Block Copolymers in Nanoscience
Massimo Lazzari, Guojun Liu, Sébastien Lecommandoux
Contents
Preface XIII
List of Contributors XV
1 An Introductionto Block Copolymer Applications
2 Guidelines for Synthesizing Block Copolymers 9
2.1 Introduction 9
2.2 Free-radical Polymerization 13
2.3 Coupling Reactions of Homopolymers 13
2.4 Se-quential Anionic Polymerization 14
2.5 Sequential Group Transfer Polymerization 16
2.6 Sequential Cationic Polymerization 17
2.7 Non-radical Metal-catalyzed Polymerization 18
2.8 Controlled Radical Polymerization 19
2.8.1 Atom Transfer Radical Polymerization (ATRP) 20
2.8.2 Nitroxide-mediated Polymerization (NMP) 23
2.8.3 Reversible Addition Fragmentation Chain Transfer (the RAFT Process) 25
2.9 Switching from One Polymer-ization Mechanism to Another 27
2.10 Use of “ Dual” Initiators in Concurrent Polymer-ization Mechanisms 29
2.11 Chemical Modification of Pre-formed Block Copolymers 30
2.12 Methods for the Synthesis of Block Copolymers with a Complex Architecture 31
2.13 Conclusion 33 References
3 Block Copolymer Vesicles 39
3.1 Introduction 39
3.2 Chemistry of Vesicle-forming Block Copoly-mers 41
3.3 Block Copolymer Vesicle Formation in Water 46
3.4 Block Copolymer Vesicle Formation in Organic Solvents 48
3.5 Properties of Polymer Vesicles 51
3.5.1 Morphology and Size of Polymer Vesicles 51
3.5.2 Membrane Properties 53
3.5.2.1 Polymer Membrane Thickness 53
3.5.2.2 Mechanical Properties of Polymer Vesicles 54
3.5.2.3 Adhesion of Polymer Vesicles 57
3.5.2.4 Fusion and Fission of Polymer Vesicles 58
3.6 Functional Polymer Vesicles 59
3.7 Biohybrid Polymer Vesicles 60
3.7.1 Polypeptide-based Copoly-mer Vesicles 60
3.7.2 Protein Incorporation into Polymer Vesicles 62
3.8 Potential Appli-cations of Polymer Vesicles 64
3.9 Concluding Remarks 66 References 66
4 Block Copolymer Micellesfor Drug Deliveryin Nanoscience 73
5.1 Introduction 91
5.2 Stimuli sensitive Micellization 92
5.2.1 Temperature sensitive Micellization 93
5.2.2 pH-sensitive Micellization 95
5.2.3 Ionic Strength Sen-sitive Micellization 98
5.3 Stimuli-responsive Micelles 100
5.4 Multi-responsive Micellar Sys-tems 103
5.5 Stimuli-responsive Thin Films from Block Copolymers 106
5.6 Stimuli-re-sponsive Block Copolymers in the Bulk 109
5.7 Conclusions and Outlook 112 References 114
6 Self-assembly of Linear Polypeptide based Block Copolymers 117
6.1 Introduction 117
6.2 Solution Self-assembly of Polypeptide-based Block Copolymers
6.2.1 Aggregation of Polypeptide-based Block Copolymers 119
6.2.1.1 Polypeptide Hybrid Block Copolymers 119
6.2.1.2 Block Copolypeptides 123
6.2.2 Polypeptide-based Hydrogels 124
6.2.3 Organic/Inorganic Hybrid Structures 124
6.3 Sol-id-state Structures of Polypeptide-based Block Copolymers 126
6.3.1 Diblock
Copolymers 126
6.3.1.1 Polydiene-based Diblock Copolymers 126
6.3.1.2 Polystyrene-based Diblock Copolymers 127
6.3.1.3 Polyether-based Diblock Copolymers 131
6.3.1.4 Polyester-based Diblock Copolymers 133
6.3.1.5 Diblock Copolypeptides 133
6.3.2 Triblock Copolymers 134
6.3.2.1 Polydiene-based Triblock Copolymers 134
6.3.2.2 Polystyrene-based Triblock Copolymers 138
6.3.2.3 Polysiloxane-based Triblock Copolymers 139
6.3.2.4 Polyether-based Triblock Copolymers 140
6.3.2.5 Miscellaneous 144
6.4 Summary and Outlook 146 References 147
7 Synthesis,Self assembly and Applications of Poly ferrocenylsilane(PFS) Block Copolymers 151
7.1 Intro-duction 151
7.2 Synthesis of PFS Block Copolymers 152
7.3 Solution Self-assembly of PFS Block Copolymers 158
7.4 Shell Cross-linked Nanocylinders and Nanotubes 161
7.5 Self-assembly of PFS Block Copolymers in the Solid State 164
7.6 Summary 166 References 167
8 Supramolecular Block Copolymers Containing Metal Ligand Binding Sites: 169
8.1 Intro-duction 169
8.2 Block Copolymers with Chain-end Containing Metal Complexes 172
8.2.1 Metal Complexes in the Center of Star Polymers 172
8.2.2 Supramolecular Diblock Copolymers Connected by Metal Complexes 174
8.3 Block Copolymers with Side-chain Metal Complexes in One Block 178
8.3.1 Polymerizing Pre-formed Metal Complexes 178
8.3.2 Block Copolymers Containing Free Metal–Ligand Side-chains 180
8.3.2.1 Polymer-ization of Metal–Ligand Containing Monomers
8.3.2.2 Post-polymerization Attachment of the Metal–Ligand 184
8.4 Conclusion 187 References 187
9 Methods for the Alignment and the Large scale Orderingof Block Copolymer Morphologies 191
9.1 Introduc-tion 191
9.1.1 Motivation 191
9.1.2 Organization of the Chapter 192
9.2 How to Help Phase Separation 193
9.3 Orientation by External Fields 195
9.3.1 Mechanical Flow Fields 196
9.3.2 Electric and Magnetic Fields 197
9.3.3 Solvent Evaporation and Thermal Gradi-ent 202
9.4 Templated Self-assembly on Nanopatterned Surfaces 203
9.5 Epitaxy and Sur-face Interactions 205
9.5.1 Preferential Wetting and Homogeneous Surface Interactions 205
9.5.2 Epitaxy 206
9.5.3 Directional Crystallization 209
9.5.4 Graphoepitaxy and Other Confining Geometries 212
9.5.5 Combination of Directional Crystallization and Graphoepitaxy 214
9.5.6 Combination of Epitaxy and Directional Crystallization 215
9.6 Summary and Outlook 223 References 225
10 Block Copolymer Nanofibers and Nanotubes 233
10.1 Introduction 233
10.2 Preparation 235
10.2.1 Nanofiber Preparation 235
10.2.2 Nanotube Preparation 238
10.3 Solution Properties 240
10.4 Chemical Reac-tions 247
10.4.1 Backbone Modification 247
10.4.2 End Functionalization 251
10.5 Con-cluding Remarks 253 References 254
11 Nanostructured Carbons from Block Copolymers 257
11.1 Introduction 257
11.2 Discussion
11.2.1 Well Defined PAN Polymers and Copolymers 259
11.2.2 Carbon Films from Phase-separated Block Copolymers 260
11.2.3 Carbon Nanoobjects from Wa-ter-soluble Precursors 265
11.2.4 Nanoporous Carbon from Block Copolymers Using Sil-ica as an Auxiliary Component 266
11.2.5 Nanoporous Carbon from Phase-separated Block Copolymers 268
11.2.6 Carbons Synthesized Using Other Block Copolymers 270
11.3 Conclusion 271 References 272
12 Block Copolymers at Interfaces
12.1 Introduction 275
12.2 Block Copolymer Films 277
12.3 Block Copolymers on Heterogeneous Surfaces 278
12.4 Environmental Control of Block Copolymer Films 279
12.5 Block Copolymer Brushes 282
12.6 Surface Regeneration 286
12.7 Conclusions and Outlook 286 References 287
13 Block Copolymersas Templates for the Generation of Mesostructured InorganicMaterials 291
13.1 Introduction 291
13.2 General Mechanism 292
13.3 Details of the BC Tem-plating Mechanism 298
13.4 Crystalline, Mesoporous Metal Oxides 299
13.5 Mesoporous Metals 304
13.6 Conclusion and Outlook 304 References 305
14 Mesostructured Polymer–Inorganic Hybrid Materials from Blocked Macromolecular Architecturesand Nanoparticles 309
14.1 Introduction 309
14.2 AB Diblock Copolymers as Structure-directing Agents for Aluminosilicate Mesostructures 310
14.2.1 Formation Mechanisms 313
14.2.2 Flow-induced Alignment of Mesostructured Block Copolymer–Sol Nanoparticle Co-assemblies 316
14.3 Generalization to Other Blocked Macromolecular Amphiphiles as Structure-directing Agents for Mesostructured Materials
14.4 Generalization to Other Inorganic Materials Systems 322
14.4.1 Mesoporous Aluminosilicate Materials with Superparamagnetic γ-Fe2O3 Particles Embedded in the Walls 322
14.4.2 Ordered Mesoporous Ceramics Stable up to 1500 °C from Diblock Copolymer Mesophases 324
14.5 Generalization from Bulk Mesostructured Hybrids to Mesostructured Thin Films 328
14.6 Conclusions 331 References 332
15 Block Ionomers-forFuelCellApplication 337
15.1 Introduction 337
15.2 Definitions and Investigations 342
15.3 Polymer Modification 344
15.3.1 Post-sulfonation 344
15.3.2 Grafting 345
15.3.3 Blends 346
15.4 Copolymerization of Functionalized Monomers 347
15.4.1 Main-chain Type Co-ionomer 347
15.4.1.1 Sulfonated Polyimides 347
15.4.1.2 Polyarylene Systems 351
15.4.2 “ Side Chain” Co-ionomers 353
15.5 Di- and Triblock Ionomers 357
15.6 Conclusion 362 References 363
16 Structure, Propertiesan- Application so fABA and ABCT riblock Copolymers with Hydrogenated Polybutadi-eneBlocks 367
16.1 Introduc-tion 367
16.2 Applications of SEBS Triblock Copolymers 371
16.2.1 Adhesives, Sealants and Coatings 372
16.2.2 Bitumen Modification 373
16.2.3 Compounding and Plastic Mod-ification 375
16.2.4 Miscellaneous Applications 377
16.2.4.1 Gels and Nanocomposites 377
16.2.4.2 Medical Applications 378
16.2.5 Future Trends 379
16.3 Semicrystalline Triblock Copolymers with One or More HPB Blocks 379
16.3.1 Semicrystalline ABA Triblock Copolymers
16.3.2 Semicrystalline ABC Triblock Copolymers 381
16.4 Conclusions 387 References 388
17 Basic Understanding of Phase Behaviorand Structure of Silicone Block Copolymers and Surfactant –Block Copolymer Mixtures 391
17.1 In-troduction 391
17.2 General Aspects of Phase Behavior and Liquid Crystal Phases 393
17.3 Phase Behavior and Microstructure of Si m C 3 EO n Melts 395
17.4 Phase Behavior and Microstructure Si m C 3 EO n in Water 400
17.4.1 Phase Diagrams of Water–Si m C 3 EO n Systems as a Function of Temperature 400
17.4.2 Phase Diagrams of Water–Si m C 3 EO n Systemsas a Function of PEO Chain Length 402
17.4.3 Phase Diagram of Water–Sim C3EO 51.6 System as a Function of PDMS Chain Length 403
17.4.4 Effect of PEO and PDMS Chain Lengths on the Effective Cross-sectional Area per Copolymer Molecule, a P 404
17.5 Phase Behavior of Sim C3EO n in Non-polar Oil 406
17.6 Phase Behavior of Sim C3EO n in Non-aqueous Polar Solvents 408
17.7 Mixing of Poly(oxyethylene)–Poly(dimethylsiloxane) Copolymer and Non-ionic Surfactant in Water 410
17.8 Conclu-sions and Outlook 415
References 415
SubjectIndex
Preface
Nanoscience
and technology deal with the preparation, study, manipulation and
application of nanometer-sized structures. “ Nanoscience and technology
have the potential for revolutionizing the ways in which ma-terials and
products are created and therange and nature off unctionalities that can
be accessed. It is aninter disci- plinary area of research and
development activity that has been growing-explosively world wide in the
past decade”.
Some
exampl eareas that nanotechnology may impact profoundly include the
continuing miniaturization of electronic and memory devices, the
development of more potent drugs that can recognize and attack only the
diseased sites, the development of more accurate and effective diagnostic
pro- cedures and the de-sign and synthesis of more robust catalysts.
Physicists and engineers prepare nanostruc-tures by taking the top-down
ap- proach using techniques such as lithography, which “ carves” a large
piece of material into smaller pieces.
They
can now routinely make struc-tures on an industrial scale with
dimensions approaching around 100 nm by lithography. Chemists make
nanostructures by assembling molecules together or taking the bottom-up
approach. Structures made from the spontaneous assembly or self-
assembly of organic and inorganic molecules are normally smaller than 10
nm. Animminent challenge facingth-enanotechnology community is the
development of methodologies for the preparation of materials with
dimensions occupying the size range between 10 and 100 nm, a task that
can be readily accomplished by block copolymer (BC) researchers.
This
book gives an overview of recent developments in the nanoscience and
technology of block polymers. Instead of a simple collection of review
chapters, our objective was to compile a handbook that careful-ly
evaluates all types of applications for block copolymers: as tools for
fabricating other nanomaterials, as structural components in hybrid
materials and nanocomposites, and as functional materials....
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