Dvornic / Owen Silicon-Containing Dendritic Polymers

1. Auflage 2009
ISBN: 978-1-4020-8174-3
Verlag: Springer Netherlands
Format: PDF
Kopierschutz: 1 - PDF Watermark

E-Book, Englisch, Band 2, 428 Seiten

Reihe: Advances in Silicon Science

During the last two decades silicon-containing dendritic polymers have become one of the fastest growing areas of development in polymer science. The eruption of interest in these new polymers stems from their unprecedented molecular architecture, unique resulting properties and the realization that they represent ideal building blocks for chemical nanotechnology. This is the first book to solely focus on silicon-containing dendritic polymers. The contributions of those experts who originally introduced each field or played a major role in its progress are reported. The developments in all major areas of this field are presented from their origins to the present. It is anticipated that this text will become an invaluable guide and vanguard of reference for experienced scientists interested in the fields of polymer and material science, synthetic chemistry, and nanotechnology. It will also serve advanced graduate students either as a source of creative inspiration or as a textbook for appropriate courses.

Autoren/Hrsg.

Dvornic, Petar R.

Owen, Michael J

Inhaltsverzeichnis

1;Preface;6
2;Contents;8
3;Contributors;14
4;The Role of Silicon in Dendritic Polymer Chemistry;17
4.1;1.1 Introduction;17
4.2;1.2 Dendrimers and Hyperbranched Polymers;20
4.2.1;1.2.1 Dendrimers;20
4.2.2;1.2.2 Hyperbranched Polymers;26
4.3;1.3 A Brief Historical Overview of the Main Developments in Dendrimers and Hyperbranched Polymers;29
4.4;1.4 Silicon in Dendritic Polymers;31
4.5;References;34
5;Polysiloxane and Siloxane-Based Dendrimers;37
5.1;2.1 Introduction: Historical Background;37
5.2;2.2 Chemistry of Siloxane Dendrimers;38
5.3;2.3 Peculiarities of Siloxane Dendrimers;41
5.4;2.4 Prospects for Further Development in the Chemistry of Siloxane Dendrimers;44
5.5;References;45
6;Carbosilane Dendrimers;47
6.1;3.1 Introduction;47
6.2;3.2 Synthesis of Carbosilane Dendrimers;48
6.2.1;3.2.1 Core Molecules;49
6.2.2;3.2.2 Interior Generations;54
6.2.3;3.2.3 Peripheral (Corona; End-Groups) Modification;59
6.3;3.3 Carbosilane Dendrimer Characterization;76
6.4;3.4 Properties of Carbosilane Dendrimers ;78
6.4.1;3.4.1 Molecular Dimensions of Carbosilane Dendrimers;78
6.4.2;3.4.2 Dynamics of Carbosilane Dendrimers;82
6.5;References;84
7;Polysilane Dendrimers;91
7.1;4.1 Introduction;91
7.2;4.2 Synthetic Approaches to Polysilane Dendrimers;92
7.2.1;4.2.1 Convergent Methods;92
7.2.2;4.2.2 Divergent Methods;95
7.2.3;4.2.3 Double-Cored Polysilane Dendrimers;97
7.2.4;4.2.4 Functionalized Polysilane Dendrimers;100
7.3;4.3 NMR Spectroscopy of Polysilane Dendrimers;101
7.4;4.4 Crystallography and Conformation of Polysilane Dendrimers;103
7.5;4.5 Electronic Spectra;107
7.6;4.6 Conclusions and Future Outlook;110
7.7;References;111
8;Polycarbosilazane and Related Dendrimers and Hyperbranched Polymers;113
8.1;5.1 Introduction;113
8.2;5.2 Polycarbosilazane Dendrimers;114
8.3;5.3 Polysilazane Dendrimers;115
8.4;5.4 Related Dendrimers;116
8.5;5.5 Hyperbranched Polycarbosilazanes;117
8.6;5.6 Concluding Remarks;118
8.7;References;119
9;Silyl Ether Containing Dendrimers with Cyclic Siloxane Cores;120
9.1;6.1 Introduction;120
9.2;6.2 Siloxane Dendrimers with Cyclic Siloxane Core ( 0G( 4)- Vinyl);121
9.3;6.3 Synthesis of Dendrimers with Si–O–C Units from Cyclic Siloxane Cores;123
9.3.1;6.3.1 General Synthetic Strategy from 0G(4)-Vinyl Core;123
9.3.2;6.3.2 Dendrimers with Organic Functional End-Groups;123
9.3.3;6.3.3 Dendrimers with Triple Bonds;124
9.3.4;6.3.4 “Double-Layered” Dendrimers with Conjugated Branches;125
9.3.5;6.3.5 Ferrocenyl-Functionalized Dendrimers as CO Gas Sensor;127
9.3.6;6.3.6 Water Soluble Dendrimers;127
9.3.7;6.3.7 Dendrimers with Terpyridine Ruthenium Complex End- Groups;129
9.3.8;6.3.8 Dendrimers with Farnesyl End-Groups;129
9.3.9;6.3.9 Diels-Alder Reaction on Dendrimer Periphery;131
9.4;6.4 Dendrimers with Silsesquioxane Core;132
9.5;6.5 Conclusion;133
9.6;References;133
10;Polyhedral Oligomeric Silsesquioxane Dendrimers;135
10.1;7.1 Introduction;135
10.2;7.2 Synthesis of Silsesquioxanes and Silicates ;137
10.2.1;7.2.1 Silsesquioxanes;137
10.2.2;7.2.2 Silicates;138
10.2.3;7.2.3 Functionalizing Silsesquioxanes and Silicates;139
10.3;7.3 Synthesis of POSS and Silicate Dendrimers ;140
10.3.1;7.3.1 POSS Dendrimer Synthesis;140
10.3.2;7.3.2 Silicate Dendrimer Synthesis;143
10.3.3;7.3.3 Characterization;144
10.4;7.4 Applications of POSS and Silicate Dendrimers ;144
10.4.1;7.4.1 Homogeneous Catalysis;144
10.4.2;7.4.2 Electro- and Redox-Active Dendrimers;147
10.4.3;7.4.3 Liquid Crystals;147
10.4.4;7.4.4 Transition Metal Binding;148
10.4.5;7.4.5 POSS-PAMAM Nanocomposites;149
10.4.6;7.4.6 Gene Transfection;150
10.5;7.5 Conclusion;151
10.6;References;151
11;Organometallic Silicon-Containing Dendrimers and Their Electrochemical Applications;154
11.1;8.1 Introduction;154
11.2;8.2 Synthetic Strategies and Redox Properties of Organometallic Silicon- Containing Dendritic Macromolecules;158
11.2.1;8.2.1 Functionalization of Silicon-Based Dendritic Scaffolds with Electroactive Organometallic Moieties;160
11.2.2;8.2.2 Silicon-Based Dendrimers from Organometallic Moieties;176
11.3;8.3 Electrochemical Applications of Ferrocenyl Silicon- Containing Dendritic Molecules ;196
11.3.1;8.3.1 Ferrocenyl Dendrimers with Si–NH Linkages as Redox Sensors for Recognition of Inorganic Anions;196
11.3.2;8.3.2 Ferrocenyl Silicon-Containing Dendrimers as Electron- Transfer Mediators in Amperometric Biosensors;199
11.3.3;8.3.3 Electrocatalytic Oxidation of Ascorbic Acid Mediated by a Ferrocenyl Siloxane- Based Network Polymer;202
11.4;8.4 Concluding Remarks;204
11.5;References;205
12;Carbosilane Dendrimers: Molecular Supports and Containers for Homogeneous Catalysis and Organic Synthesis;210
12.1;9.1 Introduction;210
12.2;9.2 Carbosilane Dendrimers with Covalently Bound Catalysts;214
12.2.1;9.2.1 Synthesis and Structural Aspects of Phosphine-Based Dendrimer Catalysts;214
12.2.2;9.2.2 Catalytic Reactivity of Phosphine-Based Dendrimer Catalysts;216
12.2.3;9.2.3 Synthesis and Structural Aspects of Non-phosphine-Based Dendrimer Catalysts;226
12.2.4;9.2.4 Catalytic Reactivity of Non-phosphine-Based Dendrimer Catalysts;227
12.3;9.3 Supported Organic Synthesis on Soluble Carbosilanes;241
12.4;9.4 Conclusions and Future Outlook;243
12.5;References;245
13;Liquid Crystalline Silicon-Containing Dendrimers with Terminal Mesogenic Groups;249
13.1;10.1 Introduction;249
13.2;10.2 Peculiarities of the Molecular Structure of LC Silicon- Containing Dendrimers;252
13.3;10.3 Polyorganosiloxane Dendrimers with Terminal Mesogenic Groups;253
13.4;10.4 Carbosilane LC Dendrimers;258
13.4.1;10.4.1 Synthesis of Carbosilane LC Dendrimers with Different Molecular Architectures;261
13.4.2;10.4.2 Structural Organization and Phase Behavior of Carbosilane LC Dendrimers;264
13.5;10.5 Chiral Carbosilane LC Dendrimers with Ferroelectric Properties;274
13.6;10.6 Photochromic LC Carbosilane Dendrimers;281
13.6.1;10.6.1 Phase Behavior and Structure;284
13.6.2;10.6.2 Photochemical and Photooptical Properties;286
13.7;10.7 Conclusions and Future Outlook;291
13.8;References;293
14;Silicon-Organic Dendrimers;296
14.1;11.1 Introduction;296
14.2;11.2 PAMAMOS: PAMAM Dendrimers with Silicon- Containing End- Groups;298
14.3;11.3 PAMAMOS Multi-arm Star Polymers;302
14.4;11.4 PAMAMOS Networks;305
14.5;11.5 PAMAMOS Networks Nanocomplexes and Nanocomposites;309
14.6;11.6 Copolymeric PAMAMOS Dendrimers;313
14.7;11.7 Other Silicon-Organic Dendrimers ;317
14.7.1;11.7.1 Dendrimers with Silicon in the Core;317
14.7.2;11.7.2 Dendrimers with Silicon in Their Interiors;319
14.7.3;11.7.3 Dendrimers (Other than PAMAMOS) with Silicon in the End- Groups;322
14.8;References;323
15;Hyperbranched Polycarbosilanes via Nucleophilic Substitution Reactions;326
15.1;12.1 Introduction;326
15.2;12.2 Hyperbranched Polycarbosilanes from AB3 Monomers;328
15.2.1;12.2.1 From Chloromethyltrichlorosilane;328
15.2.2;12.2.2 From 2-Bromo-5-trimethoxysilylthiophene;336
15.2.3;12.2.3 From 2-Bromoethyltrichlorosilane;338
15.2.4;12.2.4 From 3- or 4-Bromophenyltriethoxysilane;338
15.2.5;12.2.5 From Other Monomers;339
15.3;12.3 Hyperbranched Polycarbosilanes from AB2 Monomers;342
15.3.1;12.3.1 From Chloromethylmethyldichlorosilane;342
15.3.2;12.3.2 From ClCH2CH=CHSiMeCl2 and CH2=C(CH2Cl)SiMeCl;344
15.3.3;12.3.3 Other Monomers;346
15.4;12.4 Hyperbranched Polycarbosilanes from A2B2-Type Monomers;347
15.5;12.5 Hyperbranched Co-Polycarbosilanes;349
15.5.1;12.5.1 Co-Polycarbosilanes from Phenyltrichlorosilane, Diphenyldichlorosilane and Dibromomethane;349
15.5.2;12.5.2 Copolymer from ClCH2Si(OMe)1.75 Cl1.25 and ClCH2SiMeCl;351
15.5.3;12.5.3 Copolymer from Cl2CHSiMeCl2 and ClCH2Si(OMe)1.75Cl1.25;352
15.6;12.6 Conclusion and Future Outlook;353
15.7;References;353
16;Hyperbranched Polycarbosilanes and Polycarbosiloxanes via Hydrosilylation Polymerization;355
16.1;13.1 Introduction;355
16.2;13.2 Hydrosilylation;356
16.3;13.3 Synthesis and Characterization of Silicon-Containing Hyperbranched Polymers;359
16.4;13.4 Polycarbosilanes ;361
16.4.1;13.4.1 General Synthetic Strategy;361
16.4.2;13.4.2 Functionalization;367
16.4.3;13.4.3 Block Copolymers;371
16.5;13.5 Polycarbosiloxanes ;373
16.5.1;13.5.1 General Synthetic Strategy;373
16.5.2;13.5.2 Polymer Modification and Application;377
16.6;13.6 Polyalkoxysilanes;380
16.7;13.7 Polycarbosilazanes;381
16.8;13.8 Summary and Perspectives;382
16.9;References;383
17;Rearranging Hyperbranched Silyl Ether Polymers;386
17.1;14.1 Introduction;386
17.2;14.2 Monomer Synthesis;388
17.3;14.3 Polymerization Reactions;390
17.4;14.4 Rearrangement Reactions;393
17.5;14.5 Possible Applications;395
17.6;References;397
18;Cyclization Issues in Silicon-Containing Hyperbranched Polymers;399
18.1;15.1 Introduction;399
18.2;15.2 Intramolecular Cyclization of the Monomer;400
18.3;15.3 Intramolecular Cyclization of Oligomers;401
18.4;15.4 Controlling Cyclization;404
18.4.1;15.4.1 Controlling Monomer Cyclization;404
18.4.2;15.4.2 Controlling Cyclization of Oligomers;406
18.5;15.5 Concluding Remarks;407
18.6;References;407
19;Hyperbranched Silicon-Containing Polymers via Bimolecular Non- linear Polymerization;409
19.1;16.1 Introduction;409
19.2;16.2 Historical Development of Bimolecular Non-linear Polymerization;410
19.3;16.3 Theory of Ax + By Bimolecular Non-linear Polymerization;412
19.4;16.4 Bimolecular Non-linear Polymerization by Hydrosilylation;415
19.5;16.5 Bimolecular Non-linear Polymerization by Nucleophilic Substitution Reactions;421
19.6;16.6 Siliconized Hyperbranched Polymers by BMNLP;423
19.7;16.7 Conclusions and Future Outlook;425
19.8;References;426
20;Index;428