes for Synthesis of Polymer Networks 191

9.4 Characterization of Polymer Networks and Gels 193

9.5 Theory and Mathematical Modeling of Crosslinking 195

Appendix A Calculation of Average Chain Length 200

Appendix B Calculation of Sol and Gel Fractions 201

Acknowledgments 202

References 202

10 Polymer Modification: Functionalization and Grafting 205
José Bonilla-Cruz, Mariamne Dehonor, Enrique Saldívar-Guerra, and Alfonso González-Montiel

10.1 General Concepts 205

10.2 Graft Copolymers 207

References 219

11 Polymer Additives 225
Rudolf Pfaendner

11.1 Introduction 225

11.2 Antioxidants 227

11.3 PVC Heat Stabilizers 231

11.4 Light Stabilizers 233

11.5 Flame Retardants 235

11.6 Plasticizers 238

11.7 Scavenging Agents 239

11.8 Additives to Enhance Processing 240

11.9 Additives to Modify Plastic Surface Properties 240

11.10 Additives to Modify Polymer Chain Structures 241

11.11 Additives to Influence Morphology and Crystallinity of Polymers 242

11.12 Antimicrobials 243

11.13 Additives to Enhance Thermal Conductivity 243

11.14 Active Protection Additives (Smart Additives) 243

11.15 Odor Masking 244

11.16 Animal Repellents 244

11.17 Markers 244

11.18 Blowing Agents 244

11.19 Summary and Trends in Polymer Additives 245

References 245

Further Reading 246

Part III Polymerization Processes and Engineering 249

12 Polymer Reaction Engineering 251
Alexander Penlidis, Eduardo Vivaldo-Lima, Julio César Hernández-Ortiz, and Enrique Saldívar-Guerra

12.1 Introduction 251

12.2 Mathematical Modeling of Polymerization Processes 252

12.3 Useful Tips on Polymer Reaction Engineering (PRE) and Modeling 257

12.4 Examples of Several Free Radical (Co)Polymerization Schemes and the Resulting Kinetic and Molecular Weight Development Equations 264

Acknowledgments 270

References 270

13 Bulk and Solution Processes 273
Marco A. Villalobos and Jon Debling

13.1 Definition 273

13.2 History 273

13.3 Processes for Bulk and Solution Polymerization 274

13.4 Energy Considerations 287

13.5 Mass Considerations 289

References 292

14 Dispersed-Phase Polymerization Processes 295
Jorge Herrera-Ordóñez, Enrique Saldívar-Guerra, and Eduardo Vivaldo-Lima

14.1 Introduction 295

14.2 Emulsion Polymerization 295

14.3 Microemulsion Polymerization 303

14.4 Miniemulsion Polymerization 304

14.5 Applications of Polymer Latexes 304

14.6 Dispersion and Precipitation Polymerizations 305

14.7 Suspension Polymerization 305

14.8 Controlled Radical Polymerization (CRP) in Aqueous Dispersions 308

References 310

**15 New Polymerization Process…