Handbook of Polymer Synthesis, Characterization, and Processing

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.

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 (α-Relaxation) Controversy in Chitin, Chitosan, and PVA 16

2.3 Glass Transition Related to the α-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 α-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 Processes 317
Eduardo Vivaldo-Lima, Carlos Guerrero-Sánchez, Christian H. Hornung, Iraís A. Quintero-Ortega, and Gabriel Luna-Bárcenas

15.1 Introduction 317

15.2 Polymerizations in Benign or Green Solvents 317

15.3 Alternative Energy Sources for Polymerization Processes 327

15.4 Polymerization in Microreactors 329

Acknowledgments 331

References 331

Part IV Polymer Characterization 335

16 Polymer Spectroscopy and Compositional Analysis 337
Gladys de los Santos-Villarreal and Luis E. Elizalde

16.1 Introduction 337

16.2 Elemental Analysis 337

16.3 Infrared Spectroscopy 339

16.4 Nuclear Magnetic Resonance of Polymers in Solution 343

16.5 Mass Spectrometry 351

References 353

17 Polymer Molecular Weight Measurement 355
María Guadalupe Neira-Velázquez, María Teresa Rodríguez-Hernández, Ernesto Hernández-Hernández, and Antelmo R. Y. Ruiz-Martínez

17.1 Introduction 355

17.2 Historical Background 355

17.3 Principles of GPC 356

17.4 Measurement of Intrinsic Viscosity 362

References 365

18 Light Scattering and its Applications in Polymer Characterization 367
Roberto Alexander-Katz

18.1 Introduction 367

18.2 Principles of Static and Dynamic Light Scattering 367

18.3 Static Light Scattering by Dilute Polymer Solutions 370

18.4 Dynamic Light Scattering 377

References 387

19 Small-Angle X-Ray Scattering of Polymer Systems 391
Carlos A. Avila-Orta and Francisco J. Medellín-Rodríguez

19.1 Introduction 391

19.2 Polymer Morphology 391

19.3 Small-Angle X-Ray Scattering 393

19.4 Analysis in Reciprocal Space 395

19.5 Analysis in Real Space 399

Appendix A Procedure to Obtain Morphological Data from 1D SAXS Profiles 404

References 406

20 Microscopy 409
Mariamne Dehonor, Carlos López-Barrón, and Christopher W. Macosko

20.1 Introduction 409

20.2 Transmission Electron Microscopy 409

20.3 Three-Dimensional Microscopy 416

References 421

21 Structure and Mechanical Properties of Polymers 425
Manuel Aguilar-Vega

21.1 Structure of Polymer Chains 425

21.2 Mechanical Properties of Polymers 426

21.3 Mechanical Properties of Polymer Composites 431

References 434

Part V Polymer Processing 435

22 Polymer Rheology 437
Estanislao Ortíz-Rodríguez

22.1 Introduction to Polymer Rheology Fundamentals 437

22.2 Linear Viscoelasticity 440

22.3 Viscometric Techniques for Polymer Melts 441

22.4 Overview of Constitutive Equations 443

22.5 Brief Overview on Other Relevant Polymer Rheology Aspects 445

References 448

23 Principles of Polymer Processing 451
Luis F. Ramos-de Valle

23.1 General 451

23.2 Compounding 451

23.3 Extrusion 452

23.4 Bottle Blowing 455

23.5 Injection Molding 455

23.6 Thermoforming 460

References 461

Further Reading 461

24 Blown Films and Ribbons Extrusion 463
Jorge R. Robledo-Ortíz, Daniel E. Ramírez-Arreola, Denis Rodrigue, and Rubén González-Núñez

24.1 Introduction 463

24.2 Extrusion Processes for Blown Films and Ribbons 463

24.3 Equations 465

24.4 Ribbon and Film Dimensions 467

24.5 Cooling Process and Stretching Force 467

24.6 Morphology and Mechanical Properties 469

References 472

25 Polymer Solutions and Processing 473
Dámaso Navarro Rodríguez

25.1 Introduction 473

25.2 Polymer Solution Thermodynamics and Conformation of Polymer Chains: Basic Concepts 474

25.3 Semidilute Polymer Solutions 481

25.4 Processing of Polymer Solutions 482

References 488

26 Wood and Natural Fiber-Based Composites (NFCs) 493
Jorge R. Robledo-Ortíz, Francisco J. Fuentes-Talavera, Rubén González-Núñez, and José A. Silva-Guzmán

26.1 Introduction 493

26.2 Background 493

26.3 Raw Materials 494

26.4 Manufacturing Process 497

26.5 Properties of Composite Materials 497

26.6 Durability 498

26.7 Factors that Affect Decay of Wood–Plastic Composites 500

26.8 Uses of Wood–Plastic Composites 501

References 501

27 Polymer Blends 505
Saúl Sánchez-Valdes, Luis F. Ramos-de Valle, and Octavio Manero

27.1 Introduction 505

27.2 Miscibility in Polymer Blends 505

27.3 Compatibility in Polymer Blends 508

27.4 Techniques for Studying Blend Microstructure 509

27.5 Preparation of Polymer Blends 510

27.6 Factors Influencing the Morphology of a Polymer Blend 511

27.7 Properties of Polymer Blends 513

27.8 Applications of Polymer Blends 516

References 517

28 Thermosetting Polymers 519
Jean-Pierre Pascault and Roberto J.J. Williams

28.1 Introduction 519

28.2 Chemistries of Network Formation 520

28.3 Structural Transformations During Network Formation 521

28.4 Processing 524

28.5 Conclusions 532

References 532

Part VI Polymers for Advanced Technologies 535

29 Conducting Polymers 537
María Judith Percino and Víctor Manuel Chapela

29.1 Introduction 537

29.2 Historical Background 538

29.3 The Structures of Conducting Polymers 539

29.4 Charge Storage 539

29.5 Doping 541

29.6 Polyanilines 543

29.7 Charge Transport 544

29.8 Syntheses 545

29.9 Conducting Polymers 545

29.10 Characterization Techniques 551

29.11 Present and Future Potential 552

References 555

30 Dendritic Polymers 559
Jason Dockendorff and Mario Gauthier

30.1 Introduction 559

30.2 Dendrimers 561

30.3 Hyperbranched Polymers 567

30.4 Dendrigraft Polymers 574

30.5 Concluding Remarks 581

References 582

31 Polymer Nanocomposites 585
Octavio Manero and Antonio Sanchez-Solis

31.1 Introduction 585

31.2 Polyester/Clay Nanocomposites 586

31.3 Polyolefin/Clay Nanocomposites 590

31.4 Polystyrene/Clay Nanocomposites 593

31.5 Polymer/Carbon Black Nanocomposites 596

31.6 Nanoparticles of Barium Sulfate 597

31.7 Polymer/Graphene Nanocomposites 598

31.8 Conclusions 601

Acknowledgments 601

References 601

Index 605