Inorganic polymers

Polymer chemistry and technology form one of the major areas of molecular and materials science. This field impinges on nearly every aspect of modern life, from electronics technology, to medicine, to the wide range of fibers, films, elastomers, and structural materials on which everyone depends. Although most of these polymers are organic materials, attention is being focused increasingly toward polymers that contain inorganic elements as well as organic components. The goal of Inorganic Polymers is to provide a broad overview of inorganic polymers in a way that will be useful to both the uninitiated and those already working in this field. There are numerous reasons for being interested in inorganic polymers. One is the simple need to know how structure affects the properties of a polymer, particularly outside the well-plowed area of organic materials. Another is the bridge that inorganic polymers provide between polymer science and ceramics. More and more chemistry is being used in the preparation of ceramics of carefully controlled structure, and inorganic polymers are increasingly important precursor materials in such approaches. This new edition begins with a brief introductory chapter. That is followed with a discussion of the characteristics and characterization of polymers, with examples taken from the field. Other chapters in the book detail the synthesis, reaction chemistry, molecular structure, and uses of polyphosphazenes, polysiloxanes, and polysilanes. The coverage in the second edition has been updated and expanded significantly to cover advances and interesting trends since the first edition appeared. Three new chapters have been added, focusing on ferrocene-based polymers, other phosphorous-containing polymers, and boron-containing polymers; inorganic-organic hybrid composites; and preceramic inorganic polymers. Contents 10 About the Authors 14 1 Introduction 18 1.1 What Is a Polymer? 18 1.2 How Polymers Are Depicted 18 1.3 Reasons for Interest in Inorganic Polymers 20 1.4 Types of Inorganic Polymers 21 1.5 Special Characteristics of Polymers 22 2 Characterization of Inorganic Polymers 23 2.1 Molecular Weights 23 2.2 Molecular Weight Distributions 33 2.3 Other Structural Features 37 2.4 Chain Statistics 41 2.5 Solubility Considerations 43 2.6 Crystallinity 49 2.7 Transitions 55 2.8 Spectroscopy 64 2.9 Mechanical Properties 65 References 73 3 Polyphosphazenes 77 3.1 Introduction 77 3.2 History 80 3.3 Alternative Synthesis Routes to Linear Polymers 85 3.4 Surface Reactions of Polyphosphazenes 98 3.5 Hybrid Systems through Block, Comb, or Ring-Linked Copolymers 99 3.6 Hybrid Systems through Composites 108 3.7 Organometallic Polyphosphazenes 108 3.8 Small-Molecule Models 114 3.9 Molecular Structure of Linear Polyphosphazenes 115 3.10 Structure–Property Relationships 122 3.11 Applications of Polyphosphazenes 126 3.12 Optical and Photonic Polymers 152 3.13 Polymers Related to Polyphosphazenes 156 3.14 Conclusions 158 References 161 4 Polysiloxanes and Related Polymers 169 4.1 Introduction 169 4.2 History 170 4.3 Nomenclature 170 4.4 Preparation and Analysis 171 4.5 General Properties 177 4.6 Reactive Homopolymers 191 4.7 Elastomeric Networks 192 4.8 Some New Characterization Techniques Useful for Polysiloxanes 196 4.9 Copolymers and Interpenetrating Networks 198 4.10 Applications 199 References 204 5 Polysilanes and Related Polymers 215 5.1 Introduction 215 5.2 History 216 5.3 Synthesis 219 5.4 Chemical Modification of Polysilanes 227 5.5 Physical Properties of Polysilanes 228 5.6 Electronic Properties of Polysilanes 230 5.7 Chromotropism of Polysilanes 235 5.8 Electrical Conductivity and Photoconductivity 245 5.9 Luminescence of Polysilanes 247 5.10 Photodegradation of Polysilanes 248 5.11 Cross-Linking 249 5.12 Structural Arrangements in Polysilanes 251 5.13 Technology of Polysilanes 259 5.14 Additional Readings 265 References 265 6 Ferrocene-Based Polymers, and Additional Phosphorus- and Boron-Containing Polymers 269 6.1 Ferrocene-Based Polymers 269 6.2 Other Phosphorus-Containing Polymers 281 6.3 Boron-Containing Polymers 284 References 285 7 Miscellaneous Inorganic Polymers 288 7.1 Introduction 288 7.2 Other Silicon-Containing Polymers 288 7.3 Polygermanes 290 7.4 Polymeric Sulfur and Selenium 291 7.5 Other Sulfur-Containing Polymers 294 7.6 Aluminum-Containing Polymers 299 7.7 Tin-Containing Polymers 299 7.8 Arsenic-Containing Polymers 301 7.9 Metal Coordination Polymers 301 7.10 Other Organometallic Species for Sol-Gel Processes 304 References 305 8 Inorganic-Organic Hybrid Composites 309 8.1 Sol-Gel Ceramics 309 8.2 Fillers in Elastomers 310 8.3 Polymer-Modified Ceramics 320 References 322 9 Preceramic Inorganic Polymers 327 9.1 Overview of Ceramic Aspects 327 9.2 The Sol-Gel Process to Oxide Ceramics 328 9.3 Carbon Fiber 334 9.4 Silicon Carbide (SiC) 335 9.5 Silicon Nitride (Si[sub(3)]N[sub(4)]) 339 9.6 Boron Nitride (BN) 342 9.7 Boron Carbide (B[sub(4)]C) 344 9.8 Aluminum Nitride (AlN) 345 9.9 Phosphorus Nitride (P[sub(3)]N[sub(5)]) 345 9.10 Poly(ferrocenylsilanes) as Ceramic Precursors 346 References 347 Index 350 A 350 B 350 C 350 D 351 E 351 F 351 G 351 H 351 I 351 K 351 L 351 M 351 N 352 O 352 P 352 Q 353 R 353 S 353 T 353 U 353 V 353 W 353 X 353 Y 353 Z 353 I. Introduction 1.1. What Is a Polymer1.2. How Polymers Are Depicted1.3. Reasons for Interest in Organic Polymers1.4. Types of Inorganic Polymers1.5. Special Characteristics of PolymersII. Characterization of Inorganic Polymers 2.1. Molecular Weights2.2. Molecular Weight Distribution2.3. Other Structural Features2.4. Chain Statistics2.5. Solubility Considerations2.6. Crystallinity2.7. Transitions2.8. Spectroscopy2.9. Mechanical PropertiesIII. Polyphosphazenes 3.1. Introduction3.2. History3.3. Alternative Synthesis Routes to Linear Polymers3.4. Surface Reactions of Polyphosphazenes3.5. Hybrid S For those interested in understanding the underlying principles of inorganic polymer chemistry, Inorganic Polymers provides a concise overview and perspective of the preparation, characterisation, and utilisation of inorganic polymers