3rd Edition
Polymers Chemistry and Physics of Modern Materials, Third Edition
Extensively revised and updated to keep abreast of recent advances, Polymers: Chemistry and Physics of Modern Materials, Third Edition continues to provide a broad-based, high-information text at an introductory, reader-friendly level that illustrates the multidisciplinary nature of polymer science. Adding or amending roughly 50% of the material, this new edition strengthens its aim to contribute a comprehensive treatment by offering a wide and balanced selection of topics across all aspects of the chemistry and physics of polymer science, from synthesis and physical properties to applications.
Although the basics of polymer science remain unchanged, significant discoveries in the area of control over molecular weight, macromolecular structure and architecture, and the consequent ability to prepare materials with specific properties receive extensive mention in the third edition. Expanded chapters include controlled radical polymerizations, metallocene chemistry, and the preparation of block and graft copolymers, as well as multiarmed and dendritic structures. Reflecting the growth of polymer applications in industry, the book presents detailed examples to illustrate polymer use in electronic, biological, and medical settings. The authors introduce new understandings of rheological behavior and replace old and outmoded methods of polymer characterization with new and up-to-date techniques. Also new to this edition are a series of problems at the end of each chapter that will test whether the reader has understood the various points and in some cases expand on that knowledge. An accompanying solutions manual is also available for qualifying course adoptions.
Offering the highest quality, comprehensive coverage of polymer science in an affordable, accessible format, Polymers: Chemistry and Physics of Modern Materials, Third Edition continues to provide undergraduate and graduate students and professors with the most complete and current coverage of modern polymer science.
Birth of a Concept
Some Basic Definitions
Synthesis of Polymers
Nomenclature
Average Molar Masses and Distributions
Size and Shape
Configuration
The Glass Transition Temperature Tg and the Melting Temperature Tm
Elastomers, Fibers, and Plastics
Fiber-Forming Polymers
Plastics
Thermosetting Polymers
Elastomers
Step-Growth Polymerization
General Reactions
Reactivity of Functional Groups
Carothers Equation
Control of the Molar Mass
Stoichiometric Control of Mn
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
Free-Radical Addition Polymerization
Addition Polymerization
Choice of Initiators
Free-Radical Polymerization
Initiators
Chain Growth
Termination
Steady-State Kinetics
High-Conversion Bulk Polymerizations
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 of Vinyl Chloride
The Kinetics of CRP Processes
Application to Experimental Data
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
Metal Alkyl Initiators
Solvent and Gegen Ion Effects
Anionic Ring-opening Polymerization
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
The Q-e Scheme
Alternating Copolymers
Block Copolymer Synthesis
Graft Copolymer Synthesis
Statistical and Gradient Copolymers
Complex Molecular Architectures
Dendrimers
Polymer Stereochemistry
Architecture
Orientation
Configuration
Geometric Isomerism
Conformation of Stereoregular Polymers
Factors Influencing Stereoregulation
Homogeneous Stereospecific Cationic Polymerizations
Homogeneous Stereoselective Anionic Polymerizations
Homogeneous Diene Polymerization
Summary
Polymerization Reactions Initiated by Metal Catalysts and Transfer Reactions
Polymerization Using Ziegler-Natta Catalysts
Nature of 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
Concluding Remarks
Polymers in Solution
Thermodynamics of Polymer Solutions
Ideal Mixtures of Small Molecules
Nonideal Solutions
Flory-Huggins Theory: Entropy of Mixing
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
Polymer Characterization - Molar Masses
Introduction
Molar Masses, Molecular Weights, and SI Units
Number-Average Molar Mass Mn
End-Group Assay
Colligative Properties of Solutions
Osmotic Pressure
Light Scattering
Dynamic Light Scattering
Viscosity
Gel Permeation Chromatography
Maldi
Polymer Characterization - Chain Dimensions, Structures, and Morphology
Average Chain Dimensions
Freely Jointed Chain Model
Short-range Effects
Chain Stiffness
Treatment of Dilute Solution Data
Nuclear Magnetic Resonance (NMR)
Infrared Spectroscopy
Thermal Analysis
Wide-Angle and Small-Angle Scattering
Microscopy
The Crystalline State and Partially Ordered Structures
Introduction
Mechanism of Crystallization
Temperature and Growth Rate
Melting
Thermodynamic Parameters
Crystalline Arrangement of Polymers
Morphology and Kinetics
Morphology
Kinetics of Crystallization
Block Copolymers
Historical Development of Polymer Liquid Crystals
Liquid Crystalline Phases
Identification of the Mesophases
Lyotropic Main-Chain Liquid Crystalline Polymers
Thermotropic Main-Chain Liquid Crystal Polymers
Side-Chain Liquid Crystalline Polymers
Chiral Nematic Liquid Crystal Polymers
The Glassy State and Glass Transition
The Amorphous State
The Glassy State
Relaxation Processes in the Glassy State
Glass Transition Region
Theoretical Treatments
Dependence of Tg on Molar Mass
Structural Relaxation and Physical Aging
Rheology and Mechanical Properties
Introduction to Rheology
The Five Regions of Viscoelastic Behavior
The Viscous Region
Mechanical Properties
Mechanical Models Describing Viscoelasticity
Linear Viscoelastic Behavior of Amorphous Polymers
Dynamic Mechanical and Dielectric Thermal Analysis
Time-Temperature Superposition Principle
Dynamic Viscosity
A Molecular Theory for Viscoelasticity
The Reptation Model
The Elastomeric State
General Introduction
Experimental Vulcanization
Properties of Elastomers
Thermodynamic Aspects of Rubberlike Elasticity
Nonideal Elastomers
Distribution Function for Polymer Conformation
Statistical Approach
Swelling of Elastomeric Networks
Network Defects
Resilience of Elastomers
Structure-Property Relations
General Considerations
Control of Tm and Tg
Relation between Tm andTg
Random Copolymers
Dependence of Tm andTg on Copolymer Composition
Block Copolymers
Plasticizers
Crystallinity and Mechanical Response
Application to Fibers, Elastomers, and Plastics
Fibers
Aromatic Polyamides
Polyethylene
Elastomers and Cross-Linked Networks
Plastics
High-temperature Speciality Polymers
Carbon Fibers
Concluding Remarks
Polymers for the Electronics Industry
Introduction
Polymer Resists for IC Fabrication
The Lithographic Process
Polymer Resists
Photolithography
Electron Beam Sensitive Resists
X-ray and Ion Sensitive Resists
Electroactive Polymers
Conduction Mechanisms
Preparation of Conductive Polymers
Polyacetylene
Poly(P-phenylene)
Polyheterocyclic Systems
Polyaniline
Poly(Phenylene Sulfide)
Poly(1,6-heptadiyne)
Applications
Photonic Applications
Light-Emitting Polymers
Nonlinear Optics
Langmuir-Blodgett Films
Optical Information Storage
Thermorecording on Liquid Crystalline Polymers
Index
Biography
J.M.G. Cowie, Valeria Arrighi
". . . continues the tradition of a well-known respected textbook . . ."
– Mark Moloney, Chemistry Research Laboratory, University of Oxford, in Reviews, June 2008, Vol. 9, No. 16, Issue 1
