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<ul><li><p>Vadapalli Chandrasekhar</p><p>Inorganic and Organometallic Polymers</p></li><li><p>Vadapalli Chandrasekhar</p><p>Inorganic andOrganometallicPolymers</p><p>Springer</p></li><li><p>Prof. Dr.Vadapalli ChandrasekharIndian Institute of TechnologyDepartment Chemistry208016 KanpurIndiae-mail: vc@iitk.ac.in</p><p>Library of Congress Control Number: 2004109261</p><p>ISBN 3-540-22574-9 Springer Berlin Heidelberg New York</p><p>This work is subject to copyright. All rights are reserved, whether the whole or part of thematerial is concerned, specifically the rights of translation, reprinting, reuse of illustrations,recitation, broadcasting, reproduction on microfilm or in any other way, and storage indata banks. Duplication of this publication or parts thereof is permitted only under theprovisions of the German Copyright Law of September 9,1965, in its current version, andpermission for use must always be obtained from Springer. Violations are liable forprosecution under the German Copyright Law.</p><p>Springer is a part of Springer Science+Business Mediaspringeronline.com</p><p> Springer-Verlag Berlin Heidelberg 2005Printed in Germany</p><p>The use of designations, trademarks, etc. in this publication does not imply, even in theabsence of a specific statement, that such names are exempt from the relevant protectivelaws and regulations and therefore free for general use.</p><p>Typesetting: Computer to film by author's dataCover design: KiinkelLopka, HeidelbergProduction: Verlagsservice HeidelbergPrinted on acid-free paper 2/3130XT 5 4 3 2 10</p></li><li><p>ToMy 'Parents</p></li><li><p>Preface</p><p>This book has its origins in courses taught by the author to various under-graduate and graduate students at the Indian Institute of Technology, Kan-pur, India. The diversity of inorganic chemistry and its impact on polymerchemistry has been profound. This subject matter has grown considerablyin the last decade and the need to present it in a coherent manner to youngminds is a pedagogic challenge. The aim of this book is to present to thestudents an introduction to the developments in Inorganic and Or-ganometallic polymers.</p><p>This book is divided into eight chapters. Chapter 1 provides a generaloverview on the challenges of Inorganic polymer synthesis. This is fol-lowed by a survey of organic polymers and also includes some basic fea-tures of polymers. Chapters 3-8 deal with prominent families of inorganicand organometallic polymers. Although the target group of this book is theundergraduate and graduate students of chemistry, chemical engineeringand materials science it is also hoped that chemists and related scientistsin industry would find this book useful.</p><p>I am extremely thankful to my wife Sudha who not only encouraged methroughout but also drew all the Figures and Schemes of this book. I alsothank my children Adithya and Aarathi for their constant concern on theprogress of this book. I express my acknowledgment to the editorial teamof Springer-Verlag for their cooperation.</p><p>July 2004 Vadapalli Chandrasekhar, Kanpur</p></li><li><p>Contents</p><p>1 Inorganic Polymers: Problems and Prospects 11.1 Introduction 11.2 Procedures for Synthesizing Organic Polymers 21.3 Inorganic Polymers: A Review of Synthetic Strategies 5</p><p>1.3.1 Unsaturated Inorganic Compounds 61.3.2 Inorganic Polymers from Acyclic Monomers 71.3.3 Ring-Opening Polymerization of Cyclic Inorganic</p><p>Compounds 161.3.4 Polymers Containing Inorganic Rings or Motifs as</p><p>Pendant Groups 211.4 Summary of Polymerization Procedures for Inorganic Polymers . 22References 25</p><p>2 Organic Polymers - A Brief Survey 272.1 Introduction 272.2 Natural Polymers 282.3 Synthetic Polymers 292.4 Free-radical Polymerization 30</p><p>2.4.1 Initiators 312.4.2 Mechanism of Polymerization 332.4.3 Branching 342.4.4 Chain Transfer 352.4.5 Summary of the Main Features of Free-radical</p><p>Polymerization 362.5 Polymerization by Ionic Initiators 36</p><p>2.5.1 Anionic Polymerization 372.5.2 Cationic Polymerization 40</p><p>2.6 Ziegler-Natta Catalysis 432.6.1 Mechanism of Polymerization of Olefins Using the</p><p>Ziegler-Natta Catalysts 452.6.2 Supported Ziegler-Natta Catalysts 502.6.3 Recent Developments in Ziegler-Natta Catalysis 502.6.4 Summary of the Ziegler-Natta Catalysis 55</p></li><li><p>X Contents</p><p>2.7 Olefin Metathesis Polymerization 562.8 Atom Transfer Radical Polymerization 582.9 Ring-opening Polymerization 602.10 Group-Transfer Polymerization 622.11 Condensation Polymers 63</p><p>2.11.1 Polyesters 642.11.2 Polycarbonates 672.11.3 Polyamides 672.11.4Polyimides 692.11.5 Polysulfones 712.11.6 Thermoset Resins 71</p><p>2.12 Some Basic Features About Polymers 752.12.1 Molecular Weights of Polymers 752.12.2 Glass Transition Temperature of Polymers 762.12.3 Elastomers, Fibers and Plastics 77</p><p>References 80</p><p>3 Cyclo- and Polyphosphazenes 823.1 Introduction 823.2 Cyclophosphazenes 83</p><p>3.2.1 Preparation of Chlorocyclophosphazenes 863.2.2 Preparation of Fluorocyclophosphazenes and other</p><p>Halogeno- and Pseudohalogenocyclophosphazenes 893.2.3 Chlorine Replacement Reactions of</p><p>Chlorocyclophosphazenes 903.2.4 Other Methods of Preparing P-C Containing Compounds... 943.2.5 Reactions of Chlorocyclophosphazenes with Difunctional</p><p>Reagents 953.2.6 Isomerism in Cyclophosphazenes 993.2.7 Mechanism of the Nucleophilic Substitution Reaction 1003.2.8 Cyclophosphazenes as Ligands for Transition Metal</p><p>Complexes 1043.2.9 Structural Characterization of Cyclophosphazenes 1063.2.10 Nature of Bonding in Cyclophosphazenes 108</p><p>3.3 Polyphosphazenes 1123.3.1 Historical 1123.3.2 Poly(dichlorophosphazene) 1133.3.3 Condensation Polymerization of C13P=N-P(O)C12 1163.3.4 Polymerization of Cl3P=NSiMe3 1183.3.5 ROP of Substituted Cyclophosphazenes 1233.3.6 Poly(organophosphazene)s Prepared by Macromolecular</p><p>Substitution of [NPCl2]n 126</p></li><li><p>Contents XI</p><p>3.3.7 Preparation of Polyphosphazenes Containing P-C Bondsby Thermal Treatment of Phosphoranimines 131</p><p>3.3.8 Modification of Poly(organophosphazene)s 1363.3.9 Modification of Poly(alkyl/arylphosphazene)s 1403.3.10 Structure and Properties of Polyphosphazenes 1423.3.11 Potential Applications of Polyphosphazenes 150</p><p>References 153</p><p>4 Cyclophosphazene-Containing Polymers 1554.1 Introduction 1554.2 Polymers Containing Cyclophosphazenes as Pendant Groups 156</p><p>4.2.1 Synthesis of Cyclophosphazene Monomers ContainingVinyl Groups 158</p><p>4.2.2 Polymerization of Cyclophosphazene Monomers 1654.2.3 Other Ways of Making Polymers Containing</p><p>Cyclophosphazene Pendant Groups 1724.2.4 Applications of Polymers Containing Cyclophosphazene</p><p>Pendant Groups 1734.3 Cyclolinear and Cyclomatrix Polymers 178References 181</p><p>5 Other Inorganic Polymers that Contain Phosphorus, Boronand Sulfur 1835.1 Poly(heterophosphazene)s 1835.2 Poly(carbophosphazene)s 1845.3 Poly(thiophosphazene)s 1895.4Poly(thionylphosphazene)s 193</p><p>5.4.1 Polymerization of [{NPC12}2{NS(O)C1}] and[{NPC12}2{NS(O)F}] 194</p><p>5.5 Other P-N-S Polymers 1995.6 Metallacyclophosphazenes 2005.7 Other Phosphorus-Containing Polymers 203</p><p>5.7.1 Polyphosphinoboranes 2035.7.2 Polymers Containing P=C bonds 204</p><p>5.8 Poly(alkyl/aryloxothiazenes) 2055.9 Borazine-based Polymers 206References 207</p><p>6 Polysiloxanes 2096.1 Introduction 2096.2 Historical Aspects of Poly(dimethysiloxane) 2156.3 Ring-Opening Polymerization of Cyclosiloxanes 219</p></li><li><p>XII Contents</p><p>6.3.1 Cyclosiloxanes 2206.3.2 Ring-opening Polymerization of Cyclosiloxanes by</p><p>Ionic Initiators 2246.3.3 Preparation of Copolymers by Ring-Opening</p><p>Polymerization 2306.3.4 Summary of the Ring-Opening Polymerization of</p><p>Cyclosiloxanes 2316.4 Condensation Polymerization 2326.5 Crosslinking of Polysiloxanes 234</p><p>6.5.1 Other Ways of Achieving Crosslinking 2346.6 Hybrid Polymers 2396.7 Properties of Polysiloxanes 241</p><p>6.7.1 Glass-Transition Temperatures and ConformationalFlexibility 241</p><p>6.8 Applications of Polysiloxanes 244References 246</p><p>7 Polysilanes and Other Silicon-Containing Polymers 2497.1 Introduction 2497.2 Historical 2517.3 Synthesis of Polysilanes 254</p><p>7.3.1 Synthesis of Polysilanes by Wurtz-type CouplingReactions 255</p><p>7.3.2 Polymerization by Anionic Initiators 2607.3.3 Polysilanes Obtained by Catalytic Dehydrogenation 2657.3.4 Summary of the Synthetic Procedures for Polysilanes 268</p><p>7.4 Modification of Polysilanes 2697.5 Physical Properties of Polysilanes 272</p><p>7.5.1 NMR of Polysilanes 2737.5.2 Electronic Spectra of Polysilanes 276</p><p>7.6 Optically Active Polysilanes 2787.7 Applications of Polysilanes 2807.8 Polysilynes 2817.9 Polycarbosilanes and Polysiloles 284</p><p>7.9.1 Polycarbosilanes 2847.9.2 Polysiloles 288</p><p>References 292</p><p>8 Organometallic Polymers 2968.1 Introduction 2968.2 Polygermanes and Polystannanes 297</p><p>8.2.1 Synthesis of Polygermanes 298</p></li><li><p>Contents XIII</p><p>8.2.2 Synthesis of Polystannanes 3008.2.3 Electronic Properties of Polygermanes and Polystannanes.. 302</p><p>8.3 Ferrocene-Containing Polymers 3038.3.1 Synthetic Strategies 3048.3.2 Strained Ferrocenophanes 3108.3.3 Poly(ferrocenylsilane)s 3128.3.4 Other Ferrocenyl Polymers Prepared from Strained</p><p>Ferrocenophanes 3188.3.5 Other Related Polymers 3208.3.6 Properties and Applications of Poly(ferrocenylsilane)s</p><p>and Related Polymers 3218.4 Polyyne Rigid-rod Organometallic Polymers 324</p><p>8.4.1 Properties and Applications of Rigid-Rod Polyynes 332References 333</p><p>Index 337</p></li><li><p>1 Inorganic Polymers: Problems and Prospects</p><p>1.1 Introduction</p><p>One of the indicators of the progress of human civilization is the type ofmaterials that are accessible to society. Just as the Metal (Bronze and Iron)Age marked the beginning of a new chapter of human civilization at theend of the Stone Age, the advent of organic polymers in the last centuryhas heralded a new era. Conventional materials such as iron, steel, wood,glass or ceramics are today being either supplemented or replaced bypolymeric materials. From commonplace and routine (elastomers, fibers,thermoplastics) to special and high technology applications (electronic,electrical, optical, biological) polymers are being increasingly utilized.This dramatic impact of polymers has become possible because of two im-portant factors. Firstly, the intrinsic versatility of carbon to form bonds toitself and to other hetero atoms such as oxygen, nitrogen or sulfur has en-abled the extension of the principles of organic chemistry to polymer syn-thesis. This methodology has allowed the assembly of a large variety ofpolymers that possess varying properties which can fulfill wide and di-verse needs. Secondly, the accessibility of inexpensive petroleum feedstocks from the beginning of the last century has allowed a large-scaleavailability of the building blocks of polymer synthesis and this in turn hashelped the mass production of polymeric materials. From exotic laboratorymaterials polymers have become bulk commodities [1-3].</p><p>In spite of such wide-ranging applications and ubiquitous presence car-bon-based polymeric materials probably do not have the capability to ful-fill all the demands and needs of new applications [2]. For example, manyorganic polymers are not suitable for applications at extreme temperatures.Typically, at very low temperatures they become very brittle while at hightemperatures they are oxidatively degraded. Also, most organic polymersare a fire hazard because of their excellent flammability properties. Mostoften it is required to blend fire-retardant additives to organic polymers tomake them less hazardous with respect to inflammability. Another impor-</p></li><li><p>2 1 Inorganic Polymers: Problems and Prospects</p><p>tant limitation is that the petroleum feed stocks are not going to last forever. Clearly this stock is going to run out fairly quickly given the rate ofits consumption. Even if one considers that coal reserves are much largerand hence may provide the necessary basis for the continuation of the or-ganic polymers there is going to be a need for supplementing these con-ventional systems with polymers that contain inorganic elements. It is tobe noted that silicon is the second most widely present element in theearth's crust (27.2 % by weight), while carbon ranks seventeenth in the or-der of abundance (180 ppm). If one takes into account the presence of car-bon in oceans and atmosphere also, its abundance goes up to the fourteenthposition [4]. Thus, it makes chemical sense to look for alternative poly-meric systems based on non-carbon backbones. Lastly, another compellingreason to look for newer polymeric systems containing inorganic elementsis the line of thinking that if organic polymers themselves are so diverse interms of their structure and property, it should be possible to find entirelynew types of polymeric systems with completely different properties insome combination of inorganic elements. These are a few reasons thathave motivated research scientists across the world to find ways of assem-bling new types of polymers that are based on inorganic elements [5-9]. Itmust be stated at the outset that most of these efforts have resulted inpolymers which not only contain inorganic elements but also have organicgroups either as side groups or in the main-chain itself. While there aresome examples of pure inorganic polymers they still remain rare. In orderto appreciate the problems of inorganic polymer synthesis it is worthwhileto briefly examine the synthesis of organic polymers. A more detailed sur-vey of organic polymer synthesis is presented in Chap. 2.</p><p>1.2 Procedures for Synthesizing Organic Polymers</p><p>Most organic polymers can be synthesized by using any of the followingthree general synthetic methods: (1) Polymerization of unsaturated organicmonomers. (2) Condensation of (usually) two difunctional monomers witheach other. (3) Ring-opening polymerization of cyclic organic rings to lin-ear chain polymers [1-3].</p><p>Vinyl monomers such as CH2=CH2 (and others such as CF2=CF2), monosubstituted ethylenes CH2=CH(R) (such as propylene, styrene, vinyl chlo-ride, acrylonitrile, methyl methacrylate, etc.), some disubstituted olefmsCH2=CRR' (such as isobutylene), dienes (such as 1,3-butadiene, isoprene)and also monomers such as acetylene can be polymerized by various po-lymerization methods to afford linear chain polymers. In all of these po-</p></li><li><p>1.2 Procedures for Synthesizing Organic Polymers 3</p><p>lymerization reactions two new C-C single bonds are created in place ofone C=C double bond. This process is thermodynamically favorable. Rep-resentative examples of polymers that have been synthesized by thismethod are shown in Fig. 1.1.</p><p>- C H 2 CH 2 4-J n</p><p>Polyethylene</p><p>-f-CH2 CH-4-L 1 Jn</p><p>Cl</p><p>Poly(vinyl chloride)</p><p>- | - C H 2 C H - 1 -L j J n</p><p>PPolystyrene</p><p>-CFj CF-</p><p>Polytetrafluoroethylene</p><p>I</p><p>CH3</p><p>Polyisoprene</p><p>- | -CH 2 CCI 2 ] -L -1 n</p><p>Poly(vinylidene chloride)</p><p>-f-CH2CH-4-L I J n</p><p>CN</p><p>Polyacrylonitrile</p><p>-f-CH=CH-|-L Jn</p><p>Polyacetylene</p><p>fCH2-CH-hI- I J n</p><p>Poly(vinyl pyrrolidine)</p><p>-j-CH2-CH-|-L I J n</p><p>H2N^ ^ O</p><p>Polyacrylamide</p><p>-f-CH2-C(CH3)-l-i. I J n</p><p>c=oCH3</p><p>Poly(methyl methacrylate)</p><p>- C H 7</p><p>Poly(c/s-butadiene)</p><p>Fig. 1.1. Representative examples of organic polymers prepared from unsaturatedorganic monomers</p><p>The second method of obtaining organic polymers involves the exploita-tion of functional group chemistry of organic molecules. Thus, for exam-ple the reaction of a carboxylic acid with an alcohol affords an ester. In-stead of c...</p></li></ul>