Macromolecules Containing Metal and Metal-Like Elements, Group IVA Polymers

, by Abd-El-Aziz, Alaa S.; Carraher, Charles E.; Pittman, Charles U.; Zeldin, Martel

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ISBN: 9780471682387 | 0471682381
Cover: Hardcover
Copyright: 3/17/2005

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This series provides a useful, applications-oriented forum for the next generation of macromolecules and materials. Volume 4 provides useful descriptions of Group IV metals and their applications, including silicon-, organogermanium-, organotin-, and organolead-containing polymers. A high-quality team of macromolecular experts from around the world have put together these leading macromolecule titles.

Preface

Series Preface

xvii

1. Overview-Group IVA Polymers

(6)

Charles E. Carraher, Jr., Charles U. Pittman, Jr., Martel Zeldin, and Alaa S. Abd-El-Aziz

I. Introduction

(2)

II. Group IV Polymers

(1)

III. References

(2)

2. Hyperbranched Poly(silylenearylene)s

(30)

Ronghua Zheng, Hongchen Dong, and Ben Zhong Tang

I. Introduction

(2)

II. Results and Discussion

(17)

A. Monomer Synthesis

(1)

B. Polymerization Behaviors

(2)

C. Structural Characterizations

(11)

D. Polymer Properties

(3)

III. Conclusions

(1)

IV. Experimental Section

(8)

A. Materials and Instruments

(1)

B. Synthesis of (4-Bromophenylethynyl)- trimethylsilane

(1)

C. Synthesis of (4-Bromo-3-methylphenylethynyl)- trimethylsilane

(1)

D. Synthesis of (4-Bromo-2, 5-dimethylphenylethynyl)- trimethylsilane

(1)

E. Synthesis of Bis[4-(2-trimethylsilyethynyl)phenyl]- dimethylsilane

(1)

F. Synthesis of Bis[4-(2-trimethylsilyethynyl)phenyl]- methylphenylsilane

(1)

G. Synthesis of Bis[4-(2-trimethylsilyethynyl)phenyl]- diphenylsilane

(1)

H. Synthesis of Bis[2-methyl-4-(2-trimethylsilylethynyl)-phenyl]dimethylsilane

(1)

L Synthesis of Bis[2,5-dimethyl-4-(2-trimethylsilylethynyl)- phenyl]dimethylsilane

(1)

J. Synthesis of Bis(4-ethynylphenyl)dimethylsilane

(1)

K. Synthesis of Bis(4-ethynylphenyl)methylphenylsilane

(1)

L. Synthesis of Bis(4-ethynylphenyl)diphenylsilane

(1)

M. Synthesis of Bis(4-ethynyl-2-methylphenyl)- dimethylsilane

(1)

N. Synthesis of Bis(2,5-dimethyl-4-ethynylphenyl)- dimethylsilane

(1)

O. Diyne Polycyclotrimerization

(1)

P. Polymer Characterization

(1)

Q. Synthesis of Model Compounds 1,3,5- and 1,2,4- Triphenylbenzenes

(1)

R. Decomposition of Hyperbranched Polymers

(1)

S. Structural Simulation

(1)

V. Acknowledgments

(1)

VI. References

(1)

3. Silole-Containing Conjugated Polymers

(14)

Jacky W.Y. Lam, Junwu Chen, Hongchen Dong, and Ben Zhong Tang

I. Introduction

(1)

II. Polymer Syntheses

(3)

III. Thermal Stability

(1)

IV. Photoluminescence

(2)

V. Electroluminescence

(3)

VI. Optical Limiting

(1)

VII. Conclusions

(1)

VIII. Acknowledgments

(1)

IX. References

(3)

4. Silica Polyamine Composites: Advanced Materials for Metal Ion Recovery and Remediation

(28)

Edward Rosenberg

I. Introduction

(3)

II. Relationships between Composite Characteristics and the Starting Materials Used

(3)

A. Wide-Pore Amorphous Silica

(1)

B. Particle Size and Back Pressure

(1)

C. Capacity, Longevity, and Polymer Molecular Weight

(1)

III. Comparison with Other Resin Technologies

(3)

IV. Structural Considerations

(5)

A. The Nature of the Polymer Graft to the Silica Surface

(1)

B. Polymer Structure and Metal Ion Coordination

(2)

C. Molecular Modeling Studies

(2)

V. Applications

(10)

A. Metal Chromatography: Separation and Concentration of Multicomponent Metal Mixture from Acid Mine Drainage

(2)

B. Selective Recovery of Copper from Solvent Extraction Circuit Waste Streams of Acid Mine Leaches

(3)

C. Separation of Cobalt and Copper Using Two Different Polyamine Composites in Tandem Columns

(1)

D. Removal of Mercury from Waste Solutions Using Sulfur-Modified Silica-Polyamine Composites

(4)

VI. Future Work

(1)

VII. Acknowledgments

(1)

VIII. References

(2)

5. Polyhedral Oligomeric Silsesquioxane (POSS) Polymers, Copolymers, and Resin Nanocomposites

(54)

Guizhi Li and Charles U. Pittman, Jr

I. Introduction

(2)

II. Synthesis of Polyhedral Oligomeric Silsesquioxanes

(4)

A. Monofunctional POSS Synthesis

(1)

B. Multifunctional POSS Synthesis

(2)

III. POSS Polymers and Copolymers (Thermoplastics)

(20)

A. Styryl-POSS Polymers, Copolymers, and Nanocomposites

(6)

B. Methacrylate-POSS Polymers, Copolymers, and Nanocomposites

(5)

C. Norbornenyl-POSS Copolymers and Nanocomposites

(6)

D. POSS-Olefin Copolymers and Nanocomposites

104

(1)

E. Siloxane-POSS Copolymers

105

(1)

IV. Crosslinked POSS-Containing Resins and Materials

106

(17)

A. Vinyl Ester, Epoxy, and Phenolic Resins Containing POSS

108

(7)

B. Dicyclopentadiene Resins Containing POSS

115

(2)

C. Styrene and Methyl Methacrylates Resins Containing POSS

117

(6)

V. Other Applications

123

(3)

VI. Summary

126

(1)

VII. Acknowledgments

126

(1)

VIII. References

127

(6)

6. Silica- and Silsesquioxane-Containing Polymer Nanohybrids

133

(28)

Mohammad A. Wahab, Il Kim, and Chang-Sik Ha

I. Introduction

134

(1)

II. Polymer-Silica or Polymer-Silsesquioxane Nanohybrids

135

(8)

A. Key Parameters for Forming Nanohybrids

135

(3)

B. The Sol-Gel Method and Its Related Parameters

138

(2)

C. Polymer-Silica Nanohybrids

140

(1)

D. Polymer-Silsesquioxane (SSQ) Nanohybrids

140

(2)

E. Other Metal Oxide or Metal-Like Materials Containing Polymer Nanohybrids

142

(1)

III. Polyimide-Silica or Polyimide-Silsesquioxane Nanohybrids

143

(13)

A. Polyimide

143

(1)

B. Polyimide-Silica Nanohybrids Their Characterization and Properties

143

(8)

C. Polyimide-Silsesquioxane Nanohybrids-Their Characterization and Properties

151

(3)

D. Polyimide-Silica-Titania Nanohybrids

154

(2)

IV. Conclusions

156

(1)

V. Acknowledgments

157

(1)

VI. References

157

(4)

7. Siloxane Elastomers and Copolymers

161

(42)

Sakuntala Chatterjee Ganguly

Part 1. Siloxane-Divinylbenzene Copolymers as Elastomers

163

(12)

I. Introduction

163

(1)

A. Silicone Elastomers by Radical Polymerization

163

(1)

B. Synthesis of Silicone Elastomers by Combining Radical Polymerization and Hydrosilation

166

(1)

C. Synthesis of Silicone Elastomers by Polycondensation Reaction

167

(1)

D. Synthesis of Silicone Elastomers by Side-Chain and Main-Chain Hydrosilation Reactions

168

(3)

II. Experimental Section

171

(1)

A. Materials and Instruments

171

(1)

B. Synthesis of Poly(tetramethyldisiloxane-divinylbenzene) (PTMS-DVB)

171

(1)

III. Results and Discussions

171

(3)

IV. Conclusions

174

(1)

Part 2. Polyviologen and Siloxane-Based Polyviologen Copolymers

175

(8)

I. Introduction

175

(1)

A. Polyviologen Based on 4,4'Bipyridinium Salts

176

(1)

B. Miscellaneous Polyviologens

176

(1)

C. Modified Route to Pyridino-Terminated Oligo-(dimethylsiloxane)

178

(1)

D. Alternate Viologen Polymers from Vinylbenzyl Chloride-Modified Tetramethyldisiloxane and 4,4'-Bipyridine

179

(1)

II. Experimental Section

180

(1)

A. Materials and Instruments

180

(1)

B. Synthesis of Bis(4-Chloromethylphenyl)tetramethyl-disiloxane (BCTD)

181

(1)

C. Synthesis of Viologen Polymer from BCTD and 4,4'-Bipyridine

181

(1)

III. Results and Discussions

181

(1)

IV Conclusions

182

(1)

Part 3. Siloxane-Based Polyurethane Copolymers

183

(21)

I. Introduction

183

(1)

A. Blends of Polysiloxane with Poly(etherurethane) and Blends of Polydimethylsiloxane with Thermoplastic Polyurethane-True and Semi-Interpenetrating Networks of Silicone-Urethanes

184

(1)

B. Siloxane Groups and Urethanes Linking Units into PEO

185

(1)

C. Side-Chain Polyurethane Based on Polysiloxanes with Pendant Primarily Alcohol and Quaternary Ammonium Groups

185

(1)

D. End-Chain Silicone-Modified Segmented Polyurethane Membrane as Blood-Compatible Ion-Selective Electrode

186

(1)

E. Polyurethane Containing Side-Chain Polyhedral Oligometric Silsesquioxanes (POSS)

187

(1)

F. Diphenylsilanediol-Based Polyurethanes

187

(1)

G. Siloxane-Urethane Containing Block Copolymers

188

(1)

H. Polyurethane Modified with an Aminoethylaminopropyl-Substituted Polydimethylsiloxane

192

(1)

I. Synthesis of Waterborne Polyurethane Modified with an Aminoethylaminopropyl-Substituted Polydimethylsiloxane

193

(1)

J. Alternate Siloxane-Urethane Copolymer by Three-Step Reaction

194

(2)

II. Experimental Section

196

(1)

A. Materials and Instruments

196

(1)

B. Synthesis of Bis(3-trimethylsiloxypropyl)tetramethyl Disiloxane (BTTD) from Allyloxytrimethylsilane

197

(1)

C. Synthesis of Bis(3-hydroypropyl)tetramethyl Disiloxane (BHTD)

197

(1)

D. Synthesis of Siloxane-Urethane Copolymer from BHTD and 2,5-TDI

197

(1)

III. Results and Discussions

197

(2)

IV Acknowledgments

199

(1)

V References

199

(4)

8. Bioinspired Silica Synthesis

203

(22)

Siddharth V. Patwardhan and Stephen J. Clarson

I. Introduction

204

(4)

A. Silica

204

(1)

B. Silica: Existence, Solubility, and Synthesis

204

(1)

i. Silica Synthesis by Sol-Gel Processing

206

(1)

a. Hydrolysis

206

(1)

b. Condensation

206

(1)

ii. Silica Particle Synthesis

207

(1)

C. Biosilica: Existence and Importance

207

(1)

II. Biosilicification and Protein Interactions

208

(3)

A. Diatoms

208

(2)

B. Grasses

210

(1)

C. Sponges

211

(1)

III. Bioinspired and Biomimetic Synthesis: The Use of Poly(allylamine Hydrochloride)

211

(5)

A. Synthesis of Spherical Silica Particles

212

(1)

B. Synthesis of Nonspherical Silica Structures

213

(1)

C. Synthesis Using a Mixture of Macromolecules

213

(1)

D. Electrostatically Self-Assembled Bilayers of PAAcid and PAH

214

(1)

E. Role of Polyelectrolytes

214

(2)

IV. Use of Other Macromolecular Systems to Synthesize Silica

216

(4)

A. Silica Synthesis Using Polyamino Acids

216

(1)

B. Silica Synthesis Using Polypeptides

216

(3)

C. Silica Synthesis Using Polycations

219

(1)

D. Silica Synthesis Using Polyanions and Other Systems

219

(1)

V. Summary

220

(1)

VI. Future Work

220

(1)

VII. Acknowledgments

221

(1)

VIII. References

221

(4)

9. Organogermanium Polymers

225

(38)

Charles E. Carraher Jr., Charles U. Pittman, Jr., Martel Zeldin, and Alaa S. Abd-El-Aziz

I. Introduction

226

(1)

II. Polygermanes

227

(7)

A. Wurtz Reactions

228

(2)

B. Catalytic Routes

230

(1)

C. Ligand Substitution

230

(1)

D. Electrochemical Synthesis

231

(1)

E. Chemical Properties

232

(1)

F. Physical Properties

232

(1)

G. Miscellaneous

233

(1)

III. Organogermanium-Carbon Backbone Polymers

234

(10)

A. Organogermanium Polymers Containing σ-π Conjugation

235

(8)

B. Simple Ge-C Polymers

243

(1)

IV. Polyferroceneylgermanes

244

(1)

V. Polymers Containing Oxygen, Nitrogen, Silicon, and Sulfur in the Backbone

245

(8)

A. Ge-O Polymers

245

(3)

B. Ge-N Polymers

248

(2)

C. Ge-S Polymers

250

(1)

D. Ge-Si Polymers

250

(1)

E. Other Mixed-Bonded Polymers

251

(2)

VI. Anchored Organogermanium Products

253

(2)

VII. Stacked Phthalocyanine Polymers

255

(1)

VIII. Hyperbranched Materials

256

(2)

IX. Summary

258

(1)

X. References

258

(5)

10. Organotin Polymers

263

(48)

Charles E. Carraher, Jr

I. Introduction

264

(1)

II. Mechanisms

265

(1)

III. Structures

266

(2)

IV. Organotin Polymers

268

(1)

V. Organotin Appendages

268

(14)

A. Vinyl Introduction

268

(1)

i. Organoesters and Ethers

268

(1)

ii. Organotin Carbon

273

(2)

B. Performed Polymer

275

(4)

C. Crosslinked Mixtures

279

(3)

VI. Organotin-Containing Backbones

282

(6)

A. Noncarbon-Linked Organotin Polymers

282

(4)

B. Organotin Polyolefins

286

(2)

VII. Polystannanes

288

(1)

VIII. Organotin Aluminoxanes and Titanoxanes

288

(1)

IX. Group VA-Containing Organotin Polymers

289

(1)

X. Stannoxy Titanoxane Polymers

290

(1)

XI. Stannoxane Polymers

290

(1)

XII. Bioactivity

291

(2)

XIII. General Physical Properties

293

(6)

A. Solubility

293

(1)

B. Stability

294

(1)

C. Physical Nature

294

(1)

D. Molecular Weight

294

(1)

E. Thermal Properties

294

(1)

F Electrical Properties

295

(1)

G. Mass Spectral Behavior

295

(4)

H. Miscellaneous

299

(1)

XIV. Interfacial Polymerization

299

(4)

XV. Summary

303

(1)

XVI. References

303

(8)

11. Organolead-Containing Polymers

311

(22)

Charles E. Carraher, Jr

I. Introduction

312

(1)

II. Polymerization and Copolymerization of Vinyl Lead Compounds

313

(2)

III. Chelation Polymers and Copolymers Derived from Poly(Acrylic Acid)

315

(1)

IV. Arylene-Bridged Products

316

(1)

V. Solid-State Products

316

(8)

A. Nitrogen-Coordinated Products

317

(2)

B. Sulfur-Coordinated Products

319

(2)

C. Halide-Coordinated Products

321

(1)

D. Oxygen Coordinated Products

322

(2)

VI. Condensation Products

324

(2)

VII. Miscellaneous

326

(2)

VIII. Summary

328

(1)

IX. References

328

(5)

Index

333

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Macromolecules Containing Metal and Metal-Like Elements, Group IVA Polymers

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Macromolecules Containing Metal and Metal-Like Elements, Group IVA Polymers

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