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PREFACE xv ACKNOWLEDGMENTS xvii CONTRIBUTORS xix PART I BASIC CONCEPTS 1 1 Introduction to Polymers and Polymer Types 3 Enrique Sald´ývar–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 Gonz´alez–Campos, Gabriel Luna–B´arcenas, Diana G. Z´arate–Trivi˜no, Arturo Mendoza–Galv´an, Evgen Prokhorov, Francisco Villase˜nor–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, Jos´e L. Santiago–Garc´ýa, 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 Sald´ývar–Guerra, and Jos´e 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 Jo˜ao B. P. Soares and Odilia P´erez 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. Dub´e, Enrique Sald´ývar–Guerra, and Iv´an Zapata–Gonz´alez 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 C´esar Hern´andez–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 Jos´e Bonilla–Cruz, Mariamne Dehonor, Enrique Sald´ývar–Guerra, and Alfonso Gonz´alez–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 C´esar Hern´andez–Ortiz, and Enrique Sald´ývar–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–Ord´o˜nez, Enrique Sald´ývar–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–S´anchez, Christian H. Hornung, Ira´ýs A. Quintero–Ortega, and Gabriel Luna–B´arcenas 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 Mar´ýa Guadalupe Neira–Vel´azquez, Mar´ýa Teresa Rodr´ýguez–Hern´andez, Ernesto Hern´andez–Hern´andez, and Antelmo R. Y. Ruiz–Mart´ýnez 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. Medell´ýn–Rodr´ýguez 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 L´opez–Barr´on, 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 Ort´ýz–Rodr´ýguez 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–Ort´ýz, Daniel E. Ram´ýrez–Arreola, Denis Rodrigue, and Rub´en Gonz´alez–N´u˜nez 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 D´amaso Navarro Rodr´ýguez 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–Ort´ýz, Francisco J. Fuentes–Talavera, Rub´en Gonz´alez–N´u˜nez, and Jos´e A. Silva–Guzm´an 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 Sa´ul S´anchez–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 Mar´ýa Judith Percino and V´ýctor 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