POLYMERS: CHEMISTRY AND PHYSICS OF MODERN MATERIALS

Transcription

1 POLYMERS: CHEMISTRY AND PHYSICS OF MODERN MATERIALS THIRD EDITION J.M.G. COWIE Heriot-Watt University Scotland,UK VALERIA ARRIGHI Heriot-Watt University Scotland,UK

2 Contents Preface The Authors xv xvii Chapter 1 Introduction Birth of a Concept Some Basic Definitions Synthesis of Polymers Nomenclature Average Molar Masses and Distributions Size and Shape Configuration The Glass Transition Temperature T g and the Melting Temperature T m Elastomers, Fibers, and Plastics Fiber-Forming Polymers Plastics Thermosetting Polymers Elastomers 21 Problems 25 References 27 Bibliography 27 Chapter 2 Step-Growth Polymerization General Reactions Reactivity of Functional Groups, Carothers Equation Control of the Molar Mass Stoichiometric Control of M Kinetics Molar Mass Distribution in Linear Systems Average Molar Masses Characteristics of Step-Growth Polymerization Typical Step-Growth Reactions Ring Formation Nonlinear Step-Growth Reactions Statistical Derivation Comparison with Experiment Polyurethanes Thermosetting Polymers 49 Problems 52 References 56 Bibliography 56

3 Chapter 3 Free-Radical Addition Polymerization Addition Polymerization Choice of Initiators Free-Radical Polymerization Initiators Initiator Efficiency Chain Growth Termination Steady-State Kinetics High-Conversion Bulk Polymerizations Chain Transfer Consequences of Chain Transfer Inhibitors and Retarders Activation Energies and the Effect of Temperature Thermodynamics of Radical Polymerization Heats of Polymerization Polymerization Processes Features of Free-Radical Polymerization Controlled Radical Polymerization Nitroxide-Mediated Polymerizations Atom Transfer Radical Polymerization (ATRP) Reverse ATRP Degenerative Chain Transfer Reaction (DT) Reversible Addition Fragmentation Chain Transfer (RAFT) CRP ofvinyl Chloride The Kinetics of CRP Processes Application to Experimental Data 90 Problems 92 References 96 Bibliography 96 Chapter 4 Ionic Polymerization General Characteristics Cationic Polymerization Propagation by Cationic Chain Carriers Termination General Kinetic Scheme Energetics of Cationic Polymerization Telechelic Polymers via Cationic Polymerization Cationic Ring Opening Polymerization Stable Carbocations Anionic Polymerization Living Polymers Kinetics and Molar Mass Distribution in Living Anionic Systems 110

4 4.13 Metal Alkyl Initiators Solvent and Gegen Ion Effects Anionic Ring-Opening Polymerization 114 Problems 116 References 118 Bibliography 119 Chapter 5 Linear Copolymers and Other Architectures General Characteristics Composition Drift The Copolymer Equation Monomer Reactivity Ratios Reactivity Ratios and Copolymer Structure Monomer Reactivities and Chain Initiation Influence of Structural Effects on Monomer Reactivity Ratios Resonance Effects Polar Effects The Q-e Scheme Alternating Copolymers Block Copolymer Synthesis Transformation Reactions Cationic to CRP Anionic to CRP ROMP to ATRP Step-Growth ATRP Coupling Reactions Use of CRP Methods Graft Copolymer Synthesis Statistical and Gradient Copolymers Complex Molecular Architectures Dendrimers Divergent Growth Convergent Growth Dendrimer Molecular Weight Properties of Dendrimers Applications of Dendrimers 154 Problems 155 References 156 Bibliography 156 Chapter 6 Polymer Stereochemistry Architecture Orientation Configuration 158

5 6.3.1 Monotactic Polymers Ditactic Polymers Polyethers Geometrie Isomerism Conformation of Stereoregular Polymers Factors Influencing Stereoregulation Homogeneous Stereospecific Cationic Polymerizations Homogeneous Stereoselective Anionic Polymerizations Homogeneous Diene Polymerization Summary 172 Problems 172 References 173 Bibliography 173 Chapter 7 Polymerization Reactions Initiated by Metal Catalysts and Transfer Reactions Polymerization Using Ziegler-Natta Catalysts Nature of the Catalyst Nature of Active Centers Bimetallic Mechanism Monometallic Mechanism Stereoregulation Ring-Opening Metathesis Polymerization (ROMP) Monocyclic Monomers Bicyclo- and Tricyclomonomers Copolyalkenamers Living Systems Group Transfer Polymerization (GTP) Aldol Group Transfer Polymerization Metallocene Catalysts Metallocene/Aluminoxane Catalysts Stereoregulation Cationic Metallocenes Mechanism of Stereoregulation Concluding Remarks 193 Problems 194 References 194 Bibliography 194 Chapter 8 Polymers in Solution Thermodynamics of Polymer Solutions Ideal Mixtures of Small Molecules Nonideal Solutions Flory-Huggins Theory: Entropy of Mixing 199

6 8.5 Enthalpy Change on Mixing Free Energy of Mixing Limitations of the Flory-Huggins Theory Phase Equilibria Flory-Krigbaum Theory Location of the Theta Temperature Lower Critical Solution Temperatures Solubility and the Cohesive Energy Density Polymer-Polymer Mixtures Kinetics of Phase Separation 223 Problems 224 References 227 Bibliography 227 Chapter 9 Polymer Characterization Molar Masses Introduction Molar Masses, Molecular Weights, and SI Units Number-Average Molar Mass M n End-Group Assay Colligative Properties of Solutions Osmotic Pressure Light Scattering Scattering from Large Particles Dynamic Light Scattering Viscosity Viscosity-Average Molecular Weight Gel Permeation Chromatography MALDI 247 Problems 248 References 251 Bibliography 252 Chapter 10 Polymer Characterization Chain Dimensions, Structures, and Morphology Average Chain Dimensions Freely Jointed Chain Model Short-Range Effects Chain Stiffness Treatment of Dilute Solution Data The Second Virial Coefficient Expansion Factor a Flory-Fox Theory Indirect Estimates of Unperturbed Chain Dimensions Influence of Tacticity on Chain Dimensions 259

7 10.6 Nuclear Magnetic Resonance (NMR) Infrared Spectroscopy Thermal Analysis Wide-Angle and Small-Angle Scattering Wide-Angle X-Ray Scattering Small-Angle X-Ray Scattering (SAXS) Small-Angle Neutron Scattering (SANS) Microscopy Optical Microscopy Scanning Electron Microscopy Transmission Electron Microscopy Atomic Force Microscopy and Scanning Tunneling Microscopy 274 Problems 276 References 277 Bibliography 277 Chapter 11 The Cry stalline State and Partially Ordered Structures Introduction Mechanism of Crystallization Temperature and Growth Rate Melting Effect of Crystallite Size on Melting Thermodynamic Parameters Crystalline Arrangement of Polymers Factors Affecting Crystallinity and T m Symmetry Intermolecular Bonding Tacticity Branching and Molar Mass Morphology and Kinetics Morphology Crystallites Single Crystals Hedrites Crystallization from the Melt Spherulites Kinetics of Crystallization Isothermal Crystallization The Avrami Equation Deviations from Avrami Equation Block Copolymers Historical Development of Polymer Liquid Crystals Liquid Crystalline Phases Identification of the Mesophases 300

8 11.14 Lyotropic Main-Chain Liquid Crystal Polymers Thermotropic Main-Chain Liquid Crystal Polymers Side-Chain Liquid Crystal Polymers Chiral Nematic Liquid Crystal Polymers 311 Problems 314 References 318 Bibliography 318 Chapter 12 The Glassy State and Glass Transition The Amorphous State The Glassy State Relaxation Processes in the Glassy State Glass Transition Region The Glass Transition Temperature, T g Experimental Demonstration of T Measurement of T g from V-T Curves Thermal Methods Factors Affecting T g Chain Flexibility Steric Effects Configurational Effects Effect of Cross-Links on T g Theoretical Treatments The Free-Volume Theory Gibbs-Di Marzio Thermodynamic Theory Adam-Gibbs Theory Dependence of T g on Molar Mass Structural Relaxation and Physical Aging 338 Problems 339 References 342 Bibliography 343 Chapter 13 Rheology and Mechanical Properties Introduction to Rheology The Five Regions of Viscoelastic Behavior The Viscous Region Shear Dependence of Viscosity Kinetic Units in Polymer Chains Effect of Chain Length Temperature Dependence of r Concentration Dependence of Viscosity Time-Dependent Behavior Mechanical Properties Interrelation of Moduli 357

9 13.5 Mechanical Models Describing Viscoelasticity Linear Viscoelastic Behavior of Amorphous Polymers Creep Stress-Strain Measurements Effect of Temperature on Stress-Strain Response Boltzmann Superposition Principle Stress Relaxation Dynamic Mechanical and Dielectric Thermal Analysis Dynamic Mechanical Thermal Analysis (DMTA) Dielectric Thermal Analysis (DETA) Comparison Between DMTA and DETA Time-Temperature Superposition Principle Dynamic Viscosity A Molecular Theory for Viscoelasticity The Reptation Model 380 Problems 382 References 387 Bibliography 388 Chapter 14 The Elastomeric State General Introduction Natural Rubber Experimental Vulcanization Properties of Elastomers Thermodynamic Aspects of Rubberlike Elasticity Nonideal Elastomers Distribution Function for Polymer Conformation Statistical Approach Experimental Stress-Strain Results Simple Extension Simple Compression Pure Shear Large Elastic Deformation Swelling of Elastomeric Networks Network Defects Resilience of Elastomers 403 Problems 405 References 408 Bibliography 408 Chapter 15 Structure-Property Relations General Considerations Control of T m and T g Chain Stiffness 410

10 Intermolecular Bonding : Relation Between T m and T g Random Copolymers Dependence of T m and T g on Copolymer Composition Block Copolymers Plasticizers Crystallinity and Mechanical Response Application to Fibers, Elastomers, and Plastics Fibers Chemical Requirements Linear Polyesters Mechanical Requirements for Fibers Spinning Techniques Melt Spinning Wet and Dry Spinning Drawing, Orientation, and Crystallinity Modulus and Chain Stiffness Other Factors Aromatic Polyamides Polyethylene Elastomers and Cross-Linked Networks Cross-Linking Creep in Cross-Linked Polymers Additives Plastics Plastic Selection for Bottle Crate Manufacture Medical Applications High-Temperature Speciality Polymers Carbon Fibers Concluding Remarks 446 Problems 448 References 453 Bibliography 454 Chapter 16 Polymers for the Electronics Industry Introduction Polymer Resists for IC Fabrication The Lithographie Process Polymer Resists Sensitivity Resolution Photolithography Positive Photoresists Negative Photoresists Electron Beam Sensitive Resists 463

11 Positive Resists Negative Resists X-ray and Ion Sensitive Resists Electroactive Polymers Conduction Mechanisms Preparation of Conductive Polymers Polyacetylene Poly(jc-phenylene) Polyheterocyclic Systems Polypyrrole Sulfur Compounds Polyaniline Poly(Phenylene Sulfide) Poly(l,6-heptadiyne) Applications Photonic Applications Light-Emitting Polymers Applications Nonlinear Optics Langmuir-Blodgett Films Optical Information Storage Thermorecording on Liquid Crystalline Polymers 486 References 487 Bibliography 487 Index 489