reface 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, João 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-Gámez, Alfonso Rodríguez-Galán, Lourdes Franco, and Jordi Puiggalí
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