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Book Details
Abstract
Fluoropolymers display a wide range of remarkable properties and are used in a number of applications including high performance elastomers, thermoplastics, coatings for optical fibers, and hydrophobic and lipophobic surfaces. Fluorinated Polymers: Synthesis, Properties, Processing and Simulation covers the fundamentals of different fluorinated polymers. Topics include the kinetics of homopolymerisation and copolymerization, process chemistry, and controlled radical co-polymerisation techniques. Written by internationally recognized academic and industrial contributors, the book will be of interest to those in industry and academia working in the fields of materials science, polymer chemistry and energy applications of polymers. Together with Fluorinated Polymers: Applications, these books provide a complete overview of different fluorinated polymer materials and their uses.
Table of Contents
| Section Title | Page | Action | Price |
|---|---|---|---|
| Cover | Cover | ||
| Contents | ix | ||
| Preface | vii | ||
| Volume 1 | 1 | ||
| Synthesis | 1 | ||
| Chapter 1 Fluorinated Peroxides as Initiators of Fluorinated Polymers | 3 | ||
| 1.1 Introduction | 3 | ||
| 1.2 Computational Methods | 5 | ||
| 1.3 Results and Discussion | 6 | ||
| 1.3.1 Molecular Structure of Alkanoyl/Fluoroalkanoyl Peroxides | 7 | ||
| 1.3.2 Molecular Structure of Alkanoyl/Fluoroalkanoyl Radicals | 10 | ||
| 1.3.3 Bond Dissociation Energy of Alkanoyl/Fluoroalkanoyl Peroxides and Radicals | 12 | ||
| 1.3.4 Thermal Decomposition of Alkanoyl/Fluoroalkanoyl Peroxides | 17 | ||
| 1.4 Conclusion | 20 | ||
| Acknowledgments | 21 | ||
| References | 21 | ||
| Chapter 2 Fluoroalkylated Styrene Dimers: Synthesis, Properties, and Applications | 22 | ||
| 2.1 Introduction | 22 | ||
| 2.2 General Aspects of the Addition of Perfluoroalkyl Radicals to Olefinic Compounds | 23 | ||
| 2.3 Process for the Formation of Head-to-head Type Styrene Dimers Bearing Two Fluoroalkyl End-groups, as a Basic Principle for Reactions Between Two Radicals | 25 | ||
| 2.4 Synthesis and Characteristic Properties of Styrene Dimers, as the Smallest Model Unit for Fluoroalkyl End-capped Oligomers and Polymers | 29 | ||
| 2.5 Conclusion | 37 | ||
| Acknowledgments | 37 | ||
| References | 37 | ||
| Chapter 3 Anionic Polymerization of Fluorinated Vinyl Monomers | 40 | ||
| 3.1 Introduction | 40 | ||
| 3.2 Anionic Polymerization Reactivity of Fluorinated Acrylates and Methacrylates | 43 | ||
| 3.3 Anionic Polymerization Reactivity of Fluorinated 1,3-Butadiene | 53 | ||
| 3.4 Anionic Polymerization Reactivity of Fluorinated Styrenes | 67 | ||
| 3.5 Conclusion | 69 | ||
| References | 70 | ||
| Chapter 4 Polyaddition of Fluorinated Vinyl Monomers | 72 | ||
| 4.1 Introduction | 72 | ||
| 4.2 Anionic Polyaddition of Fluorinated Vinyl Monomers | 73 | ||
| 4.3 Radical Polyaddition of Fluorinated Vinyl Monomers | 79 | ||
| 4.4 Conclusion | 101 | ||
| References | 101 | ||
| Chapter 5 Semifluorinated Aromatic Polymers and Their Properties | 103 | ||
| 5.1 General Introduction to Aromatic Fluorinated Polymers | 103 | ||
| 5.2 Fluorinated Poly(Arylene Ether)s | 104 | ||
| 5.2.1 Preparation of Fluorinated Poly(Arylene Ether)s | 105 | ||
| 5.2.2 Properties of Fluorinated Poly(Arylene Ether)s | 108 | ||
| 5.2.3 Fluorinated Poly(Arylene Ether)s for Membrane-based Applications | 111 | ||
| 5.3 Fluorinated Poly(Ether Imide)s | 122 | ||
| 5.3.1 Preparation of Fluorinated Poly(Ether Imide)s | 124 | ||
| 5.3.2 Properties of Fluorinated Poly(Ether Imide)s | 125 | ||
| 5.3.3 Fluorinated Poly(Ether Imide)s for Membrane-based Applications | 133 | ||
| 5.4 Fluorinated Poly(Ether Amide)s | 141 | ||
| 5.4.1 Preparation of Fluorinated Poly(Ether Amide)s | 141 | ||
| 5.4.2 Properties of Fluorinated Poly(Ether Amide)s | 141 | ||
| 5.4.3 Fluorinated Poly(Ether Amide)s for Membrane-based Applications | 146 | ||
| 5.5 Fluorinated Polyazoles | 153 | ||
| 5.5.1 Preparation of Fluorinated Poly(Benzimidazole)s | 153 | ||
| 5.5.2 Preparation of Fluorinated Poly(Benzoxazole)s | 158 | ||
| 5.6 Miscellaneous Aromatic Fluorinated Polymers | 163 | ||
| 5.6.1 Fluorinated Poly(Arylene)s | 163 | ||
| 5.6.2 Fluorinated Hyperbranched Polymers | 163 | ||
| 5.6.3 Fluorinated Dendrimers | 168 | ||
| 5.6.4 Fluorinated Acrylate Polymers | 168 | ||
| 5.6.5 Fluorinated Polymers with Perfluorocyclobutyl (PFCB) Units | 168 | ||
| 5.6.6 Fluorinated Polymers with Octafluorocyclopentene Units | 175 | ||
| 5.6.7 Fluorinated Phosphorus-containing Polymers | 175 | ||
| 5.6.8 Fluorinated Microporous Copolymer as Gas Separation Membrane | 175 | ||
| 5.6.9 Quaternized Fluorinated Copolymers as Anion-conductive Membranes | 177 | ||
| 5.6.10 ETFE Film Grafted with Pentafluorostyrene as a Protein-exchange Membrane | 178 | ||
| 5.7 Conclusion | 181 | ||
| Abbreviations | 182 | ||
| References | 183 | ||
| Chapter 6 Synthesis of Fluoro-functional Conjugated Polymers by Electrochemical Methods | 190 | ||
| 6.1 Introduction | 190 | ||
| 6.2 Electropolymerization of Fluoro-aromatic Compounds | 191 | ||
| 6.2.1 Electropolymerization of Aromatic Monomers | 191 | ||
| 6.2.2 Electropolymerization of Fluoro-aromatic Monomers | 193 | ||
| 6.2.3 Surface Morphology and Properties of Fluoro-functionalized Conjugated Polymers | 194 | ||
| 6.2.4 Fluoro-functionalized Conjugated Polymers for Electronic Materials | 196 | ||
| 6.3 Electrochemical Fluorination of Conjugated Polymers | 197 | ||
| 6.3.1 Electrochemical Polymer Reactions | 197 | ||
| 6.3.2 Anodic Fluorination of Polyfluorene Derivatives | 198 | ||
| 6.3.3 Fluorination of Polyaniline by the CRS Method | 201 | ||
| 6.4 Surface Modification of Conjugated Polymers with Fluoro-functional Groups by Electrochemical Methods | 202 | ||
| 6.4.1 Conjugated Polymer Surface | 202 | ||
| 6.4.2 Electro-click Reaction on Conjugated Polymer Surfaces | 202 | ||
| 6.4.3 Gradient Surface Modification by the Electro-click Method | 204 | ||
| 6.5 Conclusion | 206 | ||
| References | 207 | ||
| Chapter 7 Supercritical Carbon Dioxide as Reaction Medium for Fluoropolymer Synthesis and Kinetic Investigations into Radical Polymerizations of VDF and HFP | 211 | ||
| 7.1 Introduction | 211 | ||
| 7.2 Supercritical Carbon Dioxide as Reaction Medium for Fluoropolymer Synthesis | 214 | ||
| 7.3 In-line Monitoring of Vinylidene Fluoride Homo- and Copolymerizations in the Homogeneous Phase with Supercritical Carbon Dioxide | 215 | ||
| 7.4 Kinetic Investigations for Vinylidene Fluoride Homo- and Copolymerizations in Supercritical Carbon Dioxide | 216 | ||
| 7.4.1 Initiator Decomposition Kinetics | 217 | ||
| 7.4.2 Propagation Rate Coefficients for VDF Homo- and Copolymerizations | 219 | ||
| 7.4.3 Termination Kinetics of VDF-HFP copolymerizations | 219 | ||
| References | 229 | ||
| Properties | 233 | ||
| Chapter 8 Structure-Property Relations in Semifluorinated Polymethacrylates | 235 | ||
| 8.1 Introduction | 235 | ||
| 8.2 Experimental | 239 | ||
| 8.2.1 Materials | 239 | ||
| 8.2.2 Polymer Synthesis | 239 | ||
| 8.2.3 Preparation of Thin Films | 240 | ||
| 8.2.4 Characterization | 241 | ||
| 8.2.5 Simulations | 244 | ||
| 8.3 Results and Discussion | 245 | ||
| 8.3.1 Synthesis Results | 245 | ||
| 8.3.2 Solid-state Structure | 246 | ||
| 8.3.3 Simulation Results | 248 | ||
| 8.3.4 Temperature Behavior | 250 | ||
| 8.4 Surface Properties | 254 | ||
| 8.4.1 Surface Structure as Investigated by XRR and GISAXS | 254 | ||
| 8.4.2 Surface Composition | 256 | ||
| 8.4.3 Wetting Behavior | 261 | ||
| 8.5 Conclusion | 269 | ||
| Acknowledgments | 270 | ||
| References | 270 | ||
| Chapter 9 Preparation and Self-assembly of Amphiphilic Fluoropolymers | 276 | ||
| 9.1 Introduction | 276 | ||
| 9.2 Preparation and Self-assembly of Linear Fluoropolymers | 278 | ||
| 9.3 Preparation and Self-assembly of Non-linear Fluoropolymers | 292 | ||
| 9.4 Conclusion | 301 | ||
| Acknowledgments | 303 | ||
| References | 303 | ||
| Processing | 307 | ||
| Chapter 10 The Melt Viscosity Properties of Fluoroplastics – Correlations to Molecular Structure and Tailoring Principles | 309 | ||
| 10.1 Introduction | 309 | ||
| 10.2 Terpolymers Under Investigation | 312 | ||
| 10.3 Fundamentals of Melt Rheology | 314 | ||
| 10.3.1 Fluoropolymer Melts in Shear Flows | 314 | ||
| 10.3.2 Superposition Principles | 317 | ||
| 10.4 Determining Molar Masses | 320 | ||
| 10.4.1 General Considerations on the Molar Mass Distribution | 320 | ||
| 10.4.2 Key Rheology Parameters and Dependence on the Average Molar Mass | 321 | ||
| 10.4.3 Diagnosing the Molar Mass Distribution of Insoluble Polymers | 325 | ||
| 10.5 Customizing Concepts for Linear Chains | 329 | ||
| 10.5.1 Controlling the Average Molar Mass | 329 | ||
| 10.5.2 End-group Considerations in View of Chain Transfer | 331 | ||
| 10.5.3 Fine Tuning the Molar Mass Distribution | 332 | ||
| 10.6 Tailoring the Polymer Topology by Long-chain Branching | 335 | ||
| 10.6.1 Evolution from Primary to Higher Order Populations | 335 | ||
| 10.6.2 Qualifying Complex Chain Architectures | 339 | ||
| 10.6.3 Long-chain Branched Fluoropolymers in Elongational Flows | 343 | ||
| 10.6.4 Benefits in Melt Processing | 348 | ||
| 10.7 Conclusion | 351 | ||
| Abbreviations and Symbols | 353 | ||
| Abbreviations | 353 | ||
| Symbols | 354 | ||
| References | 356 | ||
| Simulation | 359 | ||
| Chapter 11 Molecular Simulation of Fluorinated Telomer and Polymers | 361 | ||
| 11.1 Introduction | 361 | ||
| 11.2 Theory | 363 | ||
| 11.2.1 Arrhenius Equation | 363 | ||
| 11.2.2 Transition-state Theory | 364 | ||
| 11.3 Quantum Chemistry | 368 | ||
| 11.3.1 Resolving the Schrödinger Equation | 368 | ||
| 11.3.2 Errors | 370 | ||
| 11.4 Application | 374 | ||
| 11.4.1 Context | 374 | ||
| 11.4.2 The Molecular Structure | 375 | ||
| 11.4.3 The Symmetry Factor σ\r | 377 | ||
| 11.4.4 The TS Quasi-partition Function | 378 | ||
| 11.4.5 The Free Reactant Partition Function per Unit Volume | 378 | ||
| 11.4.6 The Activation Energy Ea | 379 | ||
| 11.4.7 The Rate Constants and the Chain Transfer Constant | 380 | ||
| 11.4.8 Intrinsic Reaction Coordinates (IRCs) | 380 | ||
| 11.4.9 Perspectives: Study of Regioselectivity for Iodine Transfer Polymerization | 381 | ||
| 11.5 Conclusion | 382 | ||
| References | 383 | ||
| Subject Index | 386 |