Free download Polymer Chemistry By Paul C. Hiemenz Second Edition

2nd Edition

Authors of:  Polymer Chemistry By Paul C. Hiemenz Second Edition

Paul C. Hiemenz

Timothy P. Lodge

Table of Contents in Polymer Chemistry By Paul C. Hiemenz Second Edition

Introduction to Chain Molecules  

1. 1 Introduction  

1.2 How Big Is Big?  

1.2.1 Molecular Weight  

1.2.2 Spatial Extent  

1.3 Linear and Branched Polymers, Homopolymers, and Copolymers  

1.3.1 Branched Structures  

1 .3.2 Copolymers  

1.4 Addition, Condensation, and Natural Polymers  

1.4.1 Addition and Condensation Polymers  

1.4.2 Natural Polymers  

1.5 Polymer Nomenclature  

1.6 Structural Isomerism  

1.6.1 Positional Isomerism

1.6.2 Stereo Isomerism  

1.6.3 Geometrical Isomerism  

1.7 Molecular Weights and Molecular Weight Averages  

1.7.1 Number-, Weight—, and z—Average Molecular Weights  

1.7.2 Polydispersity Index and Standard Deviation  

1.7.3 Examples of Distributions  

1.8 Measurement of Molecular Weight

1.8.1 General Considerations  

1.8.2 End Group Analysis  

1.8.3 MALDI Mass Spectrometry  

1.9 Preview of Things to Come

1.10 Chapter Summary  

Problems  

References  

Further Readings  

Step-Growth Polymerization  

2.1 Introduction  

2.2 Condensation Polymers: One Step at a Time  

2.2.1 Classes of Step—Growth Polymers  

2.2.2 First Look at the Distribution of Products  

2.2.3 A First Look at Reactivity and Reaction Rates  

2.3 Kinetics of Step—Growth Polymerization

2.3.1 Catalyzed Step—Growth Reactions  

2.3.2 How Should Experimental Data Be Compared with

Theoretical Rate Laws?  

2.3.3 Uncatalyzed Step-Growth Reactions  

2.4 Distribution of Molecular Sizes  

2.4.1 Mole Fractions of Species  

2.4.2 Weight Fractions of Species  

2.5 Polyesters  

2.6 Polyamides  

2.7 Stoichiometric Imbalance  

2.8 Chapter Summary  

Problems  

References  

FurtherReadings

Chain-Growth Polymerization

3.1 Introduction  

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

3.3 Initiation  

3.3.1 Initiation Reactions  

3.3.2 Fate of Free Radicals  

3.3.3 Kinetics of Initiation  

3.3.4 Photochemical Initiation

3.3.5 Temperature Dependence of Initiation  

3.4 Termination  

3.4.1 Combination and Disproportionation  

3.4.2 Effect of Termination on Conversion to Polymer  

3.4.3 Stationary-State Radical Concentration  

3.5 Propagation  

3.5.1 Rate Laws for Propagation  

3.5.2 Temperature Dependence of Propagation Rates  

3.5.3 Kinetic Chain  

3.6 Radical Lifetime  

3.7 Distribution of Molecular  

3.7.1 Distribution of i—mers: Termination by Disproportionation  

3.7.2 Distribution of i-mers: Termination by Combination  

3.8 Chain Transfer  

3.8.1 Chain Transfer Reactions  

3.8.2 Evaluation of Chain Transfer Constants  

3.8.3 Chain Transfer to Polymer  

3.8.4 Suppressing Polymerization  

3.9 Chapter Summary  

Problems  

References  

Further Readings  

4 Controlled Polymerization  

4.1 Introduction  

4.2 Poisson Distribution for an Ideal Living Polymerization  

4.2.1 Kinetic Scheme  

4.2.2 Breadth of the Poisson Distribution  

4.3 Anionic Polymerization  

4.4 Block Copolymers, End—Functional Polymers, and Branched

Polymers by Anionic  

4.4.1 Block Copolymers  

4.4.2 End-Functional Polymers  

4.4.3 Regular Branched Architectures  

4.5 Cationic Polymerization  

4.5.1 Aspects of Cationic Polymerization  

4.5.2 Living Cationic Polymerization  

4.6 Controlled Radical Polymerization  

4.6.1 General Principles of Controlled Radical Polymerization

4.6.2 Particular Realizations of Controlled Radical Polymerization  

4.6.2.1 Atom Transfer Radical Polymerization (ATRP)

4.6.2.2 Stable Free-Radical Polymerization (SFRP)  

4.6.2.3 Reversible Addition-Fragmentation Transfer (RAFT)

Polymerization  

4.7 Polymerization Equilibrium

4.8 Ring-Opening Polymerization (ROP)  

4.8.1 General Aspects  

4.8.2 Specific Examples of Living Ring—Opening Polymerizations  

4.8.2.1 Poly(ethy1ene oxide)  

4.8.2.2 Polylactide

4.8.2.3 Poly(dimethylsiloxane)  

4.8.2.4 Ring-Opening Metathesis Polymerization (ROMP)  

4.9 Dendrimers  

4.10 Chapter Summary  

Problems  

References  

Further Readings  

5 Copolymers, Microstructure, and Stereoregularity

5.1 Introduction  

5.2 Copolymer Composition  

5.2.1 Rate Laws  

5.2.2 Composition versus Feedstock  

5.3 Reactivity Ratios  

5.3.1 Effects of r Values  

5.3.2 Relation of Reactivity Ratios to Chemical Structure

5.4 Resonance and Reactivity  

5.5 A Closer Look at Microstructure  

5.5.1 Sequence Distributions  

5.5.2 Terminal and Penultimate Models  

5.6 COpolymer Composition and Microstructure: Experimental Aspects  

5.6.1 Evaluating Reactivity Ratios from Composition Data  

5.6.2 Spectroscopic Techniques  

5.6.3 Sequence Distribution: Experimental Determination  

5.7 Characterizing Stereoregularity  

5.8 A Statistical Description of Stereoregularity  

5.9 Assessing Stereoregularity by Nuclear Magnetic Resonance  

5.10 Ziegler—Natta Catalysts  

5.11 Single-Site Catalysts  

5.12 Chapter Summary  

Problems  

References  

Further Readings  

Polymer Conformations  

6.1 Conformations, Bond Rotation, and Polymer Size  

Thermodynamics of Polymer Solutions  

7.1 Review of Thermodynamic and Statistical Thermodynamic Concepts  

8 Light Scattering by Polymer Solutions  

9 Dynamics of Dilute Polymer Solutions  

Formation of Networks by Random Cross-Linking  

10.1.1 Definitions  

Linear Viscoelasticity  

11.1 Basic Concepts  

Glass Transition  

12.1 Introduction  

Crystalline Polymers

13.1 Introduction and Overview  

Appendix  

A.l Series Expansions  

A2 Summation Formulae  

A3 Transformation to Spherical Coordinates  

A.4 Some Integrals of Gaussian Functions  

A5 Complex Numbers  

Index

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