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 xvAcknowledgments xviiContributors xixPart I Basic Concepts 11 Introduction to Polymers and Polymer Types 3Enrique Saldívar-Guerra and Eduardo Vivaldo-Lima1.1 Introduction to Polymers 31.2 Classification of Polymers 81.3 Nomenclature 12References 132 Polymer States and Properties 15J. Betzabe González-Campos, Gabriel Luna-Bárcenas, Diana G. Zárate-Triviño, Arturo Mendoza-Galván, Evgen Prokhorov, Francisco Villaseñor-Ortega, and Isaac C. Sanchez2.1 Introduction 152.2 Glass Transition Temperature (α-Relaxation) Controversy in Chitin, Chitosan, and PVA 162.3 Glass Transition Related to the α-Relaxation 162.4 Moisture Content Effects on Polymer’s Molecular Relaxations 172.5 Dielectric Fundamentals 182.6 Chitin, Chitosan, and PVA Films Preparation for Dielectric Measurements 212.7 Dielectric Relaxations in Chitin: Evidence for a Glass Transition 222.8 Dielectric Relaxations in Neutralized and Nonneutralized Chitosan: The Stronger Water Content Effect on the α-Relaxation and the Glass Transition Phenomenon 302.9 PVA Dielectric Relaxations 35References 38Part II Polymer Synthesis and Modification 413 Step-Growth Polymerization 43Luis E. Elizalde, Gladys de los Santos-Villarreal, José L. Santiago-García, and Manuel Aguilar-Vega3.1 Introduction 433.2 Polymerization Kinetics 463.3 Polyamides 483.4 Polyimides 503.5 Polyesters 503.6 Inorganic Condensation Polymers 533.7 Dendrimers 543.8 Thermoset Polycondensation Polymers 553.9 Controlled Molecular Weight Condensation Polymers 57References 624 Free Radical Polymerization 65Ramiro Guerrero-Santos, Enrique Saldívar-Guerra, and José Bonilla-Cruz4.1 Introduction 654.2 Basic Mechanism 664.3 Other Free Radical Reactions 684.4 Kinetics and Polymerization Rate 714.5 Molecular Weight and Molecular Weight Distribution 744.6 Experimental Determination of Rate Constants 764.7 Thermodynamics of Polymerization 774.8 Controlled Radical Polymerization 78References 815 Coordination Polymerization 85João B. P. Soares and Odilia Pérez5.1 Introduction 855.2 Polymer Types 875.3 Catalyst Types 875.4 Coordination Polymerization Mechanism 935.5 Polymerization Kinetics and Mathematical Modeling 93References 1016 Copolymerization 105Marc A. Dubé, Enrique Saldívar-Guerra, and Iván Zapata-González6.1 Introduction 1056.2 Types of Copolymers 1066.3 Copolymer Composition and Microstructure 1076.4 Reaction Conditions: Considerations 118References 1217 Anionic Polymerization 127Roderic Quirk7.1 Introduction 1277.2 Living Anionic Polymerization 1277.3 General Considerations 1297.4 Kinetics and Mechanism of Polymerization 1347.5 Stereochemistry 1447.6 Copolymerization of Styrenes and Dienes 1487.7 Synthetic Applications of Living Anionic Polymerization 150References 1578 Cationic Polymerizations 163Filip E. Du Prez, Eric J. Goethals, and Richard Hoogenboom8.1 Introduction 1638.2 Carbocationic Polymerization 1638.3 Cationic Ring-Opening Polymerization 1728.4 Summary and Prospects 181Acknowledgment 181References 1819 Crosslinking 187Julio César Hernández-Ortiz and Eduardo Vivaldo-Lima9.1 Introduction 1879.2 Background on Polymer Networks 1879.3 Main Chemical Routes for Synthesis of Polymer Networks 1919.4 Characterization of Polymer Networks and Gels 1939.5 Theory and Mathematical Modeling of Crosslinking 195Appendix A Calculation of Average Chain Length 200Appendix B Calculation of Sol and Gel Fractions 201Acknowledgments 202References 20210 Polymer Modification: Functionalization and Grafting 205José Bonilla-Cruz, Mariamne Dehonor, Enrique Saldívar-Guerra, and Alfonso González-Montiel10.1 General Concepts 20510.2 Graft Copolymers 207References 21911 Polymer Additives 225Rudolf Pfaendner11.1 Introduction 22511.2 Antioxidants 22711.3 PVC Heat Stabilizers 23111.4 Light Stabilizers 23311.5 Flame Retardants 23511.6 Plasticizers 23811.7 Scavenging Agents 23911.8 Additives to Enhance Processing 24011.9 Additives to Modify Plastic Surface Properties 24011.10 Additives to Modify Polymer Chain Structures 24111.11 Additives to Influence Morphology and Crystallinity of Polymers 24211.12 Antimicrobials 24311.13 Additives to Enhance Thermal Conductivity 24311.14 Active Protection Additives (Smart Additives) 24311.15 Odor Masking 24411.16 Animal Repellents 24411.17 Markers 24411.18 Blowing Agents 24411.19 Summary and Trends in Polymer Additives 245References 245Further Reading 246Part III Polymerization Processes and Engineering 24912 Polymer Reaction Engineering 251Alexander Penlidis, Eduardo Vivaldo-Lima, Julio César Hernández-Ortiz, and Enrique Saldívar-Guerra12.1 Introduction 25112.2 Mathematical Modeling of Polymerization Processes 25212.3 Useful Tips on Polymer Reaction Engineering (PRE) and Modeling 25712.4 Examples of Several Free Radical (Co)Polymerization Schemes and the Resulting Kinetic and Molecular Weight Development Equations 264Acknowledgments 270References 27013 Bulk and Solution Processes 273Marco A. Villalobos and Jon Debling13.1 Definition 27313.2 History 27313.3 Processes for Bulk and Solution Polymerization 27413.4 Energy Considerations 28713.5 Mass Considerations 289References 29214 Dispersed-Phase Polymerization Processes 295Jorge Herrera-Ordóñez, Enrique Saldívar-Guerra, and Eduardo Vivaldo-Lima14.1 Introduction 29514.2 Emulsion Polymerization 29514.3 Microemulsion Polymerization 30314.4 Miniemulsion Polymerization 30414.5 Applications of Polymer Latexes 30414.6 Dispersion and Precipitation Polymerizations 30514.7 Suspension Polymerization 30514.8 Controlled Radical Polymerization (CRP) in Aqueous Dispersions 308References 31015 New Polymerization Processes 317Eduardo Vivaldo-Lima, Carlos Guerrero-Sánchez, Christian H. Hornung, Iraís A. Quintero-Ortega, and Gabriel Luna-Bárcenas15.1 Introduction 31715.2 Polymerizations in Benign or Green Solvents 31715.3 Alternative Energy Sources for Polymerization Processes 32715.4 Polymerization in Microreactors 329Acknowledgments 331References 331Part IV Polymer Characterization 33516 Polymer Spectroscopy and Compositional Analysis 337Gladys de los Santos-Villarreal and Luis E. Elizalde16.1 Introduction 33716.2 Elemental Analysis 33716.3 Infrared Spectroscopy 33916.4 Nuclear Magnetic Resonance of Polymers in Solution 34316.5 Mass Spectrometry 351References 35317 Polymer Molecular Weight Measurement 355María Guadalupe Neira-Velázquez, María Teresa Rodríguez-Hernández, Ernesto Hernández-Hernández, and Antelmo R. Y. Ruiz-Martínez17.1 Introduction 35517.2 Historical Background 35517.3 Principles of GPC 35617.4 Measurement of Intrinsic Viscosity 362References 36518 Light Scattering and its Applications in Polymer Characterization 367Roberto Alexander-Katz18.1 Introduction 36718.2 Principles of Static and Dynamic Light Scattering 36718.3 Static Light Scattering by Dilute Polymer Solutions 37018.4 Dynamic Light Scattering 377References 38719 Small-Angle X-Ray Scattering of Polymer Systems 391Carlos A. Avila-Orta and Francisco J. Medellín-Rodríguez19.1 Introduction 39119.2 Polymer Morphology 39119.3 Small-Angle X-Ray Scattering 39319.4 Analysis in Reciprocal Space 39519.5 Analysis in Real Space 399Appendix A Procedure to Obtain Morphological Data from 1D SAXS Profiles 404References 40620 Microscopy 409Mariamne Dehonor, Carlos López-Barrón, and Christopher W. Macosko20.1 Introduction 40920.2 Transmission Electron Microscopy 40920.3 Three-Dimensional Microscopy 416References 42121 Structure and Mechanical Properties of Polymers 425Manuel Aguilar-Vega21.1 Structure of Polymer Chains 42521.2 Mechanical Properties of Polymers 42621.3 Mechanical Properties of Polymer Composites 431References 434Part V Polymer Processing 43522 Polymer Rheology 437Estanislao Ortíz-Rodríguez22.1 Introduction to Polymer Rheology Fundamentals 43722.2 Linear Viscoelasticity 44022.3 Viscometric Techniques for Polymer Melts 44122.4 Overview of Constitutive Equations 44322.5 Brief Overview on Other Relevant Polymer Rheology Aspects 445References 44823 Principles of Polymer Processing 451Luis F. Ramos-de Valle23.1 General 45123.2 Compounding 45123.3 Extrusion 45223.4 Bottle Blowing 45523.5 Injection Molding 45523.6 Thermoforming 460References 461Further Reading 46124 Blown Films and Ribbons Extrusion 463Jorge R. Robledo-Ortíz, Daniel E. Ramírez-Arreola, Denis Rodrigue, and Rubén González-Núñez24.1 Introduction 46324.2 Extrusion Processes for Blown Films and Ribbons 46324.3 Equations 46524.4 Ribbon and Film Dimensions 46724.5 Cooling Process and Stretching Force 46724.6 Morphology and Mechanical Properties 469References 47225 Polymer Solutions and Processing 473Dámaso Navarro Rodríguez25.1 Introduction 47325.2 Polymer Solution Thermodynamics and Conformation of Polymer Chains: Basic Concepts 47425.3 Semidilute Polymer Solutions 48125.4 Processing of Polymer Solutions 482References 48826 Wood and Natural Fiber-Based Composites (NFCs) 493Jorge R. Robledo-Ortíz, Francisco J. Fuentes-Talavera, Rubén González-Núñez, and José A. Silva-Guzmán26.1 Introduction 49326.2 Background 49326.3 Raw Materials 49426.4 Manufacturing Process 49726.5 Properties of Composite Materials 49726.6 Durability 49826.7 Factors that Affect Decay of Wood–Plastic Composites 50026.8 Uses of Wood–Plastic Composites 501References 50127 Polymer Blends 505Saúl Sánchez-Valdes, Luis F. Ramos-de Valle, and Octavio Manero27.1 Introduction 50527.2 Miscibility in Polymer Blends 50527.3 Compatibility in Polymer Blends 50827.4 Techniques for Studying Blend Microstructure 50927.5 Preparation of Polymer Blends 51027.6 Factors Influencing the Morphology of a Polymer Blend 51127.7 Properties of Polymer Blends 51327.8 Applications of Polymer Blends 516References 51728 Thermosetting Polymers 519Jean-Pierre Pascault and Roberto J.J. Williams28.1 Introduction 51928.2 Chemistries of Network Formation 52028.3 Structural Transformations During Network Formation 52128.4 Processing 52428.5 Conclusions 532References 532Part VI Polymers for Advanced Technologies 53529 Conducting Polymers 537María Judith Percino and Víctor Manuel Chapela29.1 Introduction 53729.2 Historical Background 53829.3 The Structures of Conducting Polymers 53929.4 Charge Storage 53929.5 Doping 54129.6 Polyanilines 54329.7 Charge Transport 54429.8 Syntheses 54529.9 Conducting Polymers 54529.10 Characterization Techniques 55129.11 Present and Future Potential 552References 55530 Dendritic Polymers 559Jason Dockendorff and Mario Gauthier30.1 Introduction 55930.2 Dendrimers 56130.3 Hyperbranched Polymers 56730.4 Dendrigraft Polymers 57430.5 Concluding Remarks 581References 58231 Polymer Nanocomposites 585Octavio Manero and Antonio Sanchez-Solis31.1 Introduction 58531.2 Polyester/Clay Nanocomposites 58631.3 Polyolefin/Clay Nanocomposites 59031.4 Polystyrene/Clay Nanocomposites 59331.5 Polymer/Carbon Black Nanocomposites 59631.6 Nanoparticles of Barium Sulfate 59731.7 Polymer/Graphene Nanocomposites 59831.8 Conclusions 601Acknowledgments 601References 601Index 605

“In summary, Handbook of Polymer Synthesis, Characterization and Processing is a valuable reference work for everyone working in the area of polymer science and technology, and for advanced students who wish to get a good insight into specific aspects of this field.”  (Angew. Chem. Int. Ed, 1 February 2014)