| |

| |

| |

Introduction to Chain Molecules | |

| |

| |

| |

Introduction | |

| |

| |

| |

How Big Is Big? | |

| |

| |

| |

Molecular Weight | |

| |

| |

| |

Spatial Extent | |

| |

| |

| |

Linear and Branched Polymers, Homopolymers, and Copolymers | |

| |

| |

| |

Branched Structures | |

| |

| |

| |

Copolymers | |

| |

| |

| |

Addition, Condensation, and Natural Polymers | |

| |

| |

| |

Addition and Condensation Polymers | |

| |

| |

| |

Natural Polymers | |

| |

| |

| |

Polymer Nomenclature | |

| |

| |

| |

Structural Isomerism | |

| |

| |

| |

Positional Isomerism | |

| |

| |

| |

Stereo Isomerism | |

| |

| |

| |

Geometrical Isomerism | |

| |

| |

| |

Molecular Weights and Molecular Weight Averages | |

| |

| |

| |

Number-, Weight-, and z-Average Molecular Weights | |

| |

| |

| |

Polydispersity Index and Standard Deviation | |

| |

| |

| |

Examples of Distributions | |

| |

| |

| |

Measurement of Molecular Weight | |

| |

| |

| |

General Considerations | |

| |

| |

| |

End Group Analysis | |

| |

| |

| |

MALDI Mass Spectrometry | |

| |

| |

| |

Preview of Things to Come | |

| |

| |

| |

Chapter Summary | |

| |

| |

Problems | |

| |

| |

References | |

| |

| |

Further Readings | |

| |

| |

| |

Step-Growth Polymerization | |

| |

| |

| |

Introduction | |

| |

| |

| |

Condensation Polymers: One Step at a Time | |

| |

| |

| |

Classes of Step-Growth Polymers | |

| |

| |

| |

First Look at the Distribution of Products | |

| |

| |

| |

A First Look at Reactivity and Reaction Rates | |

| |

| |

| |

Kinetics of Step-Growth Polymerization | |

| |

| |

| |

Catalyzed Step-Growth Reactions | |

| |

| |

| |

How Should Experimental Data Be Compared with Theoretical Rate Laws? | |

| |

| |

| |

Uncatalyzed Step-Growth Reactions | |

| |

| |

| |

Distribution of Molecular Sizes | |

| |

| |

| |

Mole Fractions of Species | |

| |

| |

| |

Weight Fractions of Species | |

| |

| |

| |

Polyesters | |

| |

| |

| |

Polyamides | |

| |

| |

| |

Stoichiometric Imbalance | |

| |

| |

| |

Chapter Summary | |

| |

| |

Problems | |

| |

| |

References | |

| |

| |

Further Readings | |

| |

| |

| |

Chain-Growth Polymerization | |

| |

| |

| |

Introduction | |

| |

| |

| |

Chain-Growth and Step-Growth Polymerizations: Some Comparisons | |

| |

| |

| |

Initiation | |

| |

| |

| |

Initiation Reactions | |

| |

| |

| |

Fate of Free Radicals | |

| |

| |

| |

Kinetics of Initiation | |

| |

| |

| |

Photochemical Initiation | |

| |

| |

| |

Temperature Dependence of Initiation Rates | |

| |

| |

| |

Termination | |

| |

| |

| |

Combination and Disproportionation | |

| |

| |

| |

Effect of Termination on Conversion to Polymer | |

| |

| |

| |

Stationary-State Radical Concentration | |

| |

| |

| |

Propagation | |

| |

| |

| |

Rate Laws for Propagation | |

| |

| |

| |

Temperature Dependence of Propagation Rates | |

| |

| |

| |

Kinetic Chain Length | |

| |

| |

| |

Radical Lifetime | |

| |

| |

| |

Distribution of Molecular Weights | |

| |

| |

| |

Distribution of i-mers: Termination by Disproportionation | |

| |

| |

| |

Distribution of i-mers: Termination by Combination | |

| |

| |

| |

Chain Transfer | |

| |

| |

| |

Chain Transfer Reactions | |

| |

| |

| |

Evaluation of Chain Transfer Constants | |

| |

| |

| |

Chain Transfer to Polymer | |

| |

| |

| |

Suppressing Polymerization | |

| |

| |

| |

Chapter Summary | |

| |

| |

Problems | |

| |

| |

References | |

| |

| |

Further Readings | |

| |

| |

| |

Controlled Polymerization | |

| |

| |

| |

Introduction | |

| |

| |

| |

Poisson Distribution for an Ideal Living Polymerization | |

| |

| |

| |

Kinetic Scheme | |

| |

| |

| |

Breadth of the Poisson Distribution | |

| |

| |

| |

Anionic Polymerization | |

| |

| |

| |

Block Copolymers, End-Functional Polymers, and Branched Polymers by Anionic Polymerization | |

| |

| |

| |

Block Copolymers | |

| |

| |

| |

End-Functional Polymers | |

| |

| |

| |

Regular Branched Architectures | |

| |

| |

| |

Cationic Polymerization | |

| |

| |

| |

Aspects of Cationic Polymerization | |

| |

| |

| |

Living Cationic Polymerization | |

| |

| |

| |

Controlled Radical Polymerization | |

| |

| |

| |

General Principles of Controlled Radical Polymerization | |

| |

| |

| |

Particular Realizations of Controlled Radical Polymerization | |

| |

| |

| |

Atom Transfer Radical Polymerization (ATRP) | |

| |

| |

| |

Stable Free-Radical Polymerization (SFRP) | |

| |

| |

| |

Reversible Addition-Fragmentation Transfer (RAFT) Polymerization | |

| |

| |

| |

Polymerization Equilibrium | |

| |

| |

| |

Ring-Opening Polymerization (ROP) | |

| |

| |

| |

General Aspects | |

| |

| |

| |

Specific Examples of Living Ring-Opening Polymerizations | |

| |

| |

| |

Poly(ethylene oxide) | |

| |

| |

| |

Polylactide | |

| |

| |

| |

Poly(dimethylsiloxane) | |

| |

| |

| |

Ring-Opening Metathesis Polymerization (ROMP) | |

| |

| |

| |

Dendrimers | |

| |

| |

| |

Chapter Summary | |

| |

| |

Problems | |

| |

| |

References | |

| |

| |

Further Readings | |

| |

| |

| |

Copolymers, Microstructure, and Stereoregularity | |

| |

| |

| |

Introduction | |

| |

| |

| |

Copolymer Composition | |

| |

| |

| |

Rate Laws | |

| |

| |

| |

Composition versus Feedstock | |

| |

| |

| |

Reactivity Ratios | |

| |

| |

| |

Effects of r Values | |

| |

| |

| |

Relation of Reactivity Ratios to Chemical Structure | |

| |

| |

| |

Resonance and Reactivity | |

| |

| |

| |

A Closer Look at Microstructure | |

| |

| |

| |

Sequence Distributions | |

| |

| |

| |

Terminal and Penultimate Models | |

| |

| |

| |

Copolymer Composition and Microstructure: Experimental Aspects | |

| |

| |

| |

Evaluating Reactivity Ratios from Composition Data | |

| |

| |

| |

Spectroscopic Techniques | |

| |

| |

| |

Sequence Distribution: Experimental Determination | |

| |

| |

| |

Characterizing Stereoregularity | |

| |

| |

| |

A Statistical Description of Stereoregularity | |

| |

| |

| |

Assessing Stereoregularity by Nuclear Magnetic Resonance | |

| |

| |

| |

Ziegler-Natta Catalysts | |

| |

| |

| |

Single-Site Catalysts | |

| |

| |

| |

Chapter Summary | |

| |

| |

Problems | |

| |

| |

References | |

| |

| |

Further Readings | |

| |

| |

| |

Polymer Conformations | |

| |

| |

| |

Conformations, Bond Rotation, and Polymer Size | |

| |

| |

| |

Average End-to-End Distance for Model Chains | |

| |

| |

| |

The Freely Jointed Chain | |

| |

| |

| |

The Freely Rotating Chain | |

| |

| |

| |

Hindered Rotation Chain | |

| |

| |

| |

Characteristic Ratio and Statistical Segment Length | |

| |

| |

| |

Semiflexible Chains and the Persistence Length | |

| |

| |

| |

Persistence Length of Flexible Chains | |

| |

| |

| |

Worm-Like Chains | |

| |

| |

| |

Radius of Gyration | |

| |

| |

| |

Spheres, Rods, and Coils | |

| |

| |

| |

Distributions for End-to-End Distance and Segment Density | |

| |

| |

| |

Distribution of the End-to-End Vector | |

| |

| |

| |

Distribution of the End-to-End Distance | |

| |

| |

| |

Distribution about the Center of Mass | |

| |

| |

| |

Self-Avoiding Chains: A First Look | |

| |

| |

| |

Chapter Summary | |

| |

| |

Problems | |

| |

| |

References | |

| |

| |

Further Readings | |

| |

| |

| |

Thermodynamics of Polymer Solutions | |

| |

| |

| |

Review of Thermodynamic and Statistical Thermodynamic Concepts | |

| |

| |

| |

Regular Solution Theory | |

| |

| |

| |

Regular Solution Theory: Entropy of Mixing | |

| |

| |

| |

Regular Solution Theory: Enthalpy of Mixing | |

| |

| |

| |

Flory-Huggins Theory | |

| |

| |

| |

Flory-Huggins Theory: Entropy of Mixing by a Quick Route | |

| |

| |

| |

Flory-Huggins Theory: Entropy of Mixing by a Longer Route | |

| |

| |

| |

Flory-Huggins Theory: Enthalpy of Mixing | |

| |

| |

| |

Flory-Huggins Theory: Summary of Assumptions | |

| |

| |

| |

Osmotic Pressure | |

| |

| |

| |

Osmotic Pressure: General Case | |

| |

| |

| |

Number-Average Molecular Weight | |

| |

| |

| |

Osmotic Pressure: Flory-Huggins Theory | |

| |

| |

| |

Phase Behavior of Polymer Solutions | |

| |

| |

| |

Overview of the Phase Diagram | |

| |

| |

| |

Finding the Binodal | |

| |

| |

| |

Finding the Spinodal | |

| |

| |

| |

Finding the Critical Point | |

| |

| |

| |

Phase Diagram from Flory-Huggins Theory | |

| |

| |

| |

What's in [chi]? | |

| |

| |

| |

[chi] from Regular Solution Theory | |

| |

| |

| |

[chi] from Experiment | |

| |

| |

| |

Further Approaches to [chi] | |

| |

| |

| |

Excluded Volume and Chains in a Good Solvent | |

| |

| |

| |

Chapter Summary | |

| |

| |

Problems | |

| |

| |

References | |

| |

| |

Further Readings | |

| |

| |

| |

Light Scattering by Polymer Solutions | |

| |

| |

| |

Introduction: Light Waves | |

| |

| |

| |

Basic Concepts of Scattering | |

| |

| |

| |

Scattering from Randomly Placed Objects | |

| |

| |

| |

Scattering from a Perfect Crystal | |

| |

| |

| |

Origins of Incoherent and Coherent Scattering | |

| |

| |

| |

Bragg's Law and the Scattering Vector | |

| |

| |

| |

Scattering by an Isolated Small Molecule | |

| |

| |

| |

Scattering from a Dilute Polymer Solution | |

| |

| |

| |

The Form Factor and the Zimm Equation | |

| |

| |

| |

Mathematical Expression for the Form Factor | |

| |

| |

| |

Form Factor for Isotropic Solutions | |

| |

| |

| |

Form Factor as qR[subscript g][Right Arrow]0 | |

| |

| |

| |

Zimm Equation | |

| |

| |

| |

Zimm Plot | |

| |

| |

| |

Scattering Regimes and Particular Form Factors | |

| |

| |

| |

Experimental Aspects of Light Scattering | |

| |

| |

| |

Instrumentation | |

| |

| |

| |

Calibration | |

| |

| |

| |

Samples and Solutions | |

| |

| |

| |

Refractive Index Increment | |

| |

| |

| |

Chapter Summary | |

| |

| |

Problems | |

| |

| |

References | |

| |

| |

Further Readings | |

| |

| |

| |

Dynamics of Dilute Polymer Solutions | |

| |

| |

| |

Introduction: Friction and Viscosity | |

| |

| |

| |

Stokes' Law and Einstein's Law | |

| |

| |

| |

Viscous Forces on Rigid Spheres | |

| |

| |

| |

Suspension of Spheres | |

| |

| |

| |

Intrinsic Viscosity | |

| |

| |

| |

General Considerations | |

| |

| |

| |

Mark-Houwink Equation | |

| |

| |

| |

Measurement of Viscosity | |

| |

| |

| |

Poiseuille Equation and Capillary Viscometers | |

| |

| |

| |

Concentric Cylinder Viscometers | |

| |

| |

| |

Diffusion Coefficient and Friction Factor | |

| |

| |

| |

Tracer Diffusion and Hydrodynamic Radius | |

| |

| |

| |

Mutual Diffusion and Fick's Laws | |

| |

| |

| |

Dynamic Light Scattering | |

| |

| |

| |

Hydrodynamic Interactions and Draining | |

| |

| |

| |

Size Exclusion Chromatography (SEC) | |

| |

| |

| |

Basic Separation Process | |

| |

| |

| |

Separation Mechanism | |

| |

| |

| |

Two Calibration Strategies | |

| |

| |

| |

Limitations of Calibration by Standards | |

| |

| |

| |

Universal Calibration | |

| |

| |

| |

Size Exclusion Chromatography Detectors | |

| |

| |

| |

RI Detector | |

| |

| |

| |

UV-Vis Detector | |

| |

| |

| |

Light Scattering Detector | |

| |

| |

| |

Viscometer | |

| |

| |

| |

Chapter Summary | |

| |

| |

Problems | |

| |

| |

References | |

| |

| |

Further Readings | |

| |

| |

| |

Networks, Gels, and Rubber Elasticity | |

| |

| |

| |

Formation of Networks by Random Cross-Linking | |

| |

| |

| |

Definitions | |

| |

| |

| |

Gel Point | |

| |

| |

| |

Polymerization with Multifunctional Monomers | |

| |

| |

| |

Calculation of the Branching Coefficient | |

| |

| |

| |

Gel Point | |

| |

| |

| |

Molecular-Weight Averages | |

| |

| |

| |

Elastic Deformation | |

| |

| |

| |

Thermodynamics of Elasticity | |

| |

| |

| |

Equation of State | |

| |

| |

| |

Ideal Elastomers | |

| |

| |

| |

Some Experiments on Real Rubbers | |

| |

| |

| |

Statistical Mechanical Theory of Rubber Elasticity: Ideal Case | |

| |

| |

| |

Force to Extend a Gaussian Chain | |

| |

| |

| |

Network of Gaussian Strands | |

| |

| |

| |

Modulus of the Gaussian Network | |

| |

| |

| |

Further Developments in Rubber Elasticity | |

| |

| |

| |

Non-Gaussian Force Law | |

| |

| |

| |

Front Factor | |

| |

| |

| |

Network Defects | |

| |

| |

| |

Mooney-Rivlin Equation | |

| |

| |

| |

Swelling of Gels | |

| |

| |

| |

Modulus of a Swollen Rubber | |

| |

| |

| |

Swelling Equilibrium | |

| |

| |

| |

Chapter Summary | |

| |

| |

Problems | |

| |

| |

References | |

| |

| |

Further Readings | |

| |

| |

| |

Linear Viscoelasticity | |

| |

| |

| |

Basic Concepts | |

| |

| |

| |

Stress and Strain | |

| |

| |

| |

Viscosity, Modulus, and Compliance | |

| |

| |

| |

Viscous and Elastic Responses | |

| |

| |

| |

Response of the Maxwell and Voigt Elements | |

| |

| |

| |

Transient Response: Stress Relaxation | |

| |

| |

| |

Transient Response: Creep | |

| |

| |

| |

Dynamic Response: Loss and Storage Moduli | |

| |

| |

| |

Dynamic Response: Complex Modulus and Complex Viscosity | |

| |

| |

| |

Boltzmann Superposition Principle | |

| |

| |

| |

Bead-Spring Model | |

| |

| |

| |

Ingredients of the Bead-Spring Model | |

| |

| |

| |

Predictions of the Bead-Spring Model | |

| |

| |

| |

Zimm Model for Dilute Solutions, Rouse Model for Unentangled Melts | |

| |

| |

| |

Phenomenology of Entanglement | |

| |

| |

| |

Rubbery Plateau | |

| |

| |

| |

Dependence of M[subscript e] on Molecular Structure | |

| |

| |

| |

Reptation Model | |

| |

| |

| |

Reptation Model: Longest Relaxation Time and Diffusivity | |

| |

| |

| |

Reptation Model: Viscoelastic Properties | |

| |

| |

| |

Reptation Model: Additional Relaxation Processes | |

| |

| |

| |

Aspects of Experimental Rheometry | |

| |

| |

| |

Shear Sandwich and Cone and Plate Rheometers | |

| |

| |

| |

Further Comments about Rheometry | |

| |

| |

| |

Chapter Summary | |

| |

| |

Problems | |

| |

| |

References | |

| |

| |

Further Readings | |

| |

| |

| |

Glass Transition | |

| |

| |

| |

Introduction | |

| |

| |

| |

Definition of a Glass | |

| |

| |

| |

Glass and Melting Transitions | |

| |

| |

| |

Thermodynamic Aspects of the Glass Transition | |

| |

| |

| |

First-Order and Second-Order Phase Transitions | |

| |

| |

| |

Kauzmann Temperature | |

| |

| |

| |

Theory of Gibbs and DiMarzio | |

| |

| |

| |

Locating the Glass Transition Temperature | |

| |

| |

| |

Dilatometry | |

| |

| |

| |

Calorimetry | |

| |

| |

| |

Dynamic Mechanical Analysis | |

| |

| |

| |

Free Volume Description of the Glass Transition | |

| |

| |

| |

Temperature Dependence of the Free Volume | |

| |

| |

| |

Free Volume Changes Inferred from the Viscosity | |

| |

| |

| |

Williams-Landel-Ferry Equation | |

| |

| |

| |

Time-Temperature Superposition | |

| |

| |

| |

Factors that Affect the Glass Transition Temperature | |

| |

| |

| |

Dependence on Chemical Structure | |

| |

| |

| |

Dependence on Molecular Weight | |

| |

| |

| |

Dependence on Composition | |

| |

| |

| |

Mechanical Properties of Glassy Polymers | |

| |

| |

| |

Basic Concepts | |

| |

| |

| |

Crazing, Yielding, and the Brittle-to-Ductile Transition | |

| |

| |

| |

Role of Chain Stiffness and Entanglements | |

| |

| |

| |

Chapter Summary | |

| |

| |

Problems | |

| |

| |

References | |

| |

| |

Further Readings | |

| |

| |

| |

Crystalline Polymers | |

| |

| |

| |

Introduction and Overview | |

| |

| |

| |

Structure and Characterization of Unit Cells | |

| |

| |

| |

Classes of Crystals | |

| |

| |

| |

X-Ray Diffraction | |

| |

| |

| |

Examples of Unit Cells | |

| |

| |

| |

Thermodynamics of Crystallization: Relation of Melting Temperature to Molecular Structure | |

| |

| |

| |

Structure and Melting of Lamellae | |

| |

| |

| |

Surface Contributions to Phase Transitions | |

| |

| |

| |

Dependence of T[subscript m] on Lamellar Thickness | |

| |

| |

| |

Dependence of T[subscript m] on Molecular Weight | |

| |

| |

| |

Experimental Characterization of Lamellar Structure | |

| |

| |

| |

Kinetics of Nucleation and Growth | |

| |

| |

| |

Primary Nucleation | |

| |

| |

| |

Crystal Growth | |

| |

| |

| |

Morphology of Semicrystalline Polymers | |

| |

| |

| |

Spherulites | |

| |

| |

| |

Nonspherulitic Morphologies | |

| |

| |

| |

Kinetics of Bulk Crystallization | |

| |

| |

| |

Avrami Equation | |

| |

| |

| |

Kinetics of Crystallization: Experimental Aspects | |

| |

| |

| |

Chapter Summary | |

| |

| |

Problems | |

| |

| |

References | |

| |

| |

Further Readings | |

| |

| |

Appendix | |

| |

| |

| |

Series Expansions | |

| |

| |

| |

Summation Formulae | |

| |

| |

| |

Transformation to Spherical Coordinates | |

| |

| |

| |

Some Integrals of Gaussian Functions | |

| |

| |

| |

Complex Numbers | |

| |

| |

Index | |