Silicon-containing Dendritic Polymers

by Dvornic, Petar R.; Owen, Michael J.

• ISBN13: 9781402081736
• ISBN10: 1402081731
• Format: Hardcover
• Copyright: 2009-03-06
• Publisher: Springer Verlag

Summary

This is the first book of its kind to solely focus on silicon-containing dendritic polymers. The contributions of those experts who either originally introduced each field or who played a major role in its progress are reported. The developments in each of the major areas of this field are presented from their origins to the present.

Table of Contents

The Role of Silicon in Dendritic Polymer Chemistry	p. 1
Introduction	p. 1
Dendrimers and Hyperbranched Polymers	p. 4
Dendrimers	p. 4
Hyperbranched Polymers	p. 10
A Brief Historical Overview of the Main Developments in Dendrimers and Hyperbranched Polymers	p. 13
Silicon in Dendritic Polymers	p. 15
Polysiloxane and Siloxane-Based Dendrimers	p. 21
Introduction: Historical Background	p. 21
Chemistry of Siloxane Dendrimers	p. 22
Peculiarities of Siloxane Dendrimers	p. 25
Prospects for Further Development in the Chemistry of Siloxane Dendrimers	p. 28
Carbosilane Dendrimers	p. 31
Introduction	p. 31
Synthesis of Carbosilane Dendrimers	p. 32
Core Molecules	p. 33
Interior Generations	p. 38
Peripheral (Corona; End-Groups) Modification	p. 43
Carbosilane Dendrimer Characterization	p. 60
Properties of Carbosilane Dendrimers	p. 62
Molecular Dimensions of Carbosilane Dendrimers	p. 62
Dynamics of Carbosilane Dendrimers	p. 66
Polysilane Dendrimers	p. 75
Introduction	p. 75
Synthetic Approaches to Polysilane Dendrimers	p. 76
Convergent Methods	p. 76
Divergent Methods	p. 79
Double-Cored Polysilane Dendrimers	p. 81
Functionalized Polysilane Dendrimers	p. 84
NMR Spectroscopy of Polysilane Dendrimers	p. 85
Crystallography and Conformation of Polysilane Dendrimers	p. 87
Electronic Spectra	p. 91
Conclusions and Future Outlook	p. 94
Polycarbosilazane and Related Dendrimers and Hyperbranched Polymers	p. 97
Introduction	p. 97
Polycarbosilazane Dendrimers	p. 98
Polysilazane Dendrimers	p. 99
Related Dendrimers	p. 100
Hyperbranched Polycarbosilazanes	p. 101
Concluding Remarks	p. 102
Silyl Ether Containing Dendrimers with Cyclic Siloxane Cores	p. 105
Introduction	p. 105
Siloxane Dendrimers with Cyclic Siloxane Core (0G(4)-Vinyl)	p. 106
Synthesis of Dendrimers with Si-O-C Units from Cyclic Siloxane Cores	p. 108
General Synthetic Strategy from 0G(4)-Vinyl Core	p. 108
Dendrimers with Organic Functional End-Groups	p. 108
Dendrimers with Triple Bonds	p. 109
"Double-Layered" Dendrimers with Conjugated Branches	p. 110
Ferrocenyl-Functionalized Dendrimers as CO Gas Sensor	p. 112
Water Soluble Dendrimers	p. 112
Dendrimers with Terpyridine Ruthenium Complex End-Groups	p. 114
Dendrimers with Farnesyl End-Groups	p. 114
Diels-Alder Reaction on Dendrimer Periphery	p. 116
Dendrimers with Silsesquioxane Core	p. 117
Conclusion	p. 118
Polyhedral Oligomeric Silsesquioxane Dendrimers	p. 121
Introduction	p. 121
Synthesis of Silsesquioxanes and Silicates	p. 123
Silsesquioxanes	p. 123
Silicates	p. 124
Functionalizing Silsesquioxanes and Silicates	p. 125
Synthesis of POSS and Silicate Dendrimers	p. 126
POSS Dendrimer Synthesis	p. 126
Silicate Dendrimer Synthesis	p. 129
Characterization	p. 130
Applications of POSS and Silicate Dendrimers	p. 130
Homogeneous Catalysis	p. 130
Electro- and Redox-Active Dendrimers	p. 133
Liquid Crystals	p. 133
Transition Metal Binding	p. 134
POSS-PAMAM Nanocomposites	p. 135
Gene Transfection	p. 136
Conclusion	p. 137
Organometallic Silicon-Containing Dendrimers and Their Electrochemical Applications	p. 141
Introduction	p. 141
Synthetic Strategies and Redox Properties of Organometallic Silicon-Containing Dendritic Macromolecules	p. 145
Functionalization of Silicon-Based Dendritic Scaffolds with Electroactive Organometallic Moieties	p. 147
Silicon-Based Dendrimers from Organometallic Moieties	p. 163
Electrochemical Applications of Ferrocenyl Silicon-Containing Dendritic Molecules	p. 183
Ferrocenyl Dendrimers with Si-NH Linkages as Redox Sensors for Recognition of Inorganic Anions	p. 183
Ferrocenyl Silicon-Containing Dendrimers as Electron-Transfer Mediators in Amperometric Biosensors	p. 186
Electrocatalytic Oxidation of Ascorbic Acid Mediated by a Ferrocenyl Siloxane-Based Network Polymer	p. 189
Concluding Remarks	p. 191
Carbosilane Dendrimers: Molecular Supports and Containers for Homogeneous Catalysis and Organic Synthesis	p. 197
Introduction	p. 197
Carbosilane Dendrimers with Covalently Bound Catalysts	p. 201
Synthesis and Structural Aspects of Phosphine-Based Dendrimer Catalysts	p. 201
Catalytic Reactivity of Phosphine-Based Dendrimer Catalysts	p. 203
Synthesis and Structural Aspects of Non-phosphine-Based Dendrimer Catalysts	p. 213
Catalytic Reactivity of Non-phosphine-Based Dendrimer Catalysts	p. 214
Supported Organic Synthesis on Soluble Carbosilanes	p. 228
Conclusions and Future Outlook	p. 230
Liquid Crystalline Silicon-Containing Dendrimers with Terminal Mesogenic Groups	p. 237
Introduction	p. 237
Peculiarities of the Molecular Structure of LC Silicon-Containing Dendrimers	p. 240
Polyorganosiloxane Dendrimers with Terminal Mesogenic Groups	p. 241
Carbosilane LC Dendrimers	p. 246
Synthesis of Carbosilane LC Dendrimers with Different Molecular Architectures	p. 249
Structural Organization and Phase Behavior of Carbosilane LC Dendrimers	p. 252
Chiral Carbosilane LC Dendrimers with Ferroelectric Properties	p. 262
Photochromic LC Carbosilane Dendrimers	p. 269
Phase Behavior and Structure	p. 272
Photochemical and Photooptical Properties	p. 274
Conclusions and Future Outlook	p. 279
Silicon-Organic Dendrimers	p. 285
Introduction	p. 285
PAMAMOS: PAMAM Dendrimers with Silicon-Containing End-Groups	p. 287
PAMAMOS Multi-arm Star Polymers	p. 291
PAMAMOS Networks	p. 294
PAMAMOS Networks Nanocomplexes and Nanocomposites	p. 298
Copolymeric PAMAMOS Dendrimers	p. 302
Other Silicon-Organic Dendrimers	p. 306
Dendrimers with Silicon in the Core	p. 306
Dendrimers with Silicon in Their Interiors	p. 308
Dendrimers (Other than PAMAMOS) with Silicon in the End-Groups	p. 311
Hyperbranched Polycarbosilanes via Nucleophilic Substitution Reactions	p. 315
Introduction	p. 315
Hyperbranched Polycarbosilanes from AB3 Monomers	p. 317
From Chloromethyltrichlorosilane	p. 317
From 2-Bromo-5-trimethoxysilylthiophene	p. 325
From 2-Bromoethyltrichlorosilane	p. 327
From 3- or 4-Bromophenyltriethoxysilane	p. 327
From Other Monomers	p. 328
Hyperbranched Polycarbosilanes from AB2 Monomers	p. 331
From Chloromethylmethyldichlorosilane	p. 331
From CICH2 CH=CHSiMeCl2 and CH2=C(CH2Cl)SiMeCl2	p. 333
Other Monomers	p. 335
Hyperbranched Polycarbosilanes from A2B2-Type Monomers	p. 336
Hyperbranched Co-Polycarbosilanes	p. 338
Co-Polycarbosilanes from Phenyltrichlorosilane, Diphenyldichlorosilane and Dibromomethane	p. 338
Copolymer from ClCH2Si(OMe)1.75Cl1.25 and ClCH2SiMeCl2	p. 340
Copolymer from Cl2CHSiMeCl2 and ClCH2Si(OMe)1.75Cl1.25	p. 341
Conclusion and Future Outlook	p. 342
Hyperbranched Polycarbosilanes and Polycarbosiloxanes via Hydrosilylation Polymerization	p. 345
Introduction	p. 345
Hydrosilylation	p. 346
Synthesis and Characterization of Silicon-Containing Hyperbranched Polymers	p. 349
Polycarbosilanes	p. 351
General Synthetic Strategy	p. 351
Functionalization	p. 357
Block Copolymers	p. 361
Polycarbosiloxanes	p. 363
General Synthetic Strategy	p. 363
Polymer Modification and Application	p. 367
Polyalkoxysilanes	p. 370
Polycarbosilazanes	p. 371
Summary and Perspectives	p. 372
Rearranging Hyperbranched Silyl Ether Polymers	p. 377
Introduction	p. 377
Monomer Synthesis	p. 379
Polymerization Reactions	p. 381
Rearrangement Reactions	p. 384
Possible Applications	p. 386
Cyclization Issues in Silicon-Containing Hyperbranched Polymers	p. 391
Introduction	p. 391
Intramolecular Cyclization of the Monomer	p. 392
Intramolecular Cyclization of Oligomers	p. 393
Controlling Cyclization	p. 396
Controlling Monomer Cyclization	p. 396
Controlling Cyclization of Oligomers	p. 398
Concluding Remarks	p. 399
Hyperbranched Silicon-Containing Polymers via Bimolecular Non-linear Polymerization	p. 401
Introduction	p. 401
Historical Development of Bimolecular Non-linear Polymerization	p. 402
Theory of Ax + By Bimolecular Non-linear Polymerization	p. 404
Bimolecular Non-linear Polymerization by Hydrosilylation	p. 407
Hyperbranched Polycarbosilanes and Polycarbosiloxanes	p. 408
Hyperbranched Polymer Networks	p. 408
Perfluorinated Hyperbranched Polycarbosiloxanes	p. 411
Hyperbranched Polycarbosiloxanes with Latent Functionalities	p. 412
Bimolecular Non-linear Polymerization by Nucleophilic Substitution Reactions	p. 413
Hyperbranched Silarylenesiloxanes	p. 413
Hyperbranched Polysiloxanes	p. 414
Siliconized Hyperbranched Polymers by BMNLP	p. 415
Conclusions and Future Outlook	p. 417
Index	p. 421
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