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[½»Á÷] Silicon-Containing Dendritic Polymers (2009ÐÂÊ飬Áª½áÒѸüÐÂ)

1 The Role of Silicon in Dendritic Polymer Chemistry ........................... 1
Petar R. Dvornic and Michael J. Owen

2 Polysiloxane and Siloxane-Based Dendrimers ...................................... 21
Aziz Muzafarov and Evgenij Rebrov

3 Carbosilane Dendrimers ......................................................................... 31
Jacques Roovers and Jianfu Ding

4 Polysilane Dendrimers ............................................................................. 75
Masato Nanjo and Akira Sekiguchi

5 Polycarbosilazane and Related Dendrimers
and Hyperbranched Polymers ................................................................ 97
David Y. Son

6 Silyl Ether Containing Dendrimers with Cyclic Siloxane Cores ......... 105
Chungkyun Kim

7 Polyhedral Oligomeric Silsesquioxane Dendrimers.............................. 121
Katherine J. Haxton and Russell E. Morris

8 Organometallic Silicon-Containing Dendrimers
and Their Electrochemical Applications ................................................ 141
Isabel Cuadrado

9 Carbosilane Dendrimers: Molecular Supports
and Containers for Homogeneous Catalysis
and Organic Synthesis ........................................................................... 197
Maaike Wander, Robertus J.M. Klein Gebbink, and Gerard van Koten

10 Liquid Crystalline Silicon-Containing Dendrimers
with Terminal Mesogenic Groups......................................................... 237
Valery Shibaev and Natalia Boiko
10.1 Introduction ................................................................................... 237
10.2 Peculiarities of the Molecular Structure
of LC Silicon-Containing Dendrimers .......................................... 240
10.3 Polyorganosiloxane Dendrimers with Terminal
Mesogenic Groups ........................................................................ 241
10.4 Carbosilane LC Dendrimers .......................................................... 246
10.4.1 Synthesis of Carbosilane LC Dendrimers
with Different Molecular Architectures .......................... 249
10.4.2 Structural Organization and Phase Behavior
of Carbosilane LC Dendrimers ....................................... 252
10.5 Chiral Carbosilane LC Dendrimers with Ferroelectric Properties 262
10.6 Photochromic LC Carbosilane Dendrimers .................................. 269
10.6.1 Phase Behavior and Structure ......................................... 272
10.6.2 Photochemical and Photooptical Properties .................... 274
10.7 Conclusions and Future Outlook ................................................... 279
11 Silicon-Organic Dendrimers ................................................................. 285
Petar R. Dvornic, Michael J. Owen, and Rakesh Sachdeva
11.1 Introduction ................................................................................... 285
11.2 PAMAMOS: PAMAM Dendrimers with Silicon-Containing
End-Groups ................................................................................... 287
11.3 PAMAMOS Multi-arm Star Polymers .......................................... 291
11.4 PAMAMOS Networks .................................................................. 294
11.5 PAMAMOS Networks Nanocomplexes and Nanocomposites ..... 298
11.6 Copolymeric PAMAMOS Dendrimers ......................................... 302
11.7 Other Silicon-Organic Dendrimers ............................................... 306
11.7.1 Dendrimers with Silicon in the Core ............................... 306
11.7.2 Dendrimers with Silicon in Their Interiors ..................... 308
11.7.3 Dendrimers (Other than PAMAMOS) with Silicon
in the End-Groups ........................................................... 311
12 Hyperbranched Polycarbosilanes via Nucleophilic
Substitution Reactions ........................................................................... 315
Leonard Interrante and Qionghua Shen
12.1 Introduction ................................................................................... 315
12.2 Hyperbranched Polycarbosilanes from AB3 Monomers ............... 317
12.2.1 From Chloromethyltrichlorosilane .................................. 317
12.2.2 From 2-Bromo-5-trimethoxysilylthiophene .................... 325
12.2.3 From 2-Bromoethyltrichlorosilane .................................. 327
12.2.4 From 3- or 4-Bromophenyltriethoxysilane ..................... 327
12.2.5 From Other Monomers .................................................... 328
12.3 Hyperbranched Polycarbosilanes from AB2 Monomers ............... 331
12.3.1 From Chloromethylmethyldichlorosilane ....................... 331
12.3.2 From ClCH2CH=CHSiMeCl2
and CH2=C(CH2Cl)SiMeCl2............................................ 333
12.3.3 Other Monomers ............................................................. 335
12.4 Hyperbranched Polycarbosilanes from A2B2-Type Monomers ..... 336
12.5 Hyperbranched Co-Polycarbosilanes ............................................ 338
12.5.1 Co-Polycarbosilanes from Phenyltrichlorosilane,
Diphenyldichlorosilane and Dibromomethane ............... 338
12.5.2 Copolymer from ClCH2Si(OMe)1.75Cl1.25
and ClCH2SiMeCl2 .......................................................... 340
12.5.3 Copolymer from Cl2CHSiMeCl2
and ClCH2Si(OMe)1.75Cl1.25 ............................................. 341
12.6 Conclusion and Future Outlook .................................................... 342
13 Hyperbranched Polycarbosilanes and Polycarbosiloxanes
via Hydrosilylation Polymerization ...................................................... 345
Hanna Sch¨¹le and Holger Frey
13.1 Introduction ................................................................................... 345
13.2 Hydrosilylation .............................................................................. 346
13.3 Synthesis and Characterization of Silicon-Containing
Hyperbranched Polymers .............................................................. 349
13.4 Polycarbosilanes ............................................................................ 351
13.4.1 General Synthetic Strategy .............................................. 351
13.4.2 Functionalization ............................................................. 357
13.4.3 Block Copolymers ........................................................... 361
13.5 Polycarbosiloxanes ........................................................................ 363
13.5.1 General Synthetic Strategy .............................................. 363
13.5.2 Polymer Modification and Application ........................... 367
13.6 Polyalkoxysilanes .......................................................................... 370
13.7 Polycarbosilazanes ........................................................................ 371
13.8 Summary and Perspectives ............................................................ 372
14 Rearranging Hyperbranched Silyl Ether Polymers ........................... 377
Daniel Graiver
14.1 Introduction ................................................................................... 377
14.2 Monomer Synthesis ....................................................................... 379
14.3 Polymerization Reactions.............................................................. 381
14.4 Rearrangement Reactions.............................................................. 384
14.5 Possible Applications .................................................................... 386
15 Cyclization Issues in Silicon-Containing
Hyperbranched Polymers...................................................................... 391
David Y. Son
15.1 Introduction ................................................................................... 391
15.2 Intramolecular Cyclization of the Monomer ................................. 392
15.3 Intramolecular Cyclization of Oligomers...................................... 393
15.4 Controlling Cyclization ................................................................. 396
15.4.1 Controlling Monomer Cyclization .................................. 396
15.4.2 Controlling Cyclization of Oligomers ............................. 398
15.5 Concluding Remarks ..................................................................... 399
16 Hyperbranched Silicon-Containing Polymers
via Bimolecular Non-linear Polymerization ........................................ 401
Petar R. Dvornic and Dale J. Meier
16.1 Introduction ................................................................................... 401
16.2 Historical Development of Bimolecular
Non-linear Polymerization ............................................................ 402
16.3 Theory of Ax + By Bimolecular Non-linear Polymerization ......... 404
16.4 Bimolecular Non-linear Polymerization by Hydrosilylation ........ 407
16.4.1 Hyperbranched Polycarbosilanes
and Polycarbosiloxanes ................................................... 408
16.4.2 Hyperbranched Polymer Networks ................................. 408
16.4.3 Perfluorinated Hyperbranched Polycarbosiloxanes ........ 411
16.4.4 Hyperbranched Polycarbosiloxanes with Latent
Functionalities ................................................................. 412
16.5 Bimolecular Non-linear Polymerization by Nucleophilic
Substitution Reactions ................................................................... 413
16.5.1 Hyperbranched Silarylenesiloxanes ................................ 413
16.5.2 Hyperbranched Polysiloxanes ......................................... 414
16.6 Siliconized Hyperbranched Polymers by BMNLP ....................... 415
16.7 Conclusions and Future Outlook ................................................... 417


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