Hartmann-Thompson Applications of Polyhedral Oligomeric Silsesquioxanes

2011
ISBN: 978-90-481-3787-9
Verlag: Springer Netherlands
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, Band 3, 420 Seiten

Reihe: Advances in Silicon Science

The commercial availability and decreasing cost of polyhedral oligomeric silsesquioxanes in recent years has opened up the field to everybody who wishes to apply these unique properties in their own technologies. This is the first book to provide a comprehensive overview of these applications, and covers the synthesis, characterization and history of polyhedral oligomeric silsesquioxanes, their use as metallasilsesquioxane catalysts, their effect upon polymer properties and plastics performance, and their use in superhydrophobic nanocomposites, and electronics, energy, space and biomedical applications. 'Applications of Polyhedral Oligomeric Silsesquioxanes' is a valuable reference for those working across a range of disciplines, including chemists, materials scientists, polymer physicists, plastics engineers, surface scientists, and anybody with a commercial or academic interest in plastics, composite materials, space materials, dental materials, tissue engineering, drug delivery, lithography, fuel cells, batteries, lubricants, or liquid crystal, LED, sensor, photovoltaic or biomedical devices.

Autoren/Hrsg.

Hartmann-Thompson, Claire

Inhaltsverzeichnis

1;Foreword: The Re-Birth of PolyhedralOligosilsesquioxane Chemistry;5
2;Preface;11
3;Biographical Note;14
4;Contents;15
5;Contributors;23
6;Chapter 1 Polyhedral Oligomeric Silsesquioxanes: From Early and Strategic Development through to Materials Application;26
6.1;1.1 Introduction;26
6.2;1.2 Early Synthesis of Polyhedral Oligosilsesquioxanes (POS);29
6.3;1.3 Hydrolysis and Condensation in Making Oligosilsesquioxanes;30
6.4;1.4 Synthesis of Hydridooctasilsesquioxane, H8Si8O12 (T8H8) and Octakis-(Hydridodimethylsiloxy)Octasilsesquioxane, [H(CH3)2SiO]8Si8O12 (Q8M8H8);33
6.5;1.5 Hydrosilylation;35
6.6;1.6 Octa-Functionalized POS Macromonomers;36
6.6.1;1.6.1 Macromonomers Derived by the Hydrosilylation of Octahydridosilsesquioxane (H8Si8O12; T8 H )36
6.6.2;1.6.2 Macromonomers Derived by the Hydrosilylation of Octa(Hydridodimethylsiloxy)Octasilsesquioxane[(HSiMe2O)8Si8O12; (Q8M8H8)]38
6.7;1.7 Organic-Inorganic Hybrid Materials Prepared from POS: Octasilsesquioxanecontaining Polymers;40
6.7.1;1.7.1 Hybrid Organic-Inorganic Crosslinked Materials Containing POS;40
6.7.2;1.7.2 Star-Shaped Hybrid Organic-Inorganic Materials Containing POS as a Macroinitiator;43
6.8;1.8 Mono-Substituted Polyhedral Oligomeric Silsesquioxane Macromonomers;45
6.8.1;1.8.1 Synthesis of Mono-Substituted Silsesquioxanes by Hydrolysis of Trifunctional Silanes;46
6.8.2;1.8.2 Synthesis of Mono-Substituted Silsesquioxanes by Hydrosilylation;47
6.8.3;1.8.3 Synthesis of Mono-Substituted Silsesquioxanes by Corner-Capping Reactions;49
6.9;1.9 Chemistry of Incompletely Condensed Silsesquioxanes;50
6.9.1;1.9.1 Synthesis of Incompletely Condensed Silsesquioxanes;51
6.9.2;1.9.2 Chemistry of Incompletely Condensed Silsesquioxanes;56
6.9.3;1.9.3 Hybrid Organic-Inorganic Materials Derived from Mono-Substituted POS Monomers;57
6.10;1.10 Summary;61
6.11;1.11 References;62
7;Chapter 2 Preparation and Characterization of Polyhedral Oligosilsesquioxanes;72
7.1;2.1 General Comments;72
7.2;2.2 Synthesis of TnRn Compounds where R = H, Alkyl or Alkenyl ;73
7.2.1;2.2.1 Hydrolysis;73
7.2.1.1;2.2.1.1 T4 and T6 Compounds;73
7.2.1.2;2.2.1.2 T8 Compounds;74
7.2.1.3;2.2.1.3 T10, T12 and Larger Compounds;76
7.2.2;2.2.2 Substitution;76
7.2.3;2.2.3 Cage Rearrangement;78
7.2.4;2.2.4 Modification of R;79
7.2.4.1;2.2.4.1 T8 Compounds;79
7.2.4.2;2.2.4.2 T10 and T12 Compounds;84
7.2.5;2.2.5 Other Synthetic Methods;84
7.2.5.1;2.2.5.1 T6 Compounds;84
7.2.5.2;2.2.5.2 T8 Compounds;85
7.2.5.3;2.2.5.3 T10 and T12 Compounds;85
7.3;2.3 Synthesis of TnRn Compounds where R = Aryl ;86
7.3.1;2.3.1 Hydrolysis;86
7.3.1.1;2.3.1.1 T8 Compounds;86
7.3.1.2;2.3.1.2 T10 and T12 Compounds;87
7.3.2;2.3.2 Modification of R;87
7.3.2.1;2.3.2.1 T8 Compounds;87
7.3.2.2;2.3.2.2 T10 and T12 Compounds;90
7.3.3;2.3.3 Other Synthetic Methods;90
7.4;2.4 Synthesis of Tn Rn Compounds where R =Alkoxy ;91
7.5;2.5 Synthesis of TnRn Compounds whereR = Siloxy;91
7.5.1;2.5.1 Corner Capping;91
7.5.2;2.5.2 Substitution;91
7.5.2.1;2.5.2.1 T8 Compounds;91
7.5.2.2;2.5.2.2 T10, T12, and T14 Compounds;92
7.5.3;2.5.3 Modification of R;92
7.5.3.1;2.5.3.1 T6 Compounds;92
7.5.3.2;2.5.3.2 T8 Compounds;92
7.5.3.3;2.5.3.3 T10 Compounds;95
7.6;2.6 Synthesis of TnRn Compounds where R = Metal Complex ;95
7.6.1;2.6.1 Hydrolysis;95
7.6.2;2.6.2 Substitution;96
7.6.2.1;2.6.2.1 T8 Compounds;96
7.6.2.2;2.6.2.2 T10 Compounds;96
7.6.3;2.6.3 Modification of R;96
7.7;2.7 Synthesis of Miscellaneous TnRn Compounds;99
7.7.1;2.7.1 Hydrolysis;99
7.7.1.1;2.7.1.1 T6 Compounds;99
7.7.1.2;2.7.1.2 T8 Compounds;99
7.7.1.3;2.7.1.3 T10 Compounds;100
7.7.2;2.7.2 Co-Hydrolysis;100
7.7.3;2.7.3 Substitution and Modification of Functional Groups;101
7.7.4;2.7.4 Other Synthetic Methods;101
7.7.4.1;2.7.4.1 T4 Compounds;101
7.7.4.2;2.7.4.2 T8 Compounds;101
7.7.4.3;2.7.4.3 T10 Compounds;102
7.8;2.8 Synthesis of Endohedral T8R8 Compounds;102
7.9;2.9 Introduction to the Physical Properties of POS Compounds;103
7.10;2.10 NMR and EPR Spectroscopy of POS Compounds;103
7.10.1;2.10.1 Solution 29Si NMR Studies;103
7.10.2;2.10.2 Solid State NMR Studies;108
7.10.3;2.10.3 EPR Spectra;110
7.11;2.11 Vibrational Spectra of Polyhedral Oligomeric Silsesquioxane Compounds;110
7.12;2.12 Mass Spectra of POS Compounds;113
7.13;2.13 Electronic Spectra of POS Compounds;115
7.14;2.14 Structural Studies of POS Compounds;116
7.14.1;2.14.1 Single Crystal X-Ray Diffraction Studies;116
7.14.2;2.14.2 Structures Derived from Computational and Gas-Phase Electron Diffraction Studies;120
7.14.3;2.14.3 X-ray Diffraction Studies on Powders, Thin Films, etc.;121
7.14.3.1;2.14.3.1 T8R8 Compounds;122
7.14.3.2;2.14.3.2 T8R7R’ Compounds;123
7.15;2.15 TGA, DSC and Related Studies of POS Compounds;124
7.15.1;2.15.1 T8R8 Compounds (R = H, Alkyl, Vinyl, Aryl or Silyl Derivatives) ;124
7.15.2;2.15.2 T8R8 Compounds (R = Siloxy Derivatives);125
7.15.3;2.15.3 T8R7R’ Compounds;126
7.16;2.16 Microscopy Studies of T8 POS Compounds;127
7.16.1;2.16.1 T8R8 Compounds;127
7.16.2;2.16.2 T8R7R’ Compounds;127
7.17;2.17 X-Ray Photoelectron Spectra of POS Compounds;128
7.18;2.18 Electrochemistry of POS Compounds;128
7.19;2.19 Chromatographic Methods Applied to POS Compounds;129
7.20;2.20 Miscellaneous Physical Properties of POS Compounds;130
7.21;2.21 Acknowledgments;131
7.22;2.22 References;131
8;Chapter 3 Metallasilsesquioxanes: Molecular Analogues of Heterogeneous Catalysts;159
8.1;3.1 Introduction;159
8.2;3.2 Metallasilsesquioxanes;160
8.2.1;3.2.1 Group 4 – Ti, Zr, Hf;160
8.2.2;3.2.2 Group 5 – V;169
8.2.3;3.2.3 Group 6 – Mo;171
8.2.4;3.2.4 Group 8 – Fe;172
8.2.5;3.2.5 Group 12 – Zn;173
8.2.6;3.2.6 Group 13 – Al;174
8.2.7;3.2.7 Group 14 – Si;175
8.2.8;3.2.8 Lanthanides – Nd;177
8.2.9;3.2.9 Hetero-bimetallic Systems;178
8.3;3.3 Phosphasilsesquioxanes as Ligands;180
8.4;3.4 Catalytic Materials Derived From Metalla-Silsesquioxanes;183
8.5;3.5 Conclusions and Future Prospects;186
8.6;3.6 References;187
9;Chapter 4 Polymers and Copolymers Containing Covalently Bonded Polyhedral Oligomeric Silsesquioxanes Moieties;191
9.1;4.1 Introduction;191
9.2;4.2 Synthetic Strategies;192
9.2.1;4.2.1 Free Radical Polymerization;192
9.2.2;4.2.2 Living Radical Polymerization (ATRP, RAFT and NMP);193
9.2.3;4.2.3 Anionic Polymerization;196
9.2.4;4.2.4 Ring-Opening Metathesis Polymerization (ROMP);196
9.2.5;4.2.5 Metallocene-Catalyzed Polymerization;198
9.2.6;4.2.6 Step-Growth Polymerization;199
9.2.7;4.2.7 Grafting;204
9.3;4.3 POS Pendant-Random Copolymers;206
9.3.1;4.3.1 Glass Transition Temperature;206
9.3.2;4.3.2 Mechanical Properties;207
9.3.3;4.3.3 Crystallinity in POS Pendant-Random Copolymers;207
9.4;4.4 POS Pendant-Block Copolymers;210
9.4.1;4.4.1 Diblocks;210
9.4.2;4.4.2 Triblocks;212
9.4.3;4.4.3 Hemitelechelic (‘Tadpole’-Shaped) Polymers;213
9.4.4;4.4.4 Telechelic (Dumbbell-Shaped) Polymers;215
9.5;4.5 POS-Polyimide and POS-Urethanes;216
9.5.1;4.5.1 POS-Polyimide;216
9.5.2;4.5.2 POS-Urethane;217
9.6;4.6 Multifunctional POS in Network or Core Structures;219
9.6.1;4.6.1 Epoxy Networks;219
9.6.2;4.6.2 Other POS Networks;220
9.6.3;4.6.3 POS Star or Core Structures;222
9.7;4.7 Conclusion;223
9.8;4.8 References;224
10;Chapter 5 Polyhedral Oligomeric Silsesquioxanes in Plastics;232
10.1;5.1 Introduction;232
10.2;5.2 POS are Molecules;233
10.3;5.3 POS as Plastics Additives;236
10.4;5.4 POS Solubility;237
10.5;5.5 Effects of POS on Polymer Properties;237
10.5.1;5.5.1 POS Solubilized in the Polymer;238
10.5.2;5.5.2 POS Insoluble Present at Concentrations Above the Solubility Limit;239
10.5.3;5.5.3 POS Chemically Attached to the Polymer;240
10.5.4;5.5.4 POS Network Thermosets;241
10.6;5.6 POS Dispersants;242
10.7;5.7 POS Metal Deactivators;246
10.8;5.8 New Applications and the Future;247
10.9;5.9 Conclusions;248
10.10;5.10 References;248
11;Chapter 6 Fluorinated Polyhedral Oligosilsesquioxane Surfaces and Superhydrophobicity;252
11.1;6.1 Introduction;252
11.2;6.2 Experimental;254
11.2.1;6.2.1 Materials;254
11.2.2;6.2.2 Single Crystal X-Ray Structural Characterization;254
11.2.3;6.2.3 Fluorinated POS Coating and Composite Preparation;255
11.2.3.1;6.2.3.1 Spin Cast Fluorinated POS Coating;255
11.2.3.2;6.2.3.2 Fluorinated POS Solvent Blended Composites with 6F-BP PFCB Aryl Ether Polymer;255
11.2.3.3;6.2.3.3 Fluorinated POS Melt Blended PCTFE;255
11.2.4;6.2.4 Thermo-Mechanical Analysis;256
11.2.5;6.2.5 Microscopy;256
11.2.5.1;6.2.5.1 Atomic Force Microscopy (AFM);256
11.2.5.2;6.2.5.2 Scanning Electron Microscopy (SEM);256
11.2.6;6.2.6 Static and Dynamic Contact Angle;257
11.3;6.3 Results and Discussion;257
11.3.1;6.3.1 Fluorinated POS Synthesis;257
11.3.2;6.3.2 Fluorinated POS Properties;258
11.3.3;6.3.3 POS Fluoropolymers;261
11.3.3.1;6.3.3.1 Dispersion;261
11.3.3.2;6.3.3.2 Melt Processability;264
11.3.3.3;6.3.3.3 Thermo-Mechanical Analysis;265
11.3.3.4;6.3.3.4 Surface Properties;266
11.4;6.4 Conclusions;267
11.5;6.5 Acknowledgments;268
11.6;6.6 References;268
12;Chapter 7 Polyhedral Oligomeric Silsesquioxanes in Electronics and Energy Applications;270
12.1;Introduction;270
12.2;7.1 Polyhedral Oligomeric Silsesquioxanes in Liquid Crystal Systems;270
12.3;7.2 Polyhedral Oligomeric Silsesquioxanes in Electroluminescent (EL) Materials and Light Emitting Devices (LEDs);284
12.3.1;7.2.1 Polyhedral Oligomeric Silsesquioxane End-capped EL Polymers;286
12.3.2;7.2.2 EL Polymers with Pendant Polyhedral Oligomeric Silsesquioxane Groups;287
12.3.3;7.2.3 EL Star Architectures with Polyhedral Oligomeric Silsesquioxane Cores;289
12.3.4;7.2.4 Polyhedral Oligomeric Silsesquioxane Iridium Complexes;293
12.3.5;7.2.5 Physical Blending of Polyhedral Oligomeric Silsesquioxanes into EL Polymers;296
12.4;7.3 Polyhedral Oligomeric Silsesquioxanes in Non-linear Optic (NLO), Optical Limiting (OL) and Laser Applications;297
12.5;7.4 Polyhedral Oligomeric Silsesquioxanes in Lithographic Applications;299
12.6;7.5 Polyhedral Oligomeric Silsesquioxanes in Sensor Systems;305
12.6.1;7.5.1 Fluorophore-Functionalized Polyhedral Oligomeric Silsesquioxanes as Sensors;306
12.6.2;7.5.2 Polyhedral Oligomeric Silsesquioxane Sensors for Gas and Vapor Detection;311
12.6.3;7.5.3 Polyhedral Oligomeric Silsesquioxanes in Conducting Composite and Electrochemical Sensors;315
12.7;7.6 Polyhedral Oligomeric Silsesquioxanes in Fuel Cell Applications;318
12.8;7.7 Polyhedral Oligomeric Silsesquioxanes in Battery Applications;327
12.9;7.8 Polyhedral Oligomeric Silsesquioxanes as Lubricants;331
12.10;7.9 References;332
13;Chapter 8 Polyhedral Oligomeric Silsesquioxanes in Space Applications;349
13.1;8.1 The Space Environment;349
13.2;8.2 Resistance of Siloxane Copolymers to Atomic Oxygen in Low Earth Orbit;352
13.3;8.3 Polyhedral Oligomeric Silsesquioxanes in Space Solar Power Systems;363
13.4;8.4 Summary;379
13.5;8.5 References;380
14;Chapter 9 Biomedical Application of Polyhedral Oligomeric Silsesquioxane Nanoparticles;384
14.1;9.1 Introduction;384
14.2;9.2 Nanocomposites;385
14.3;9.3 Polyhedral Oligomeric Silsesquioxanes;386
14.4;9.4 Biomedical Applications of Polyhedral Oligomeric Silsesquioxane-Containing Polymers;389
14.4.1;9.4.1 Drug Delivery;389
14.4.2;9.4.2 Dental Nanocomposites;392
14.4.3;9.4.3 Biosensors;394
14.4.4;9.4.4 Cardiovascular Implants;395
14.4.4.1;9.4.4.1 Mechanical Properties;397
14.4.4.2;9.4.4.2 Degradative Resistance;398
14.4.4.3;9.4.4.3 Biocompatibility and Biostability;399
14.4.4.4;9.4.4.4 Endothelialization Property;400
14.4.4.5;9.4.4.5 Anti-Thrombogenic Potential;403
14.4.4.6;9.4.4.6 Resistance to Calcifi cation and Fatigue;403
14.4.4.7;9.4.4.7 Reduced In Vitro Infl ammatory Response;404
14.4.5;9.4.5 Breast Implants;405
14.4.6;9.4.6 Coating Material for Quantum Dot Nanocrystals;406
14.4.7;9.4.7 Silver Nanoparticle-Containing Polyhedral Oligosilsesquioxane Polymers;408
14.4.8;9.4.8 Tissue Engineering;409
14.5;9.5 Other Applications;413
14.6;9.6 Future Prospects;413
14.7;9.7 References;414
15;Index;421
16;Abbreviations;434