Polymer Chemistry

ISBN-10: 1574447793

ISBN-13: 9781574447798

Edition: 2nd 2007 (Revised)

List price: $115.95
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Written by well-established professors in the field, Polymer Chemistry, Second Edition provides a well-rounded and articulate examination of polymer properties at the molecular level. It focuses on fundamental principles based on underlying chemical structures, polymer synthesis, characterization, and properties. Consistent with the previous edition, the authors emphasize the logical progression of concepts, rather than presenting just a catalog of facts. The book covers topics that appear prominently in current polymer science journals. It also provides mathematical tools as needed, and fully derived problems for advanced calculations. This new edition integrates new theories and experiments made possible by advances in instrumentation. It adds new chapters on controlled polymerization and chain conformations while expanding and updating material on topics such as catalysis and synthesis, viscoelasticity, rubber elasticity, glass transition, crystallization, solution properties, thermodynamics, and light scattering. Polymer Chemistry, Second Edition offers a logical presentation of topics that can be scaled to meet the needs of introductory as well as more advanced courses in chemistry, materials science, and chemical engineering.
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Book details

List price: $115.95
Edition: 2nd
Copyright year: 2007
Publisher: CRC Press LLC
Publication date: 2/15/2007
Binding: Hardcover
Pages: 608
Size: 7.25" wide x 10.25" long x 1.25" tall
Weight: 3.168

Introduction to Chain Molecules
How Big Is Big?
Molecular Weight
Spatial Extent
Linear and Branched Polymers, Homopolymers, and Copolymers
Branched Structures
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
Further Readings
Step-Growth Polymerization
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
Stoichiometric Imbalance
Chapter Summary
Further Readings
Chain-Growth Polymerization
Chain-Growth and Step-Growth Polymerizations: Some Comparisons
Initiation Reactions
Fate of Free Radicals
Kinetics of Initiation
Photochemical Initiation
Temperature Dependence of Initiation Rates
Combination and Disproportionation
Effect of Termination on Conversion to Polymer
Stationary-State Radical Concentration
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
Further Readings
Controlled Polymerization
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)
Ring-Opening Metathesis Polymerization (ROMP)
Chapter Summary
Further Readings
Copolymers, Microstructure, and Stereoregularity
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
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
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
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
Samples and Solutions
Refractive Index Increment
Chapter Summary
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
Chapter Summary
Further Readings
Networks, Gels, and Rubber Elasticity
Formation of Networks by Random Cross-Linking
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
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
Further Readings
Glass Transition
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
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
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
Nonspherulitic Morphologies
Kinetics of Bulk Crystallization
Avrami Equation
Kinetics of Crystallization: Experimental Aspects
Chapter Summary
Further Readings
Series Expansions
Summation Formulae
Transformation to Spherical Coordinates
Some Integrals of Gaussian Functions
Complex Numbers
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