About the Editors xxiii List of Contributors xxv Preface xxix Acknowledgments xxxi Volume 1 1 Introduction to Polymers and Polymer Types 1 Enrique Saldívar-Guerra and Eduardo Vivaldo-Lima 1.1 Introduction to Polymers 1 1.1.1 Basic Concepts 1 1.1.2 History 2 1.1.3 Mechanical and Rheological Properties 2 1.

1.3.1 Mechanical Properties 2 1.1.3.2 Rheological Properties 3 1.1.4 Polymer States 4 1.

1.5 Molecular Weight 4 1.1.5.1 Moments of the Molar Mass Distribution 6 1.1.6 Main Types and Uses 8 1.2 Classification of Polymers 9 1.

2.1 Classification Based on Structure 9 1.2.2 Classification Based on Mechanism 10 1.2.2.1 Step-Growth Polymerization (SGP) 10 1.2.

2.2 Chain or Chain-growth Polymerization (CP) 10 1.2.3 Classification by Chain Topology 11 1.2.4 Other Classification Criteria 14 1.2.4.

1 Homo and Copolymers 14 1.2.4.2 Origin 14 1.2.4.3 Biodegradability and Sustainability 14 1.2.

4.4 Production Volume 15 1.3 Nomenclature 15 1.3.1 Conventional Nomenclature 15 1.3.2 IUPAC Structure-based Nomenclature 16 1.3.

3 Trade, Common Names, and Abbreviations 16 1.4 Further Reading 16 Acknowledgments 17 References 17 2 Polycondensation 19 Luis Ernesto Elizalde, Gladys de losSantos, Rita del Rosario Sulub-Sulub, and Manuel Aguilar-Vega 2.1 Introduction 19 2.1.1 General Principles 19 2.1.2 Number-Average Degree of Polymerization 21 2.1.

3 Molecular Weight Distribution 23 2.1.4 Polymers Obtained by Polycondensation Polymerization 24 2.2 Polycondensation Kinetics 27 2.3 Polyamides 28 2.3.1 Polyamidation 28 2.3.

2 Aromatic Polyamides 30 2.4 Polyimides 30 2.5 Polyesters 32 2.5.1 Polyesters from Diols 32 2.5.2 Polyethers 34 2.5.

3 Polyurethanes 35 2.5.4 Polyureas 35 2.5.5 Polycarbonates 36 2.5.6 Polysulfones 37 2.5.

7 Polybenzimidazole 37 2.5.8 Depolymerization and Recycling 39 2.6 Inorganic Condensation Polymers 41 2.6.1 Polysiloxanes 41 2.6.2 Polysilanes 42 2.

6.3 Polyphosphazenes 43 2.7 Dendrimers 44 2.8 Thermoset Polycondensation Polymers 45 2.8.1 Polyester Resins 45 2.8.2 Epoxy Resins 45 2.

8.3 Alkyd Resins 47 2.8.4 Phenolic Resins 47 2.8.5 Urea-Formaldehyde Resins 47 2.9 Bio-based Step-Growth Polymers 48 2.10 Bio-based Polycondensation Polymers 50 2.

10.1 Dicarboxylic Acids and Diols 52 2.10.2 Hydroxy Acids and Hydroxyl Esters 52 2.10.3 Amino Acids and Lactams 52 2.10.4 Diamines 52 2.

11 Controlled Molecular Weight Condensation Polymers 53 2.11.1 Solid Phase Synthesis 54 2.11.2 Use of Macromonomers in Condensation Reactions 54 References 57 3 Free-Radical Polymerization 65 Ramiro Guerrero-Santos, Enrique Saldívar-Guerra, Iván Zapata-González, José Bonilla-Cruz, and Eduardo Vivaldo-Lima 3.1 Introduction 65 3.2 Basic Mechanism 66 3.2.

1 Chemical Initiation 67 3.2.2 Propagation 68 3.2.3 Termination 69 3.3 Other Free Radical Reactions 70 3.3.1 Chain Transfer to Small Species 70 3.

3.2 Chain Transfer to Monomer 71 3.3.3 Chain Transfer to Initiator 71 3.3.4 Chain Transfer to Solvent and Chain Transfer Agents 71 3.3.5 Chain Transfer to Impurities 72 3.

3.6 Chain Transfer to Polymer 72 3.3.7 Backbiting 74 3.3.8 Reactions to Internal and Terminal Double Bonds and Crosslinking 75 3.3.9 Inhibition 76 3.

4 Kinetics and Polymerization Rate 77 3.4.1 Diffusion-Controlled (DC) Effects 79 3.5 Molecular Weight and Molecular Weight Distribution 83 3.5.1 Full Molecular Weight Distribution 84 3.6 Experimental Determination of Rate Constants 86 3.7 Thermodynamics of Polymerization 86 Acknowledgment 89 References 89 4 Reversible-Deactivation Radical Polymerization (RDRP) 97 Graeme Moad, Eduardo Vivaldo-Lima, Michael F.

Cunningham, Robin A. Hutchinson, Connor Sanders, Enrique Saldívar-Guerra, and Alexander Penlidis 4.1 Introduction to RDRP 97 4.1.1 Terminology for RDRP 97 4.1.1.1 RDRP with Unimolecular Activation - Stable radical-mediated Polymerization 97 4.

1.1.2 RDRP with Bimolecular Activation - Atom-Transfer Radical Polymerization 98 4.1.1.3 RDRP with Activation by Degenerative Chain Transfer - Degenerative Chain-Transfer Radical Polymerization 100 4.1.1.

4 Multiple Mechanism RDRP 100 4.2 Nitroxide-Mediated Polymerization (NMP) 102 4.2.1 Historical Background 102 4.2.2 Polymer Chemistry of NMP 102 4.2.2.

1 Mechanistic Aspects and Chemical Routes 102 4.2.2.2 Nitroxides Most Commonly Used 103 4.2.2.3 Structure Control and Macromolecular Architectures 106 4.2.

3 A Polymer Reaction Engineering (PRE) View of NMP 107 4.2.3.1 Kinetics and Mathematical Modeling 107 4.2.3.2 Dispersed-Phase Polymerizations 109 4.2.

3.3 NMP in scCO2 109 4.2.3.4 Continuous NMP 109 4.2.4 Applications and Perspectives 109 4.2.

5 Closing Remarks 110 4.3 Atom-Transfer Radical Polymerization (ATRP) 111 4.3.1 Normal ATRP 111 4.3.2 ATRP Variants 113 4.3.3 Future Outlook 115 4.

4 Reversible-Addition-Fragmentation Chain-Transfer Polymerization (RAFT) 115 4.4.1 RAFT Mechanism 116 4.4.2 Monomers in RAFT Polymerization 117 4.4.3 Initiation and Termination in RAFT Polymerization 117 4.4.

4 RAFT Agents 118 4.4.4.1 Z Group Selection 120 4.4.4.2 R Group Selection 121 4.4.

4.3 Other Considerations in RAFT Agent Selection 122 4.4.5 Sequence-defined Oligomers 122 4.4.6 (Multi)Block Copolymer Synthesis 122 4.4.7 Star Synthesis 124 4.

5 Other RDRP Systems 125 4.5.1 Degenerative Transfer Controlled Radical Polymerization Mediated by Organotellurium (TERP) 125 4.5.2 Degenerative Transfer RDRP Mediated by Organostibine (SBRP) and Organobismuthine (BIRP) 126 4.5.3 Iodine Transfer Polymerization (ITP) and Variants 127 4.5.

4 Reversible Chain-Transfer Catalyzed Polymerization (RTCP) 127 4.5.5 Organometallic Mediated Radical Polymerization 128 4.6 RDRP in Aqueous Dispersions 129 4.6.1 Introduction 129 4.6.2 Nitroxide-mediated Polymerization (NMP) 130 4.

6.2.1 Emulsion Polymerization 130 4.6.2.2 Miniemulsion Polymerization 130 4.6.2.

3 Microemulsion Polymerization 130 4.6.3 Atom-Transfer Radical Polymerization (ATRP) 130 4.6.3.1 Emulsion Polymerization 130 4.6.3.

2 Miniemulsion Polymerization 131 4.6.3.3 Microemulsion Polymerization 132 4.6.4 Reversible-Addition-Fragmentation Chain-Transfer (RAFT) Polymerization 132 4.6.4.

1 Emulsion Polymerization 132 4.6.4.2 Miniemulsion Polymerization 133 4.6.4.3 Microemulsion Polymerization 133 4.6.

5 Tellurium-Mediated Radical Polymerization (TERP) 133 4.6.6 Iodine Transfer Polymerization 134 4.6.7 Concluding Remarks 134 Acknowledgments 134 References 135 5 Coordination Polymerization 161 João Soares, Odilia Pérez, and Arash Alizadeh 5.1 Introduction 161 5.2 Polyolefin Types 162 5.3 Catalysts Types 162 5.

3.1 Phillips Catalyst 162 5.3.2 Classical Ziegler-Natta Catalysts 163 5.3.2.1 Conjugated and Nonconjugated Dienes Polymerizations 164 5.3.

3 Single-Site Catalysts 164 5.3.3.1 Metallocenes and Constrained Geometry Catalysts 164 5.3.3.2 Nonmetallocene Early Transition Metal-Based SSCs 167 5.3.

3.3 Late Transition Metal Catalysts 168 5.3.3.4 Supported Single-Site Catalysts 168 5.4 Coordination Polymerization Mechanism 169 5.5 Polymerization Kinetics and Mathematical Modeling 170 5.5.

1 Polymer Microstructural Models 170 5.6 Modeling Particle-Scale Phenomena 176 5.7 Polymerization Reactor Models 181 References 183 6 Copolymerization 191 Marc A. Dubé, Enrique Saldívar-Guerra, Iván Zapata-González, and Eduardo Vivaldo-Lima 6.1 Introduction 191 6.1.1 What Are Copolymers? 191 6.1.

2 Commercial Copolymer Examples 192 6.1.2.1 Step-Growth Copolymerization 192 6.2 Types of Copolymers 192 6.2.1 Statistical Copolymers 192 6.2.

2 Alternating Copolymers 193 6.2.3 Block Copolymers 193 6.2.4 Gradient Copolymers 194 6.2.5 Graft Copolymers 194 6.2.

6 Notes on Nomenclature 194 6.3 Copolymer Composition and Microstructure 194 6.3.1 Terminal Model Kinetics 194 6.3.1.1 Copolymer Composition Behavior 197 6.3.

2 Other Copolymerization Models 199 6.3.2.1 Penultimate Model 200 6.3.2.2 Depropagation Models 201 6.3.

2.3 Models Involving the Participation of Complexes 202 6.3.2.4 Model Discrimination 202 6.3.3 Reactivity Ratio Estimation 203 6.3.

4 Sequence Length Distribution 204 6.3.5 Composition Measurement Methods 205 6.3.6 Extensions to Multicomponent Copolymerization 206 6.4 Reaction Condition Considerations 208 6.4.1 Copolymerization Rate 208 6.

4.2 Effect of Temperature 210 6.4.3 Reaction Medium 211 6.4.4 Monomer Concentration Effects 212 6.4.5 Effect of Pressure 213 6.

4.6 Achieving Uniform Copolymer Composition 213 6.4.6.1 Policy I 213 6.4.6.2 Policy II 214 6.

5 Reversible-Deactivation Radical Copolymerization (RDRcoP) 215 6.5.1 Reactivity Ratios for Linear Structures 215 6.5.2 Conventional Copolymerizations and RDRcoP Lead.