In-Situ Synthesis of Polymer Nanocomposites (Innbundet (stive permer))

Vikas Mittal is a polymer engineer at BASF Polymer Research in Ludwigshafen, Germany. He obtained his PhD in Polymer and Materials Engineering from the Swiss Federal Institute of Technology in Zurich, Switzerland. Later, he worked as a materials scientist in the Active and Intelligent Coatings section of SunChemical in London, UK. His research interests include polymer nanocomposites, novel filler surface modifications and thermal stability enhancements. He has authored more than 20 scientific publications and book chapters and hold various patents.

This book familiarizes readers with the proven strategies -- as well as the pitfalls -- involved in successfully synthesizing the different types of composites together with their various demands concerning the processing conditions and other influencing factors. Following an overview of the synthesis methodologies, the text goes on to discuss the most relevant polymer materials, including polyamides, polyolefines, polyacrylates, polyethylenes, polyurethanes, polyesters and polyepoxides.

Preface XIII List of Contributors XV 1 In-situ Synthesis of Polymer Nanocomposites 1 Vikas Mittal 1.1 Introduction 1 1.2 Synthesis Methods 9 1.3 In-situ Synthesis of Polymer Nanocomposites 12 References 24 2 Polyamide Nanocomposites by In-situ Polymerization 27 Anastasia C. Boussia, Stamatina N. Vouyiouka, and Constantine D. Papaspyrides 2.1 Introduction 27 2.2 Manufacturing Processes of Commercially Important Polyamides 29 2.2.1 Poly(caproamide) (PA 6) 29 2.2.2 Poly(hexamethylene adipamide) (PA 6.6) 30 2.2.3 Low-Temperature Polymerization Processes 31 2.3 Polyamide Nanocomposites 34 2.3.1 Introduction 34 2.3.2 Lactam/Amino Acid-Based In-situ Intercalated PA Nanocomposites 36 2.3.3 Diamine- and Diacid-Based In-situ Intercalated PA Nanocomposites 41 2.3.3.1 Solution-Melt Polymerization Technique 41 2.3.3.2 Anhydrous Melt Polymerization Technique 43 2.3.3.3 Direct SSP Technique 44 2.3.3.4 Interfacial Polycondensation Technique 46 2.4 Conclusions 48 References 49 3 Polyolefin-Clay Nanocomposites by In-situ Polymerization 53 Abolfazl Maneshi, Joao Soares, and Leonardo Simon 3.1 Introduction 53 3.2 Clays 54 3.2.1 General Structure 54 3.2.2 Smectites 54 3.2.3 Clay Particle Morphological Hierarchy 56 3.2.4 Clay Chemical Reactions 58 3.2.4.1 Cation Exchange Reactions 58 3.2.4.2 Interaction with Organic Compounds 58 3.3 In-situ Polymerization of Olefins with Coordination Catalysts Supported on Clays 59 3.3.1 Olefi n Polymerization with Coordination Catalysts 60 3.3.2 Polymerization Mechanism with Coordination Catalysts 60 3.3.3 Coordination Catalysts for in In-situ Polymerization 62 3.3.4 Catalyst Supporting 63 3.3.4.1 Catalyst Supporting Methods 63 3.3.5 Clay Surface Modification Methods for In-situ Polymerization 64 3.3.5.1 Organic Modification 64 3.3.5.2 Thermal Treatment 66 3.3.5.3 Treatment with Alkylaluminum Compounds 66 3.3.6 Particle Break-Up and Exfoliation 67 3.3.7 In-situ Polymerization Approaches 69 3.3.7.1 Clay as a Polymerization Additive 71 3.3.7.2 Clay as a Polymerization Catalyst Support 72 3.3.7.3 Clay as an Activator for Polymerization Catalysts 74 3.3.7.4 In-situ Production of Alkylaluminoxanes 76 3.3.7.5 Other Techniques 76 3.3.8 Factors Determining the Success of In-situ Polymerization 78 3.3.8.1 Clay Type 78 3.3.8.2 Swellability 79 3.3.8.3 Effect of Clay Surface Treatment 80 3.3.8.4 Catalyst : Clay Ratio 81 3.3.8.5 Effect of Polymerization Conditions 82 3.3.9 Clay Effect on the Polymerization Behavior and Polymer Molecular Structure 83 3.3.10 Future Approaches 84 References 85 4 Gas-Phase-Assisted Surface Polymerization and Thereby Preparation of Polymer Nanocomposites 89 Haruo Nishida, Yoshito Andou, and Takeshi Endo 4.1 Introduction 89 4.2 In-situ Polymerization for Nanocomposite Preparation 89 4.3 Characteristics of GASP 91 4.3.1 Thin Layer Coating of Solid-Substrate Surfaces 91 4.3.2 Physically Controlled Polymerization Behavior 92 4.3.3 Photo-Induced Controlled Polymerization 93 4.4 Composite Preparation by GASP 95 4.4.1 Polymer/Clay Nanocomposites 95 4.4.2 Polymer/Inorganic Compound (Nano)composites 96 4.4.3 Polymer/Cellulose Fiber (Nano)composites 99 4.4.4 Polymer/Carbon Nanotube (Nano)composites 100 4.5 Outlook and Perspective 100 Abbreviations 101 References 101 5 PET Clay Nanocomposites by In-situ Polymerization 105 Hua Deng, Ke Wang, Qin Zhang, Feng Chen, and Qiang Fu 5.1 Introduction 105 5.2 Preparation of PET/Clay Nanocomposites 106 5.3 Morphology of the Nanocomposites 108 5.4 Crystallization of the Nanocomposites 109 5.5 Properties of the Nanocomposites 112 5.5.1 Thermal Properties 112 5.5.2 Mechanical Properties 117 5.5.3 Barrier Properties 118 5.6 Conclusion and Outlook 121 References 122 6 Control of Filler Phase Dispersion in Bio-Based Nanocomposites by In-situ Reactive Polymerization 123 Lawrence A. Pranger, Grady A. Nunnery, and Rina Tannenbaum 6.1 Introduction 123 6.2 Background 125 6.2.1 Polymer Matrix Nanocomposites 125 6.2.1.1 Cellulose Whisker Nanocomposites 128 6.2.1.2 Layered Silicate Nanocomposites 132 6.2.2 Reactive Molding Techniques for Composite Manufacture 133 6.2.2.1 Materials and Methods for Reactive Molding of Nanocomposites 134 6.2.2.2 Furfuryl Alcohol as a Precursor for Polymer Matrix Composites 135 6.3 Experimental Procedures 136 6.3.1 Reactive Molding of Cellulose Whisker Nanocomposites 136 6.3.1.1 Conceptual Approach 136 6.3.1.2 Preparation of CW 137 6.3.1.3 Resinifi cation of FA with CW 137 6.3.1.4 Curing of CW-PFA Composites 137 6.3.1.5 Characterization Techniques 138 6.3.2 Reactive Molding of MMT Nanocomposites 138 6.3.2.1 Conceptual Approach 138 6.3.2.2 Types of MMT Clays Used 139 6.3.2.3 Resinifi cation of FA with MMT Clay 139 6.3.2.4 Curing of MMT-PFA Composites 139 6.3.2.5 Characterization Techniques 139 6.4 Results and Discussion 140 6.4.1 Reactive Molding of Cellulose Whisker Nanocomposites 140 6.4.1.1 Morphology of CW 141 6.4.1.2 Resinifi cation of FA in the Presence of CWs 142 6.4.1.3 Thermal Resistance of CW-FA Nanocomposites 148 6.4.2 Reactive Molding of MMT Nanocomposites 149 6.4.2.1 Morphology of MMT Clay 150 6.4.2.2 Resinifi cation of FA in the Presence of MMT Clay 150 6.4.2.3 Thermal Resistance of MMT-FA Nanocomposites 161 6.5 Conclusions 164 Abbreviations 164 Acknowledgments 165 References 165 7 Polyurethane Nanocomposites by In-situ Polymerization Approach and Their Properties 169 Mo Song and Dongyu Cai 7.1 Introduction 169 7.2 PU/Carbon Nanotube Nanocomposites (PUCNs) 170 7.2.1 Fabrication 170 7.2.2 Morphology and Characterizations of PUCNs 176 7.2.3 Physical Properties of PUCNs 183 7.3 PU/Clay Nanocomposites (PUCLN) 188 7.3.1 Fabrication 189 7.3.1.1 Exfoliation and Intercalation of Nanoclays in PU Matrix 189 7.3.1.2 Rheological Behavior of Polyol-Nanoclay Mixture 194 7.3.2 Morphology and Characterization 196 7.3.3 Physical Properties 200 7.3.3.1 Mechanical Properties 200 7.3.3.2 Scratch Resistance and Barrier Performance 204 7.3.3.3 Thermal Stability and Flame Retardancy 207 7.4 PU/Functionalized Graphene Nanocomposites (PUFGNs) 208 7.4.1 Fabrication 209 7.4.2 Morphology and Characterization 210 7.4.3 Physical Properties 214 7.5 Prospective of PUNs 217 References 218 8 In-situ Synthesis and Properties of Epoxy Nanocomposites 221 Vikas Mittal 8.1 Introduction 221 8.2 Optimization of the Curing Conditions 222 8.3 Fillers, Surface Modifications, and Ion Exchange 224 8.4 Nanocomposite Synthesis 229 8.5 Morphology 231 8.6 Barrier Properties 238 8.7 Effect of Excess Surface Modification Molecules 240 References 244 9 Unsaturated Polyester-Montmorillonite Nanocomposites by In-situ Polymerization 245 Michal Kedzierski 9.1 Introduction 245 9.2 Nanocomposites with MMT Introduced into UP Prepolymer or Resin 246 9.2.1 Synthesis, Morphology, and Mechanical Properties 246 9.2.2 Rheology and Cure Properties 253 9.2.3 Flammability 258 9.2.4 Mixed-Resin and Filler Systems 259 9.3 Nanocomposites with MMT Introduced during the Synthesis of Prepolymer 260 9.4 Conclusions 263 References 265 10 Polymer Clay Nanocomposites by In-situ Atom Transfer Radical Polymerization 267 Hanying Zhao References 279 11 Polybutadiene Clay Nanocomposites by In-situ Polymerization 283 Giuseppe Leone and Giovanni Ricci 11.1 Introduction 283 11.2 Generalities 284 11.2.1 Clays 284 11.2.2 Polymer Nanocomposite Structures 286 11.2.3 Methods of Preparation of Polymer Nanocomposites 287 11.3 Polybutadiene Nanocomposites 287 11.3.1 1,3-Butadiene Polymerization Methods 287 11.3.2 In-situ Anionic Polymerization 289 11.3.3 In-situ Stereospecific Polymerization 293 11.4 Conclusions and Perspectives 299 Abbreviations 299 References 300 12 P3HT-MWNT Nanocomposites by In-situ Polymerization and Their Properties 303 Zhongrui Li and Liqiu Zheng 12.1 Introduction 303 12.2 Multiwall CNTs 305 12.3 In-situ Synthesis of P3HT-MWNT Composites 307 12.4 The Properties and Characterization of P3HT-MWNT Nanocomposites 310 12.4.1 The Dispersion and Morphology of the P3HT-MWNT Nanocomposites 310 12.4.2 HT Regioregularity 311 12.4.3 Mechanical Properties 311 12.4.4 Thermal Stability 313 12.4.5 Optical Properties 316 12.4.6 Charge Transportability 321 12.5 Conclusion and Outlook 325 References 326 13 Polystyrene-Montmorillonite Nanocomposites by In-situ Polymerization and Their Properties 331 Ranya Simons, Greg G. Qiao, and Stuart A. Bateman 13.1 Introduction 331 13.2 Morphology of Polymer-Clay Nanocomposites 331 13.3 Modification of MMT 332 13.3.1 NonReactive Modifications 333 13.3.2 Reactive Modifications 343 13.3.3 Polymeric Initiator-Based Modifications 345 13.4 In-situ Polymerization Methods 346 13.4.1 Free Radical Polymerization Techniques 347 13.4.1.1 Bulk Polymerization 347 13.4.1.2 Emulsion Polymerization 348 13.4.1.3 Solution Polymerization 349 13.4.2 Controlled Polymerization Techniques 350 13.4.2.1 Atom Transfer Radical Polymerization 351 13.4.2.2 Reverse Addition-Fragmentation Transfer 351 13.4.2.3 Nitroxide-Mediated Polymerization 351 13.4.3 Dispersion of MMT in Styrene 352 13.5 Properties of PS-MMT Nanocomposites Prepared via In-situ Techniques 352 13.5.1 Mechanical Properties 353 13.5.1.1 Tensile 353 13.5.1.2 Impact and Flexural Properties 354 13.5.1.3 Dynamic Mechanical Thermal Analysis 354 13.5.1.4 Rheological Properties 355 13.5.1.5 Barrier Properties 355 13.5.2 Thermal Properties 356 13.5.2.1 Thermal Gravimetric Analysis 356 13.5.2.2 Dynamic Scanning Calorimetry (DSC) 358 13.5.2.3 Fire Performance 359 13.6 Summary 361 References 362 14 Aliphatic Polyester and Poly(ester amide) Clay Nanocomposites by In-situ Polymerization 367 Laura Morales-Gamez, Alfonso Rodriguez-Galan, Lourdes Franco, and Jordi Puiggali 14.1 Introduction: Biodegradable Polymers and Their Nanocomposites 367 14.2 Aliphatic Polyester Clay Nanocomposites by In-situ Polymerization 368 14.2.1 Poly(e-Caprolactone)-Based Nanocomposites 368 14.2.2 Polylactide-Based Nanocomposites 375 14.2.3 PBS-Based Nanocomposites 380 14.2.4 PPDO-Based Nanocomposites 381 14.3 PEAs Clay Nanocomposites by In-situ Polymerization 382 14.4 Conclusion 384 Acknowledgments 384 References 384 Index 387