Polymer Science: A Comprehensive Reference

1st Edition - June 2, 2012
Editors: Martin Moeller, Krzysztof Matyjaszewski
Language: English
Hardback ISBN:
9 7 8 - 0 - 4 4 4 - 5 3 3 4 9 - 4
eBook ISBN:
9 7 8 - 0 - 0 8 - 0 8 7 8 6 2 - 1

The progress in polymer science is revealed in the chapters of Polymer Science: A Comprehensive Reference, Ten Volume Set. In Volume 1, this is reflected in the improved unders… Read more

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The progress in polymer science is revealed in the chapters of Polymer Science: A Comprehensive Reference, Ten Volume Set. In Volume 1, this is reflected in the improved understanding of the properties of polymers in solution, in bulk and in confined situations such as in thin films. Volume 2 addresses new characterization techniques, such as high resolution optical microscopy, scanning probe microscopy and other procedures for surface and interface characterization. Volume 3 presents the great progress achieved in precise synthetic polymerization techniques for vinyl monomers to control macromolecular architecture: the development of metallocene and post-metallocene catalysis for olefin polymerization, new ionic polymerization procedures, and atom transfer radical polymerization, nitroxide mediated polymerization, and reversible addition-fragmentation chain transfer systems as the most often used controlled/living radical polymerization methods. Volume 4 is devoted to kinetics, mechanisms and applications of ring opening polymerization of heterocyclic monomers and cycloolefins (ROMP), as well as to various less common polymerization techniques. Polycondensation and non-chain polymerizations, including dendrimer synthesis and various "click" procedures, are covered in Volume 5. Volume 6 focuses on several aspects of controlled macromolecular architectures and soft nano-objects including hybrids and bioconjugates. Many of the achievements would have not been possible without new characterization techniques like AFM that allowed direct imaging of single molecules and nano-objects with a precision available only recently. An entirely new aspect in polymer science is based on the combination of bottom-up methods such as polymer synthesis and molecularly programmed self-assembly with top-down structuring such as lithography and surface templating, as presented in Volume 7. It encompasses polymer and nanoparticle assembly in bulk and under confined conditions or influenced by an external field, including thin films, inorganic-organic hybrids, or nanofibers. Volume 8 expands these concepts focusing on applications in advanced technologies, e.g. in electronic industry and centers on combination with top down approach and functional properties like conductivity. Another type of functionality that is of rapidly increasing importance in polymer science is introduced in volume 9. It deals with various aspects of polymers in biology and medicine, including the response of living cells and tissue to the contact with biofunctional particles and surfaces. The last volume is devoted to the scope and potential provided by environmentally benign and green polymers, as well as energy-related polymers. They discuss new technologies needed for a sustainable economy in our world of limited resources.

Editors-in-Chief

Volume Editors

Editors-in-Chief: Biographies

Editors: Biographies

Preface

Foreword

Permission Acknowledgments

VOLUME 1. Basic Concepts and Polymer Properties

1.01. Basic Concepts and Polymer Properties

1.02. Statistical Description of Chain Molecules

1.02.1 The Main Characteristics of Polymer Chain Structures

1.02.2 Linear Homopolymers: Ideal Chain Models

1.02.3 Living Polymers

1.02.4 Systems of Ideal Polymer Chains in Confined Conditions

1.02.5 Real Polymer Chains with Excluded-Volume Interactions

1.02.6 Long-Range Correlation Effects in Polymer Melts

1.02.7 Concluding Remark

REFERENCES

1.03. Polymer Synthesis

1.03.1 Introduction

1.03.2 Anionic Chain Polymerization of Styrene

1.03.3 Radical Chain Polymerization

1.03.4 Cationic and Metal-Catalyzed Chain Polymerizations

1.03.5 Polymerization Thermodynamics

1.03.6 Chain Copolymerizations

1.03.7 Polymer Stereochemistry

1.03.8 Ring-Opening Polymerization

1.03.9 Step Polymerizations

1.03.10 Nonlinear Polymers

1.03.11 Postpolymerization Functionalization

1.03.12 Summary

REFERENCES

1.04. Static and Dynamic Properties

1.04.1 Introduction

1.04.2 Diversity of Macromolecular Architectures

1.04.3 Dilute Solutions of Linear-Chain Macromolecules

1.04.4 Semidilute Solutions of Chain Macromolecules

1.04.5 Polymer Globules and Phase Separation

1.04.6 Solutions of Star-Branched Macromolecules

1.04.7 Solutions of Comblike Polymers

1.04.8 Dendritic Polymers in Solutions

1.04.9 Randomly Branched Polymers in Solutions

1.04.10 Solutions of Block Copolymers

1.04.11 Concluding Remarks

REFERENCES

1.05. Solutions of Charged Polymers

1.05.1 What Are Charged Polymers and Why Are They Important?

1.05.2 A Model of Charged Chains

1.05.3 Dilute Salt-Free Polyelectrolyte Solutions

1.05.4 Effect of Added Salt on Chain Conformations in Dilute Solutions

1.05.5 Semidilute Polyelectrolyte Solutions

1.05.6 Phase Separation in Polyelectrolyte Solutions

1.05.7 Polyampholyte Solutions

1.05.8 Conclusions and Outlook

REFERENCES

1.06. Viscoelasticity and Molecular Rheology

1.06.1 Introduction

1.06.2 Experimental Techniques and Physical Observables

1.06.3 Unentangled Polymer Models

1.06.4 Entangled Polymer Models

1.06.5 Summary and Outlook

Appendix: Continuous Rouse Model

REFERENCES

1.07. Rubberlike Elasticity

1.07.1 Introduction

1.07.2 Structure of Networks

1.07.3 Molecular Theories of Rubber Elasticity

1.07.4 Phenomenological Theories

1.07.5 Computer Simulations

1.07.6 Swelling of Networks and Responsive Gels

1.07.7 The Enthalpic Component of Rubber Elasticity

1.07.8 Multimodal Elastomers

1.07.9 Liquid-Crystalline Elastomers

1.07.10 Reinforced Elastomers

1.07.11 Characterization Techniques

REFERENCES

1.08. Amorphous Polymers

1.08.1 Introduction

1.08.2 Structure of Amorphous Polymers

1.08.3 Dynamics of Amorphous Polymers

1.08.4 Amorphous Polymers in Nanometer Thin Layers

1.08.5 Conclusions

REFERENCES

1.09. Semicrystalline Polymers

1.09.1 Introduction

1.09.2 Flexible-Chain Polymers

1.09.3 Semirigid Chain Polymers

1.09.4 Large-Scale Supramolecular Structure of Semicrystalline Polymers

REFERENCES

1.10. Liquid Crystalline Polymers

1.10.1 Introduction

1.10.2 Constitution and Structure of Low-Molecular-Mass Liquid Crystals

1.10.3 LC Polymers: General Consideration

1.10.4 Main-Chain LC Polymers

1.10.5 Side-Chain LC Polymers

1.10.6 Properties and Application of Side-Chain LC Polymers

1.10.7 LC Dendrimers with Mesogenic Groups

1.10.8 Liquid Crystals Dispersed in Polymers and LC Composites

1.10.9 Miscellaneous LC Polymers

1.10.10 Conclusion

REFERENCES

1.11. Phase Segregation/Polymer Blends/Microphase Separation

1.11.1 Phase Segregation

1.11.2 Polymer Blends

1.11.3 Block Copolymers

1.11.4 Conclusion

REFERENCES

1.12. Polymer/Colloid Interactions and Soft Polymer Colloids

1.12.1 General Introduction

1.12.2 Depletion Interaction

1.12.3 Star Polymers as Model Soft Sphere Colloids

1.12.4 Responsive Microgels as Model Colloids

REFERENCES

1.13. Polymer Gels

1.13.1 Introduction

1.13.2 Synthesis of Polymer Gels

1.13.3 Subchains and Their Conformations

1.13.4 Elasticity of Polymer Gels

1.13.5 Peculiarities of Ion-Containing Gels

1.13.6 Polyelectrolyte Gels

1.13.7 Manifestation of Ionomer Behavior

1.13.8 Responsive Gels

1.13.9 Some Applications of Superabsorbent Gels

1.13.10 Some Applications of Responsive Gels

REFERENCES

1.14. Chain Conformation and Manipulation

1.14.1 Introduction

1.14.2 Chain Conformation

1.14.3 PEs at Surfaces

1.14.4 Study of Helical Conformations by AFM

1.14.5 Conformation of Polymer Stars

1.14.6 Motion of Single Molecules

1.14.7 Manipulation of Polymer Conformation in Shear Flow

1.14.8 Nanomanipulations with AFM Tip

1.14.9 Chemical Modification of Single Polymer Molecules

1.14.10 Nanodevices from Single Polymer Molecules

1.14.11 Conclusions and Outlook

REFERENCES

1.15. Polymers at Interfaces and Surfaces and in Confined Geometries

1.15.1 Introduction

1.15.2 Polymers at Solid Substrates

1.15.3 Surfaces of One-Component Polymer Liquids and Wetting

1.15.4 Inhomogeneous Polymer Blends

1.15.5 Summary and Outlook

REFERENCES

1.16. Molecular Dynamics Simulations in Polymer Science

1.16.1 Introduction

1.16.2 What Can Molecular Dynamics Do?

1.16.3 Philosophy of Molecular Dynamics

1.16.4 Concepts and Methodologies

1.16.5 Multiscale Simulations: Bridging Different Time and Length Scales

1.16.6 Advanced Simulation Techniques

1.16.7 Concluding Remarks

REFERENCES

1.17. Monte Carlo Simulations in Polymer Science

1.17.1 Introduction: What Monte Carlo Simulations Want to Achieve

1.17.2 Models Used in MC Simulations of Polymers

1.17.3 General Aspects of Dynamic MC Methods

1.17.4 Exploiting the Freedom to Choose Suitable MC Moves

1.17.5 Other MC Methods to Simulate Models for Polymers

1.17.6 Concluding Remarks

REFERENCES

1.18. General Polymer Nomenclature and Terminology

1.18.1 Introduction

1.18.2 A Short History

1.18.3 Projects

1.18.4 Examples of Most Successful Projects

1.18.5 Final Remarks

REFERENCES

VOLUME 2. Polymer Characterization

2.01. Introduction and Perspectives

2.01.1 Introduction

2.01.2 Perspectives

REFERENCES

Characterization of Solutions

2.02. Polymer Properties in Solutions

2.02.1 Introduction

2.02.2 Global Conformations and Statistical Properties

2.02.3 Thermodynamic Properties

2.02.4 Viscosity

2.02.5 Sedimentation and Diffusion

2.02.6 Some Topics

REFERENCES

Characterization by Separation Methods

2.03. Chromatography

2.03.1 Introduction

2.03.2 Principles of Liquid Chromatography of Polymers

2.03.3 Interactive Modes of Polymer Liquid Chromatography

2.03.4 Multidetector Size-Exclusion Chromatography

2.03.5 Coupling of Liquid Chromatography and Spectroscopic Detectors

2.03.6 Two-Dimensional Liquid Chromatography

2.03.7 High-Temperature Interaction Liquid Chromatography

REFERENCES

2.04. Fractionation

2.04.1 Introduction

2.04.2 Fractionation by Liquid–Liquid Phase Separation

2.04.3 Crystallization–Dissolution Fractionation

2.04.4 Field-Flow Fractionation

REFERENCES

Characterization by Spectroscopy

2.05. Mass Spectrometry

2.05.1 History

2.05.2 Principles

2.05.3 Polymer Analysis by MALDI and ESI-TOF MS

2.05.4 Outlook

REFERENCES

2.06. Solution NMR

2.06.1 Introduction

2.06.2 Principles of NMR

2.06.3 Multipulse NMR Experimental Methods

2.06.4 Applications of NMR to Polymer Structure Problems

2.06.5 Conclusions

REFERENCES

2.07. Solid-State NMR of Polymers

2.07.1 Introduction

2.07.2 Fundamentals of Solid-State NMR

2.07.3 Polymer Applications of Solid-State NMR

2.07.4 Conclusions

REFERENCES

2.08. Electron Spin Resonance Spectroscopy

2.08.1 Introduction

2.08.2 Electron Spin Resonance Methods

2.08.3 ESR Imaging

2.08.4 Application of ESR Methods to Polymeric Systems

2.08.5 Conclusions

REFERENCES

2.09. Vibrational Spectroscopy

2.09.1 Introduction

2.09.2 Basic Principles of Vibrational Spectroscopy

2.09.3 Vibrational Spectroscopic Interpretation of the Structure of Polymers

2.09.4 FIR Spectroscopy and Low-Frequency Vibrations

2.09.5 Vibrational Spectroscopy of Polymers Under External Perturbations and in Combination with Other Measurement Techniques

2.09.6 Reaction Monitoring and Process Control by Vibrational Spectroscopy

2.09.7 IR and Raman Spectroscopic Imaging

2.09.8 Calculation of Vibrational Spectra of Polymers*

REFERENCES

Structure Characterization in Fourier Space

2.10. Light Scattering

2.10.1 Introduction

2.10.2 Theoretical Background

2.10.3 Instrumentation and Experimental Practice

2.10.4 Application to the Characterization of Macromolecular Systems

REFERENCES

2.11. Neutron Scattering

2.11.1 Introduction

2.11.2 Methods

2.11.3 Representative SANS Results

2.11.4 Polymer Dynamics

2.11.5 Conclusions

Appendix

REFERENCES

2.12. X-ray Scattering

2.12.1 Introduction

2.12.2 Reciprocal Space and Fourier Transformation

2.12.3 Intensity Distribution and Autocorrelation Function

2.12.4 Scattering from Crystals

2.12.5 Dilute Systems

2.12.6 Ordered Nanostructures: Macrolattices

2.12.7 Layered Structures

2.12.8 SAXS from Two-Phase Systems

2.12.9 Fiber Scattering: Preferred Orientation

2.12.10 Conclusion

REFERENCES

2.13. Combined Small-Angle Scattering for Characterization of Hierarchically Structured Polymer Systems over Nano-to-Micron Meter

2.13.1 Introduction

2.13.2 Artificially Synthesized Cellulose versus Biosynthesized Cellulose

2.13.3 Artificially Synthesized Cellulose Systems

2.13.4 Biosynthesized Cellulose

2.13.5 Perspectives

REFERENCES

2.14. Combined Small-Angle Scattering for Characterization of Hierarchically Structured Polymer Systems over Nano-to-Micron Meter

2.14.1 Introduction

2.14.2 Structural Levels

2.14.3 Unified Function

2.14.4 Hierarchy of Structural Levels

2.14.5 Structural Models and the Unified Function

2.14.6 Examples of Structural Models and the Unified Function

2.14.7 Polydispersity and Asymmetry for Porod Scattering

2.14.8 Restrictions for the Unified Function Parameters

2.14.9 Software for Unified Fits

2.14.10 Conclusion

REFERENCES

2.15. Reflectivity, Off-Specular Scattering, and GI-SAS

2.15.1 Introduction

2.15.2 Grazing-Incidence Kinematics and Coherence

2.15.3 Specular Reflection

2.15.4 Off-Specular Scattering

2.15.5 GI-SAS and Complete Reflectometry

2.15.6 Conclusion

REFERENCES

2.16. Reflectivity, GI-SAS and GI-Diffraction

2.16.1 Introduction

2.16.2 Theories

2.16.3 XR and GIXS Applications in Nanostructured Polymers

2.16.4 Conclusions

REFERENCES

Structure Characterization in Real Space

2.17. Optical Microscopy

2.17.1 Introduction

2.17.2 Conventional Imaging Modes

2.17.3 Polarized Light Microscopy

2.17.4 Digital Microscopy

REFERENCES

2.18. Fluorescence Microscopy, Single Fluorophores and Nano-Reporters, Super-Resolution Far-Field Microscopy

2.18.1 Introduction

2.18.2 A Confocal Single-Molecule Setup

2.18.3 Wide-Field Single-Molecule Microscopy

2.18.4 Single Molecules?

2.18.5 Sample Preparation

2.18.6 Examples of Polymer Studies by Single-Molecule Measurements

2.18.7 Super-Resolution Optical Far-Field Microscopy, Theory, and Applications in Polymer Studies

REFERENCES

2.19. Electron Microscopy of Organic Materials

2.19.1 Introduction

2.19.2 Sample Preparation

2.19.3 Beam Sensitivity of Polymer and Organic Samples

2.19.4 Electron Beam-Induced Structural Transitions in Organic Molecular Crystals

2.19.5 Low-Dose HREM

2.19.6 Molecular Simulations

2.19.7 Low-Voltage Electron Microscope

2.19.8 Dispersed Carbon Nanotubes

2.19.9 Low-Voltage Scanning Electron Microscopy

2.19.10 FIB Imaging of Polymers on Inorganic Substrates

2.19.11 Cryo-TEM Techniques

2.19.12 Aberration-Corrected Microscopy

2.19.13 Dynamic TEM

2.19.14 Conclusions

REFERENCES

2.20. Transmission Electron Microtomography

2.20.1 Introduction

2.20.2 3D Microscopy

2.20.3 Some Basics of Electron Tomography

2.20.4 Recent Developments in TEMT

REFERENCES

2.21. Environmental Scanning Electron Microscopy

2.21.1 Introduction

2.21.2 The Instrument: A Comparison with Conventional SEM

2.21.3 Static Experiments

2.21.4 Dynamic Experiments

2.21.5 Biopolymers and Biofilms

2.21.6 Conclusions

REFERENCES

2.22. Micro X-Ray CT

2.22.1 Introduction

2.22.2 Principle of the X-Ray CT

2.22.3 Micro X-Ray CT with Microfocus X-Ray Generator

2.22.4 Micro X-Ray CT with SR

2.22.5 Use of X-Ray Phase Information

2.22.6 Summary and Outlook

REFERENCES

Surface and Interface Characterization

2.23. Scanning Probe Microscopy of Polymers

2.23.1 Introduction

2.23.2 Experiment in AFM

2.23.3 Imaging of Molecules, Molecular Assemblies, and Processes

2.23.4 Compositional Mapping of Multicomponent Polymer Systems

2.23.5 Toward Quantitative Measurements of Local Properties

REFERENCES

2.24. Adhesion, Friction, and Lubrication between Polymer-Bearing Surfaces

2.24.1 Introduction

2.24.2 Monomeric Fluids Under Confinement

2.24.3 Polymer-Modified Surfaces

2.24.4 Summary and Future Perspective

REFERENCES

2.25. Single-Molecule Detection and Manipulation

2.25.1 Introduction

2.25.2 Instrumentation

2.25.3 Calibration

2.25.4 Data Fitting and Selection

2.25.5 Examples

2.25.6 Outlook

REFERENCES

2.26. Plasmonics

2.26.1 Introduction

2.26.2 Fundamentals of Guided Wave Optics

2.26.3 Observation of Thin Polymer Films

2.26.4 Applications

2.26.5 Conclusion

REFERENCES

2.27. Ion Beam Analysis

2.27.1 Introduction

2.27.2 Applications of IBA in Polymer Science

2.27.3 Technique Development

2.27.4 Outlook for IBA in Polymer Science

REFERENCES

Thermal, Mechanical, Dielectric & Electrical Characterization

2.28. Rheological Characterization of Polymeric Liquids

2.28.1 Basics

2.28.2 Characterization of Homopolymers

2.28.3 Characterization of Multiphase Polymeric Materials

2.28.4 Concluding Remarks

Appendix A General Microscopic Expression of Stress Tensor

REFERENCES

2.29. Mechanical Characterization of Glassy Polymers

2.29.1 Introduction

2.29.2 Phenomenology

2.29.3 Origin of Mobility

2.29.4 Factors Influencing Mobility

2.29.5 Avoiding Localization: The Intrinsic Deformation of Polymers

2.29.6 Competition between Lifetime and Embrittlement

2.29.7 Modeling

2.29.8 Characterization

2.29.9 Multimode Model

2.29.10 Multiprocess Model

2.29.11 Epilogue

Appendix: Simplification to 1D

REFERENCES

2.30. Rheo-Optics

2.30.1 General Outline

2.30.2 Rheo-optics at Mesoscopic Scale

2.30.3 Rheo-optics at the Submolecular Level

2.30.4 General Conclusions and Perspectives

REFERENCES

2.31. Calorimetry

2.31.1 Introduction

2.31.2 Fundamentals and Modes of Operation

2.31.3 Fast Scanning Calorimetry

2.31.4 Selected Applications of Advanced Calorimetry

2.31.5 Summary

REFERENCES

2.32. Dielectric Spectroscopy

2.32.1 Introduction

2.32.2 Theoretical Background

2.32.3 Analysis of Dielectric Spectra

2.32.4 Recent Advances in Dielectrics

2.32.5 Concluding Remarks

REFERENCES

2.33. Conductivity Measurements

2.33.1 Introduction

2.33.2 Electrical Properties of Polymer Materials

2.33.3 Experimental Techniques

REFERENCES

VOLUME 3. Chain Polymerization of Vinyl Monomers

3.01. Introduction and Overview

3.01.1 Introduction

3.01.2 Overview

3.02. Fundamental Aspects of Chain Polymerization

3.02.1 Introduction

3.02.2 The Nobel Prize Award Ceremony Speech of A. Ölander on Behalf of the Nobel Committee

3.02.3 Bodenstein Observation of the First Chain Reactions

3.02.4 Nernst’s Mechanism of the Cl2 + H2 Reaction (Finally Accepted as the Correct One)

3.02.5 Kinetic Scheme of the Fundamental Chain Reaction: Cl2 + H2

3.02.6 Stationary State, Bodenstein Approximation, and Final Solution

3.02.7 Definitions Pertinent to Chain Reactions

3.02.8 Definitions Pertinent to Chain Polymerizations

3.02.9 Two Kinds of Steady States in Chain Polymerizations

3.02.10 Discovery of Living Polymerization by Michael Szwarc

3.02.11 Living Polymerization

3.02.12 Nearly Steady-State Polymerizations: Controlled Polymerizations Involving Quasi-Equilibria between Active and Dormant Species

3.02.13 Second Kind of the Steady State: The Rate of Formation of Active Centers Balanced by the Rate of Their Disappearance. Classical Radical Polymerization

3.02.14 Non-Steady-State Polymerizations

3.02.15 Chain Polymerizations and Structure of Macromolecules

3.02.16 Condensative Chain Polymerizations: Biopolymers

3.02.17 Polymerize Chain Reaction. DNA Syntheses

3.02.18 Conclusions

Appendix: Lifetime and Half-Life: Definitions and Their Relationship

REFERENCES

3.03. Radical Reactivity by Computation and Experiment

3.03.1 Introduction

3.03.2 Radical Stability

3.03.3 Other Important Properties

3.03.4 Tools for Linking Structure to Reactivity

REFERENCES

3.04. Radical Polymerization

3.04.1 Introduction

3.04.2 Initiation

3.04.3 Propagation

3.04.4 Termination

3.04.5 Chain Transfer

3.04.6 Reversible Deactivation Radical Polymerization

REFERENCES

3.05. Controlled and Living Radical Polymerization – Principles and Fundamentals

3.05.1 Introduction

3.05.2 Principles and Classification of LRP Techniques

3.05.3 Kinetic Theory of LRP: Polymerization Rates

3.05.4 Kinetic Theory of LRP: Polydispersities

3.05.5 Nitroxide-Mediated Polymerization

3.05.6 Atom Transfer Radical Polymerization

3.05.7 Degenerative Chain Transfer-Mediated Polymerization

3.05.8 Experiments on Some Newer Systems

3.05.9 Summary on Activation and Deactivation Rate Constants

3.05.10 Conclusions

REFERENCES

3.06. Degenerative Transfer with Alkyl Iodide

3.06.1 Introduction

3.06.2 Alkyl Iodide Transfer Agents Used in Degenerative Transfer Polymerization with Alkyl Iodides

3.06.3 Mechanism and Kinetics of Degenerative Transfer Polymerization with Alkyl Iodide

3.06.4 Other Related Methods

3.06.5 Monomers Used in Degenerative Transfer Polymerization with Iodo-Compounds

3.06.6 Processes

3.06.7 Macromolecular Architectures Prepared by Degenerative Transfer with Iodo-Compounds

3.06.8 Applications of Polymers Prepared by Degenerative Transfer with Iodo-Compounds

3.06.9 Prospects

3.06.10 Conclusions

REFERENCES

3.07. Radical Addition–Fragmentation Chemistry and RAFT Polymerization

3.07.1 Introduction

3.07.2 Compounds Providing Irreversible Addition–Fragmentation Chain Transfer

3.07.3 Compounds Providing Reversible Addition–Fragmentation Chain Transfer

REFERENCES

3.08. Other Degenerative Transfer Systems

3.08.1 Introduction

3.08.2 Background

3.08.3 Organoheteroatom-Mediated LRP

3.08.4 Mechanism

3.08.5 Macromolecular Engineering

3.08.6 Conclusions

REFERENCES

3.09. Cobalt-Catalyzed Chain Transfer Polymerization

3.09.1 Introduction and Overview

3.09.2 Polymerization Mechanism

3.09.3 Catalysts

3.09.4 Monomers for CCT

3.09.5 Applications

3.09.6 Summary

REFERENCES

3.10. Nitroxide-Mediated Polymerization

3.10.1 Introduction

3.10.2 Synthesis of Nitroxides and Alkoxyamines

3.10.3 Features of Nitroxide-Mediated Polymerization

3.10.4 Advanced Architectures and Materials by NMP

3.10.5 Conclusions and Perspectives

REFERENCES

3.11. Organometallic-Mediated Radical Polymerization

3.11.1 Introduction: Discovery of OMRP

3.11.2 Mechanistic Interplays

3.11.3 Tuning the Metal–Carbon Bond Strength

3.11.4 Interplay of Dissociative and Associative Processes

3.11.5 ‘Clean’ OMRP-RT Processes

3.11.6 OMRP-RT versus CCT

3.11.7 Interplay of OMRP-RT and ATRP

3.11.8 Metal Elimination and Recycling

3.11.9 Conclusions and Perspectives

REFERENCES

3.12. Copper-Mediated Atom Transfer Radical Polymerization

3.12.1 Introduction

3.12.2 ATRP Equilibrium

3.12.3 Initiating an ATRP

3.12.4 Removal of Copper

3.12.5 ATRP Thermodynamics and Kinetics

3.12.6 Components/Phenomenology/Process

3.12.7 Control over Polymer Composition

3.12.8 Polymer Topology

3.12.9 Site-Specific Functionality

3.12.10 Hybrid Materials

3.12.11 Applications

3.12.12 Conclusions

REFERENCES

3.13. Transition Metal Complexes for Metal-Catalyzed Atom Transfer Controlled/Living Radical Polymerization

3.13.1 Introduction

3.13.2 Scope of Transition Metal-Catalyzed Living Radical Polymerization

3.13.3 Late Transition Metal Complexes for Living Radical Polymerization

3.13.4 Early Transition Metal Complexes for Living Radical Polymerization

3.13.5 Prospective View of Catalysts for Living Radical Polymerization

REFERENCES

3.14. Vinyl Polymerization in Heterogeneous Systems

3.14.1 Introduction

3.14.2 Vinyl Polymerization in Aqueous Dispersed Systems

3.14.3 Vinyl Polymerization in Nonaqueous Dispersed Systems

3.14.4 Conclusion

REFERENCES

3.15. Cationic Polymerization of Nonpolar Vinyl Monomers

3.15.1 Introduction

3.15.2 Fundamentals of Cationic Polymerization

3.15.3 Monomers

3.15.4 Initiating Systems

3.15.5 Solvent Polarity and Temperature

3.15.6 Controlled Initiation

3.15.7 Living Cationic Polymerization

3.15.8 Functional Polymers by Living Cationic Polymerization

3.15.9 Block Copolymers

3.15.10 Branched and Hyperbranched Polymers

3.15.11 Conclusions

REFERENCES

3.16. Cationic Polymerization of Polar Monomers

3.16.1 Introduction

3.16.2 General Aspects

3.16.3 Living Cationic Polymerization

3.16.4 Design of Initiating Systems for Living Polymerization

3.16.5 Recent Developments in Living Polymerization

3.16.6 New Monomers

3.16.7 Sequence or Shape-Regulated Functional Polymers

3.16.8 Stimuli-Responsive Polymers

REFERENCES

3.17. Anionic Polymerization of Nonpolar Monomers

3.17.1 Introduction to Carbanions, Living Polymerization, and Anionic Polymerization

3.17.2 Initiators, Initiation Mechanisms, and Kinetics

3.17.3 Propagation Kinetics and Mechanisms

3.17.4 Chain Termination Reactions

3.17.5 Chain Transfer Reactions

3.17.6 Stereochemistry

3.17.7 Copolymerization

REFERENCES

3.18. Anionic Polymerization of Protected Functional Monomers

3.18.1 Introduction

3.18.2 Functional Styrene Derivatives

3.18.3 Functional 1,3-Butadiene Derivatives

3.18.4 Functional (Meth)acrylate Derivatives

3.18.5 N-Isopropylacrylamide

3.18.6 Concluding Remarks

REFERENCES

3.19. Anionic Polymerization of Polar Vinyl Monomers

3.19.1 Introduction

3.19.2 Mechanism of the Anionic Polymerization of Alkyl (Meth)acrylates

3.19.3 Anionic Polymerization of Other Acrylic Monomers

3.19.4 Anionic Polymerization of Other Polar Vinyl Monomers

3.19.5 Conclusions

REFERENCES

3.20. Industrial Catalysts for Alkene Polymerization

3.20.1 Catalysts for Polyolefin Production

3.20.2 Historical Development of Commercially Practiced Alkene Polymerization Catalysts

3.20.3 Global Polyolefin Catalyst and Product Markets

3.20.4 Conclusion

REFERENCES

3.21. Metallocene Alkene Polymerization Catalysts

3.21.1 Introduction

3.21.2 Definition of a Metallocene Polymerization Catalyst

3.21.3 General Mechanism

3.21.4 Ethylene Polymerization

3.21.5 1-Alkene Polymerization

3.21.6 Diene Polymerization

3.21.7 Copolymerization

3.21.8 Conclusions

3.21.9 Outlook

REFERENCES

3.22. Chain Shuttling Catalysis and Olefin Block Copolymers

3.22.1 Introduction

3.22.2 Block Copolymers from Living Polymerization

3.22.3 Olefin Block Copolymers from Reversible Chain Transfer

3.22.4 Identifying Reversibility in Chain Transfer

3.22.5 CCTP Characteristics in Single Catalyst Systems

3.22.6 Reactor Choice for OBC Synthesis

3.22.7 Diblock OBCs via Sequential Monomer Addition

3.22.8 Synthesis of OBCs with Dual-Catalyst Systems

3.22.9 Characterization of Olefin Block Copolymers

3.22.10 Olefin Block Copolymer Design and Applications

3.22.11 Functional Polyolefins from CCTP Systems

3.22.12 Conclusion and Outlook

REFERENCES

3.23. Living Transition Metal-Catalyzed Alkene Polymerization

3.23.1 Introduction

3.23.2 Living Olefin Polymerization

3.23.3 Early Metal Olefin Polymerization Catalysts

3.23.4 Non-group 4 Early Metal Polymerization Catalysts

3.23.5 Rare-Earth Metal Catalysts

3.23.6 Late Metal Olefin Polymerization Catalysts

3.23.7 Outlook and Summary

REFERENCES

3.24. Copolymerization of Alkenes and Polar Monomers by Early and Late Transition Metal Catalysts

3.24.1 Introduction

3.24.2 Coordination of Polar Groups to Transition Metals: Challenges for the Copolymerization of Olefins with Polar Comonomers

3.24.3 Methods for the Synthesis of Polar Copolymers with Early Transition Metals

3.24.4 Late Transition Metals in the Copolymerization of Functional and Nonpolar Olefins

3.24.5 Conclusion

REFERENCES

3.25. Alkene/CO Copolymerization

3.25.1 Introduction

3.25.2 Alternating Copolymer of Ethylene and CO

3.25.3 Nonalternating Copolymer of Ethylene and CO

3.25.4 Alternating Copolymerization of Mono-substituted Ethylene and CO

3.25.5 Copolymerization of Imines with Carbon Monoxide

3.25.6 Chemical Transformation of Polyketones

3.25.7 Physical Properties and Industrial Application of the Olefin/CO Copolymers

REFERENCES

3.26. Cycloolefin Polymerization

3.26.1 Introduction

3.26.2 Polycycloolefins: Homopolymerization

3.26.3 Cycloolefin Copolymers

3.26.4 Conclusions

REFERENCES

3.27. Alkyne Polymerization

3.27.1 Introduction

3.27.2 Polymerization Catalysts

3.27.3 Monosubstituted Acetylene Polymers

3.27.4 Disubstituted Acetylene Polymers

REFERENCES

VOLUME 4. Ring-Opening Polymerization and Special Polymerization Processes

4.01. Introduction

4.02. Thermodynamic and Kinetic Polymerizability

4.02.1 Introduction

4.02.2 Major Definitions

4.02.3 Equilibrium and Ceiling (Floor) Temperatures (Te and Tc/Tf)

4.02.4 Methods for Determination of Tc (or [M]e)

4.02.5 Factors Affecting Polymerizability: Enthalpy of Polymerization

4.02.6 Entropy-Driven Polymerization

4.02.7 Nonideal (Real) Systems

4.02.8 Influence of Degree of Polymerization

4.02.9 Influence of Phase Separation

4.02.10 Final Remarks on the Thermodynamic Polymerizability

4.02.11 Kinetic Polymerizability

4.02.12 Kinetic Polymerizability versus Macroions and Macroion Pairs in Propagation

4.02.13 Outlook

REFERENCES

4.03. Living Ring-Opening Olefin Metathesis Polymerization

REFERENCES

4.04. Ring–Chain Equilibria in Ring-Opening Polymerization

4.04.1 Phenomenon of the Ring–Chain Equilibria in Ring-Opening Polymerization

4.04.2 Thermodynamics of the Ring–Chain Equilibria in ROP

4.04.3 Thermodynamics of Ring–Chain Equilibria in Copolymerization

4.04.4 Effects of Pressure and Solvents on the Ring–Chain Equilibria

4.04.5 Kinetics of the Ring–Chain Equilibria in ROP

4.04.6 Ring–Chain Equilibria in Selected ROP Systems

4.04.7 Conclusions and Outlook

REFERENCES

4.05. Equilibrium Copolymerization in Ring-Opening Polymerization

4.05.1 Phenomenon of the Equilibrium Copolymerization in Ring-Opening Polymerization

4.05.2 The Concept of the Equilibrium Copolymerization

4.05.3 Copolymerization Equilibrium

4.05.4 Thermodynamics of Copolymerization

4.05.5 Determination of the Equilibrium Constants on the Basis of the Analysis of the Copolymerization Equilibrium

4.05.6 Selected Examples of the Equilibrium Copolymerization

4.05.7 Conclusions and Outlook

REFERENCES

4.06. Organocatalyzed Ring-Opening Polymerizations

4.06.1 Introduction

4.06.2 Metal-Free Initiated versus Metal-Free Organocatalyzed Polymerizations

4.06.3 Organocatalytic Platforms, Monomer Candidates, and Related Mechanisms

4.06.4 Polymerizations Catalyzed by 4-(Dialkylamino)pyridines

4.06.5 Polymerizations Catalyzed by Amidines

4.06.6 Polymerizations Catalyzed by TUs and TU-Amino Derivatives

4.06.7 Polymerizations using Phosphorus-Based Catalysts: Phosphines and Phosphazenes

4.06.8 Polymerizations Catalyzed by NHCs

4.06.9 Polymerization Catalyzed by Weak, Strong, and ‘Super Strong’ Bronsted Acids

4.06.10 Conclusion

REFERENCES

4.07. Anionic Ring-Opening Polymerization of Epoxides and Related Nucleophilic Polymerization Processes

4.07.1 Introduction

4.07.2 Anionic Epoxide Polymerization Initiated by Alkali Metal Derivatives

4.07.3 Initiation by Organic Bases as Initiators

4.07.4 Coordination Anionic Polymerization

4.07.5 Polymerization Involving Monomer Activation by a Lewis Acid Additive

4.07.6 Summary

REFERENCES

4.08. Cationic Ring-Opening Polymerization of Cyclic Ethers

4.08.1 General Considerations

4.08.2 CROP of Oxiranes

4.08.3 CROP of Oxetanes

4.08.4 CROP of THFs (Oxolanes)

4.08.5 Outlook

REFERENCES

4.09. Stereoselective Ring-Opening Polymerization of Epoxides

4.09.1 Introduction

4.09.2 Basic Concepts in Stereoselective Epoxide Polymerization

4.09.3 Stereoselective Epoxide Polymerization

4.09.4 Conclusion/Outlook

REFERENCES

4.10. Ring-Opening Polymerization of Cyclic Acetals

4.10.1 Introduction

4.10.2 Mechanism of Homogeneous Polymerization of Cyclic Acetals

4.10.3 Heterogeneous Polymerization of 1,3,5-Trioxane

Outlook

REFERENCES

4.11. ROP of Cyclic Esters. Mechanisms of Ionic and Coordination Processes

4.11.1 Introduction

4.11.2 Thermodynamics of ROP of Cyclic Esters

4.11.3 Kinetics of the ROP of Cyclic Esters

4.11.4 Livingness of Polymerization in Processes Initiated with Multivalent Metal Alkoxides

4.11.5 Extent of Molar Mass Control in Processes Initiated with Multivalent Metal Alkoxides

4.11.6 Controlled Polymerization of Cyclic Esters Initiated with Single-Site Metal Alkoxides

4.11.7 Transfer Processes in the Anionic and Coordination Polymerizations of Cyclic Esters

4.11.8 Stereochemically Asymmetric ROP of Cyclic Esters

4.11.9 Conclusions

REFERENCES

4.12. ROP of Cyclic Carbonates and ROP of Macrocycles

4.12.1 Introduction

4.12.2 Synthesis of Cyclic Carbonates

4.12.3 Polymerization of Aliphatic Cyclic Carbonates

4.12.4 Copolymerization of Cyclic Carbonates with Other Heterocyclic Monomers

4.12.5 Polymerization of Cyclic Thiocarbonates

4.12.6 Polymerization of Macrocycles

4.12.7 Conclusions

REFERENCES

4.13. ROP of Cyclic Amines and Sulfides

4.13.1 Introduction

4.13.2 Cyclic Amines

4.13.3 Cyclic Sulfides

4.13.4 Conclusions and Outlook

REFERENCES

4.14. Ring-Opening Polymerization of Cyclic Amides (Lactams)

4.14.1 Introduction

4.14.2 Lactams and Their Polymerizability

4.14.3 Outline of Lactam Polymerization Routes

4.14.4 Hydrolytic Polymerization

4.14.5 Cationic Polymerization

4.14.6 Acidolytic and Aminolytic Polymerizations

4.14.7 Anionic Polymerization

4.14.8 Enzymatic Polymerization

4.14.9 Spontaneous Polymerization

4.14.10 Anionic Polymerization of CL

4.14.11 Anionic Polymerization of Other Lactams

4.14.12 Anionic Copolymers

4.14.13 Industrial Applications

REFERENCES

4.15. Polymerization of Oxazolines

4.15.1 Introduction

4.15.2 Cationic Ring-Opening Polymerization

4.15.3 Ring-Opening Polyaddition

4.15.4 ROPA for Polysaccharide Synthesis

4.15.5 Ring-Opening Polymerizations of Other Oxazoline Derivative Monomers

4.15.6 Sythesis of Functional Polymers via CROP Process and Their Applications

REFERENCES

4.16. Ring-Opening Polymerization of Amino Acid -Carboxyanhydrides

4.16.1 Introduction

4.16.2 Polypeptide Synthesis using NCAs

4.16.3 Copolypeptide Synthesis via ROP

4.16.4 Side-Chain Functionalized Polypeptides

4.16.5 Poly(β-Peptides)

4.16.6 Polypeptide Deprotection and Purification

4.16.7 Conclusions

REFERENCES

4.17. Polymerization of Cyclic Siloxanes, Silanes, and Related Monomers

4.17.1 Monomers Polymerizable by Breaking the Siloxane Bonds

4.17.2 Ring-Opening Polymerization of Cyclic Organosilicon Monomers Not Involving Si–O Bond Cleavage

4.17.3 Final Remarks

REFERENCES

4.18. Ring-Opening Polymerization of Cyclic Phosphorus Monomers

4.18.1 Scope of the Chapter

4.18.2 Polymerization of Cyclic Organophosphorus Compounds

4.18.3 Polyaddition

4.18.4 Transformation of Poly(alkylene phosphate)s

4.18.5 Some Properties and Applications of Poly(alkylene phosphate)s

4.18.6 Polymerization of Cyclic Inorganic P-Containing Compounds

4.18.7 Some Properties and Applications of Linear Poly(organophosphazene)s

4.18.8 Outlook

REFERENCES

4.19. Radical Ring-Opening Polymerization

4.19.1 General

4.19.2 Cycloalkanes

4.19.3 Cyclic Ethers and Cyclic Sulfides

4.19.4 Cyclic Acetals

4.19.5 Spiroorthocarbonates and Spiroorthoesters

4.19.6 α-exo-Methylene Lactones

4.19.7 Cyclic Sulfones with Vinyl Group

4.19.8 Controlled Radical Ring-Opening Polymerization

4.19.9 Summary

REFERENCES

4.20. Architectures of Polymers Synthesized using ROMP

4.20.1 Introduction

4.20.2 Catalysts (Grubbs and Schrock Type)

4.20.3 Basic Categories

4.20.4 Monomers

4.20.5 Linear Architectures

4.20.6 Polyacetylene

4.20.7 Diblocks/Triblocks

4.20.8 Random

4.20.9 Alternating

4.20.10 Cyclic

4.20.11 Grafted

4.20.12 Polyalkynes

4.20.13 Nano

4.20.14 Micelles

4.20.15 Polyrotaxanes and Polycatenane

4.20.16 Dendrimers

4.20.17 Star Polymers

4.20.18 Other

4.20.19 Conclusion

REFERENCES

4.21. High-Molecular-Weight Poly(ethylene oxide)

4.21.1 Introduction

4.21.2 Oxirane Polymerization

4.21.3 Anionic Coordination Polymerization

4.21.4 Applications of High-MW Polyoxiranes

REFERENCES

4.22. Nonlinear Macromolecules by Ring-Opening Polymerization

4.22.1 Introduction

4.22.2 Background and History

4.22.3 Specific Concepts in the Synthesis of Nonlinear Polymers by Ring-Opening Polymerization

4.22.4 Complex Polymer Architectures Containing Nonlinear Macromolecules Generated by ROP

4.22.5 Conclusion and Perspectives

REFERENCES

4.23. Current and Forthcoming Applications of ROMP-Derived Polymers

4.23.1 Introduction to Ring-Opening Metathesis Polymerization

4.23.2 Initiators for ROMP

4.23.3 1-Alkyne Polymerization

4.23.4 Supports

4.23.5 Summary

REFERENCES

4.24. Chain Extension by Ring Opening

4.24.1 General

4.24.2 Chain Extension

4.24.3 Diepoxides

4.24.4 Cyclic Imino Ethers

4.24.5 Cyclic Anhydrides

4.24.6 Bisoxazolinones

4.24.7 Coupling with Release of Blocking Groups

4.24.8 Mixed Systems

4.24.9 Conclusions

REFERENCES

4.25. Ring-Opening Dispersion Polymerization

4.25.1 Introduction

4.25.2 Cationic Ring-Opening Dispersion Polymerization

4.25.3 Anionic and Pseudoanionic Ring-Opening Dispersion Polymerization

4.25.4 Practical Importance of Ring-Opening Dispersion Polymerization

REFERENCES

4.26. Ring-Opening Metathesis Polymerization in the Synthesis of Conjugated Polymers

4.26.1 Introduction

4.26.2 Ring-Opening Polymerization of Monocyclic Polyenes

Summary

REFERENCES

4.27. Oligomeric Poly(ethylene oxide)s. Functionalized Poly(ethylene glycol)s. PEGylation

4.27.1 Introduction

4.27.2 Properties of PEGs

4.27.3 Chemistry of PEGylation

4.27.4 PEG Conjugation to Peptides and Proteins

4.27.5 PEG Conjugation with Small Drugs

4.27.6 PEGylated Dendrimers as Drug Delivery Systems

4.27.7 PEGylated Inorganic–Organic Core-Shell Nanoparticles

REFERENCES

4.28. Current and Forthcoming Applications of ROMP Polymers – Biorelated Polymers

4.28.1 Bioactive Polymers from the Ring-Opening Metathesis Polymerization

REFERENCES

4.29. Polyphosphoesters

4.29.1 Introduction and Historical Background

4.29.2 Controlled Syntheses of PPEs by Ring-Opening Polymerization

4.29.3 Topological Structure of PPE

4.29.4 Thermoresponsive PPEs

4.29.5 Functional PPEs

4.29.6 Biomedical Applications of PPEs

4.29.7 Conclusions and Outlook

REFERENCES

4.30. Industrial Applications of ROMP

4.30.1 Introduction

4.30.2 Olefin Metathesis in the Petrochemical Industry

4.30.3 Polymer Modification

4.30.4 ROMP Polymers Based on Dicyclopentadiene

4.30.5 Linear Polyalkenamers

4.30.6 Conclusion

REFERENCES

4.31. Ring-Opening Polymerization of Cyclic Esters

4.31.1 Introduction

4.31.2 ROP of Cyclic Esters: Generalities

4.31.3 Industrial Aliphatic Polyesters Implemented by ROP

4.31.4 Conclusions and Outlook

REFERENCES

4.32. Polymerization Kinetic Modeling and Macromolecular Reaction Engineering

4.32.1 Introduction

4.32.2 Stepwise Polymerization

4.32.3 Free-Radical Polymerization

4.32.4 Ionic Polymerization

4.32.5 Controlled Radical Polymerization

4.32.6 Ziegler–Natta Polymerization

4.32.7 Metallocene Polymerization

4.32.8 Emulsion Polymerization

4.32.9 Dispersion and Suspension Polymerization

4.32.10 Copolymerization

4.32.11 Semibatch Control of Copolymer Composition

4.32.12 Continuous Polymerization Processes

4.32.13 Industrial Examples of Polymer Production

4.32.14 Conclusion and Outlook

REFERENCES

4.33. Template Polymerization

4.33.1 Introduction

4.33.2 Mechanism of Template Polymerization

4.33.3 Radical Template Polymerization and Copolymerization

4.33.4 Template Polycondensation

4.33.5 Ring-Opening Template Polymerization

4.33.6 Special Kinds of Template Polymerization

4.33.7 Products of Template Polymerization and Potential Applications

4.33.8 Polymerization in Confined Space

4.33.9 Conclusion

REFERENCES

4.34. Mechanistic Aspects of Solid-State Polycondensation

4.34.1 Introduction

4.34.2 Direct Solid-State Polycondensation

4.34.3 Post-Solid-State Polycondensation

4.34.4 Conclusions

REFERENCES

4.35. Radical Polymerization at High Pressure

4.35.1 Introduction

4.35.2 Experiments and Data Treatment

4.35.3 Initiation, Propagation, and Termination Rate Coefficients of Radical Polymerization up to High Pressure

4.35.4 High-Pressure Ethene Polymerization

4.35.5 High-Pressure Ethene Copolymerization

4.35.6 Reversible Deactivated Radical Polymerization

4.35.7 Homogeneous-Phase Polymerization in scCO2

4.35.8 Kinetics of Radical Polymerization in Homogeneous Mixture with scCO2

REFERENCES

4.36. Electroinitiated Polymerization

4.36.1 Introduction

4.36.2 Electroinitiated Polymerization of Vinyl Monomers for Promoting Coatings Adhesive to Metals

4.36.3 Electropolymerization of Conjugated Polymers as Active Layers in Advanced Devices

4.36.4 Electrografting of Conjugated Polymers

4.36.5 Conclusion

REFERENCES

4.37. Photopolymerization

4.37.1 Introduction

4.37.2 Photochemical Condensation Reactions

4.37.3 Photoinduced Active Center Polymerizations

4.37.4 Conclusions

REFERENCES

4.38. Frontal Polymerization

4.38.1 What Is Frontal Polymerization?

4.38.2 Photofrontal Polymerization

4.38.3 Isothermal Frontal Polymerization

4.38.4 Cryogenic Fronts

4.38.5 Thermal Frontal Polymerization

4.38.6 Conclusions

REFERENCES

4.39. Microwave-Assisted Polymerization

4.39.1 Interaction of Microwaves with Materials

4.39.2 Chain-Growth Polymerization Reactions

4.39.3 Step-Growth Polymerization Reactions

4.39.4 Polymer Composites and Nanocomposites

4.39.5 Scaling-Up Reactions under Microwave Irradiation

REFERENCES

VOLUME 5. Polycondensation

5.01. Introduction and Overview

5.01.1 Introduction

5.01.2 Overview

Principles and Opportunities

5.02. Principles of Step-Growth Polymerization (Polycondensation and Polyaddition)

5.02.1 Introduction and Historical Perspective

5.02.2 Structure–Property Relationships in Step-Growth Polymers

5.02.3 Synthesis of Step-Growth Polymers

5.02.4 Future Direction for Step-Growth Polymers

5.02.5 Concluding Remarks

REFERENCES

5.03. Opportunities in Bio-Based Building Blocks for Polycondensates and Vinyl Polymers

5.03.1 Introduction

5.03.2 Monomers

5.03.3 Approaches in Commodity Polymers

5.03.4 Approaches in Engineering Polymers

5.03.5 Approaches for High Performance Polymers

5.03.6 Conclusions

REFERENCES

5.04. Sequence Control in One-Step Polycondensation

5.04.1 Introduction

5.04.2 Analysis of Constitutional Regularity

5.04.3 Sequential Polymers from Symmetric and Nonsymmetric Monomers

5.04.4 Sequential Polymers from Two Nonsymmetric Monomers

5.04.5 Sequential Polymer from Three Nonsymmetric Monomers

5.04.6 Conclusions

REFERENCES

Novel Synthetic Approaches

5.05. Nonstoichiometric Polycondensation

5.05.1 Introduction

5.05.2 Nonstoichiometric Polycondensation Caused by the Change in Reactivity

5.05.3 Nonstoichiometric Polycondensation Caused by the Change in the Higher Structure of Polymers

5.05.4 Conclusion

REFERENCES

5.06. Chain-Growth Condensation Polymerization

5.06.1 Introduction

5.06.2 p-Substituted Aromatic Polymers

5.06.3 m-Substituted Aromatic Polymers

5.06.4 Nonaromatic Polymers

5.06.5 π-Conjugated Polymers

5.06.6 Future Remarks

REFERENCES

5.07. Oxidative Coupling Polymerization

5.07.1 Introduction

5.07.2 Oxidative Polymerization of Phenols and Naphthols

5.07.3 Thiophenols and Their Derivatives

5.07.4 Anilines

5.07.5 Pyrroles

5.07.6 Thiophenes

5.07.7 Other Aromatic Heterocycles

5.07.8 Aromatic Hydrocarbons

5.07.9 Other Monomers

5.07.10 Conclusion

REFERENCES

5.08. Condensation Polymers via Metal-Catalyzed Coupling Reactions

5.08.1 Introduction

5.08.2 An Overview of Conjugated Polymers

5.08.3 Metal-Catalyzed Carbon–Carbon Bond Forming Reactions

5.08.4 Metathesis Reactions – Acyclic Diene and Acyclic Diyne Metathesis

5.08.5 An Overview of Various Polymers Prepared Using Metal-Mediated Coupling Reactions

5.08.6 Conclusion

REFERENCES

5.09. Advances in Acyclic Diene Metathesis Polymerization

5.09.1 Introduction

5.09.2 Functional Polymers and Materials via ADMET

5.09.3 Exotic Polymer Structures

5.09.4 Precision Polyolefins

5.09.5 Meeting the Benchmark: Linear Acyclic Diene Metathesis Polyethylene

5.09.6 Precision Halogenated Polyolefins

5.09.7 Precision Polyolefins with Alkyl Branches

5.09.8 Precision Polyolefins with Ether Branches

5.09.9 Precision Polyolefins with Pendant Acid Groups

5.09.10 Precision Amphiphilic Copolymers

5.09.11 Summary and Outlook

REFERENCES

5.10. Enzymatic Polymerization

5.10.1 Introduction

5.10.2 Enzymatic Polycondensation

5.10.3 Enzymatic Polyaddition

5.10.4 Summary

REFERENCES

5.11. Nonlinear Polycondensates

5.11.1 Introduction

5.11.2 Insoluble Cross-Linked Polymers

5.11.3 Soluble Branched Polymers

REFERENCES

5.12. Post-Polymerization Modification

5.12.1 Historical Background and Definitions

5.12.2 General Considerations

5.12.3 Functional Groups Employed in Chemical Modifications

5.12.4 Conclusions and Outlook

REFERENCES

5.13. Supramolecular Polymers

5.13.1 Introduction

5.13.2 Metallo-supramolecular Polymers

5.13.3 Supramolecular Polymers Based on Ionic Interactions

5.13.4 Supramolecular Polymers Based on Hydrogen Bonding

5.13.5 Supramolecular Polymers Based on Multiple Supramolecular Motifs

5.13.6 Conclusion and Outlook

REFERENCES

Chemistry and Technology of Polycondensates

5.14. Chemistry and Technology of Step-Growth Polyesters

5.14.1 Introduction

5.14.2 Synthetic Processes for Polyesters

5.14.3 Aliphatic Polyesters

5.14.4 Aryl–Alkyl Polyesters

5.14.5 All-aromatic Polyesters

5.14.6 Summary

REFERENCES

Relevant Website

5.15. Biodegradable Polyesters

5.15.1 Introduction

5.15.2 Synthetic Routes to Polyesters

5.15.3 Classification, Biodegradability, and Applications of Polyesters

5.15.4 Different Macromolecular Architectures and Speciality Biodegradable Polyesters

5.15.5 Biodegradable Polyester Nanoparticles

5.15.6 Conclusions

REFERENCES

5.16. Polycarbonates

5.16.1 Introduction

5.16.2 Historical Development of PCs

5.16.3 Properties and Uses of PCs

5.16.4 Synthesis of PCs

5.16.5 Interfacial Synthesis Process (Phosgene Process)

5.16.6 Transesterification Synthesis Process (Melt or Solventless Process)

5.16.7 ROP of Cyclic Oligomers

5.16.8 Oxidative Carbonylation Process (One-Step Process)

5.16.9 CO2 Process (Synthesis Process Using Carbon Dioxide or Carbonates)

5.16.10 Conclusion

REFERENCES

5.17. Aromatic Polyethers, Polyetherketones, Polysulfides, and Polysulfones

5.17.1 Introduction

5.17.2 Poly(arylene ether)s

5.17.3 Poly(arylene ether ketone)s

5.17.4 Poly(arylene sulfone)s

5.17.5 Poly(arylene sulfide)s

REFERENCES

5.18. Chemistry and Technology of Polyamides

5.18.1 Introduction

5.18.2 Hydrolytically Synthesized Fully Aliphatic Polyamides

5.18.3 Semiaromatic Polyamides

5.18.4 Segmented Block Copolymers of Polyamides and Elastomeric Polyethers

5.18.5 Polyamide Blends

5.18.6 Applications of Polyamides

5.18.7 Summary, Main Conclusions, and Future Perspectives

REFERENCES

5.19. Lyotropic Polycondensation including Fibers

5.19.1 Introduction

5.19.2 Aramids

5.19.3 Polybenzazole

5.19.4 Beyond PBZ

REFERENCES

5.20. Polyimides

5.20.1 Introduction

5.20.2 Conventional PI

5.20.3 Functional PI

5.20.4 Conclusions

REFERENCES

5.21. High-Performance Heterocyclic Polymers

5.21.1 Introduction

5.21.2 Polyazoles

5.21.3 Polybenzazoles

5.21.4 Molecular Composites Based on Rigid-Rod Polybenzazoles

5.21.5 Aromatic Polyimides

5.21.6 Ladder and Semi-ladder Polymers

REFERENCES

5.22. Polyphenylenes, Polyfluorenes, and Poly(phenylene vinylene)s by Suzuki Polycondensation and Related Methods

5.22.1 Introduction

5.22.2 Synthesis Background and Strategy

5.22.3 Fundamental Synthetic Aspects

5.22.4 Recent Progress

5.22.5 Selected Examples

5.22.6 Poly(phenylene vinylene)s

5.22.7 Conclusions and Outlook

REFERENCES

5.23. Metal-Containing Macromolecules

5.23.1 Introduction

5.23.2 Coordination Polymers

5.23.3 Polymers Containing Sandwich Complexes

5.23.4 Macromolecules Containing Metal Carbonyl Complexes

5.23.5 Transition Metal Polyynes

5.23.6 Metal–Metal Bonded Systems

5.23.7 Conclusion

REFERENCES

5.24. Phosphorus-Containing Dendritic Architectures

5.24.1 Introduction

5.24.2 Syntheses of Phosphorus-Containing Dendrimers

5.24.3 Syntheses of Phosphorus-Containing Dendrons

5.24.4 Syntheses of Special Phosphorus-Containing Dendritic Architectures

5.24.5 Conclusions

REFERENCES

5.25. Epoxy Resins and Phenol-Formaldehyde Resins

5.25.1 Introduction of Epoxy Resins

5.25.2 Basic Characteristics of Epoxy Resins

5.25.3 Synthesis of Epoxy Resins

5.25.4 Curing of Epoxy Resin

5.25.5 General Properties of Epoxy Resins

5.25.6 Introduction of Phenolic resins

5.25.7 Novolac

5.25.8 Resol

5.25.9 Transformation of Phenolics

5.25.10 Natural Products as Phenolics

5.25.11 Modification by Alloys and Co-curing

5.25.12 Hybrids and Composites

5.25.13 Conclusion

REFERENCES

5.26. High-Temperature Thermosets

5.26.1 Introduction

5.26.2 Thermosetting Monomers and Oligomers

5.26.3 Thermosetting Liquid Crystals

5.26.4 Concluding Remarks

REFERENCES

VOLUME 6. Macromolecular Architectures and Soft Nano-Objects

6.01. Introduction

6.01.1 Introduction

6.01.2 Topology

6.01.3 Composition and Functionality

6.01.4 Shape-Controlled Polymers and Nanoobjects

Topology

6.02. Synthesis and Properties of Macrocyclic Polymers

6.02.1 Introduction

6.02.2 Synthesis of Cyclic Macromolecules

6.02.3 Physical Properties of Cyclic Polymers

REFERENCES

6.03. Polymers with Star-Related Structures

6.03.1 Synthesis of Star Polymers

6.03.2 Properties of Star Polymers

6.03.3 Applications of Star Polymers

6.03.4 Conclusions

REFERENCES

6.04. Dendrimers

6.04.1 Introduction

6.04.2 Synthesis of Dendrimers

6.04.3 Properties and Characterization of Dendrimers

6.04.4 Biomedical Applications of Dendrimers

6.04.5 Commercial Applications and Sources

6.04.6 Conclusions and Outlook in the Research Area

REFERENCES

6.05. Hyperbranched Polymers

6.05.1 Introduction: Definitions and Synthetic Strategies

6.05.2 Theoretical Aspects: Degree of Branching

6.05.3 Polycondensation and Polyaddition

6.05.4 Complex Architectures Containing Hyperbranched Blocks

6.05.5 Conclusion and Outlook

REFERENCES

6.06. Molecular Brushes

6.06.1 Introduction

6.06.2 Synthesis

6.06.3 Properties

6.06.4 Applications

6.06.5 Closing Remarks and Perspectives

REFERENCES

6.07. Spherical Polymer Brushes

6.07.1 Introduction

6.07.2 Preparation of Brushes Anchored to Spherical Supports

6.07.3 Characterization

6.07.4 Physical Properties

6.07.5 Applications

6.07.6 Summary

REFERENCES

6.08. Model Networks and Functional Conetworks

6.08.1 Introduction

6.08.2 Definitions

6.08.3 Model Networks

6.08.4 Quasi-Model Networks

6.08.5 Amphiphilic Conetworks

6.08.6 Conclusions

REFERENCES

6.09. Polymer Nanogels and Microgels

6.09.1 Aqueous Microgels

6.09.2 Synthetic Routes

6.09.3 Characterization by Scattering Methods

6.09.4 Applications of Microgels

REFERENCES

Composition and Functionality

6.10. Controlled End-Group Functionalization (Including Telechelics)

6.10.1 Introduction

6.10.2 Characterization Methods for Chain-End-Functionalized Polymers

6.10.3 Anionic Synthesis of Chain-End-Functionalized Polymers

6.10.4 Radical Synthesis of Chain-End-Functionalized Polymers

6.10.5 Cationic Synthesis of Chain-End-Functionalized Polymers

6.10.6 Conclusion

REFERENCES

6.11. Robust, Efficient, and Orthogonal Chemistries for the Synthesis of Functionalized Macromolecules

6.11.1 Introduction

6.11.2 Functional Polymers and Architectures

6.11.3 Step Growth Polymerization via CuAAC or TEC

6.11.4 Polymer Backbone and Pendant Group Functionalization

6.11.5 Star and Miktoarm Architectures

6.11.6 Dendrimers

6.11.7 Cross-linked Network Architectures

6.11.8 Three-Dimensional (3D) Objects

6.11.9 Conclusions and Outlook

REFERENCES

6.12. Controlled Composition

6.12.1 Introduction

6.12.2 Copolymerization Models

6.12.3 Statistical Copolymers

6.12.4 Alternating Copolymers

6.12.5 Solvent Effects

6.12.6 Copolymers versus Homopolymers

6.12.7 Gradient Copolymers

6.12.8 Properties of Copolymers

6.12.9 Epilogue

REFERENCES

6.13. Well-Defined Block Copolymers

6.13.1 Introduction

6.13.2 Principles of Block Copolymerization

6.13.3 Linear Topologies

6.13.4 Synthetic Methods Involving a Single Polymerization Mechanism

6.13.5 Synthetic Methods through Mechanistic Transformations

6.13.6 Summary

REFERENCES

6.14. Graft Copolymers and Comb-Shaped Homopolymers

6.14.1 Introduction

6.14.2 Some General Remarks on Graft Copolymers

6.14.3 Polymerization Processes Aimed to Be Used in Graft Copolymer Synthesis

6.14.4 Principles of Graft Copolymer Synthesis

6.14.5 ‘Grafting Onto’ Methods

6.14.6 ‘Grafting From’ Methods

6.14.7 ‘Grafting Through’ Processes: The Macromonomer Method

6.14.8 Other Grafting Processes

6.14.9 Conclusions

REFERENCES

6.15. Synthetic–Biological Hybrid Polymers

6.15.1 Introduction and Potential Scope of Biohybrid Polymers

6.15.2 Strategies to Synthesize Biohybrid Polymers

6.15.3 Implementing Biopolymer Properties into Synthetic Polymer Systems

6.15.4 Conclusion and Outlook

REFERENCES

6.16. Dynamic Supramolecular Polymers

6.16.1 Introduction

6.16.2 Linear SPs

6.16.3 Multivalent Supramolecular Assemblies

6.16.4 Hierarchical Assemblies

6.16.5 Conclusions and Outlook

REFERENCES

Shape-Controlled Polymers and Nano-Objects

6.17. Stereocontrolled Chiral Polymers

6.17.1 Introduction

6.17.2 Helical Polymers

6.17.3 Optically Active Polymers with Main-Chain Configurational Chirality

6.17.4 Enantiomer-Selective Polymerization

6.17.5 Summary

REFERENCES

6.18. Conformation-Dependent Design of Synthetic Functional Copolymers

6.18.1 Introduction

6.18.2 Theoretical Approaches

6.18.3 Synthesis of Designed Copolymers

6.18.4 Concluding Remarks

REFERENCES

6.19. Rigid–Flexible and Rod–Coil Copolymers

6.19.1 Introduction

6.19.2 Synthetic Aspects

6.19.3 Organizational Features

6.19.4 Applications

6.19.5 Alternating Rigid–Flexible Polymers

6.19.6 Conclusions

REFERENCES

6.20. Individual Nano-Objects Obtained via Hierarchical Assembly of Polymer Building Blocks

6.20.1 Introduction to Nano-Objects

6.20.2 Synthetic Methodologies for the Preparation of Nano-Objects

6.20.3 Assembly of Nano-Objects into Complex Hierarchical Structures

6.20.4 Manipulation of Nano-Objects

6.20.5 Conclusions and Outlook

REFERENCES

VOLUME 7. Nanostructured Polymer Materials and Thin Films

7.01. Introduction

7.02. Block Copolymers in the Condensed State

7.02.1 Introduction

7.02.2 Amorphous Block Copolymers

7.02.3 Semicrystalline Block Copolymers

7.02.4 Mechanical Properties of Block Copolymers

7.02.5 Alignment of Block Copolymer Morphologies under External Fields

7.02.6 Block Copolymer Thin Films

7.02.7 Summary

REFERENCES

7.03. Block Copolymer Thin Films

7.03.1 Introduction

7.03.2 Symmetric BCP Thin Films: Lamellar Morphologies

7.03.3 Symmetric BCP Thin Films: Phase-Mixed Morphology

7.03.4 Asymmetric BCP Thin Films: Cylindrical Morphologies

7.03.5 Asymmetric BCP Thin Films: Spherical Morphologies

7.03.6 BCP Thin Films: Controlled Interfacial Interactions

7.03.7 BCP Thin Films: Electric Fields

7.03.8 BCP Thin Films: Magnetic Fields

7.03.9 BCP Thin Films: Solvent Evaporation

7.03.10 BCP Thin Films: Gradient Fields

7.03.11 BCP Thin Films: Surface Topography

7.03.12 BCP Thin Films: Faceted Surfaces

7.03.13 BCP Thin Films: Chemical Patterning

7.03.14 Nanopatterning from BCP Thin Films

7.03.15 Applications: Nanoporous Membrane for Filtration of Viruses

7.03.16 Applications: Nanoreactors

7.03.17 Applications: Nanoscaffolding

7.03.18 Applications: Templates from Nanodots to Nanorods

7.03.19 BCP Thin Films: Summary

REFERENCES

7.04. Block Copolymers under Confinement

7.04.1 Introduction

7.04.2 Block Copolymers under Confinement

7.04.3 Principles of Complex Structure Formation from Block Copolymers under Confinement

7.04.4 Conclusion

REFERENCES

7.05. Assemblies of Polymer-Based Nanoscopic Objects

7.05.1 Introduction

7.05.2 Polymer-Mediated Self-Assembly

7.05.3 Polymer-Templated Self-Assembly

7.05.4 TNP Self-Assembly

REFERENCES

7.06. Self-Assembly of Inorganic Nanoparticles in Polymer-Like Structures

7.06.1 Introduction

7.06.2 Experimental Methods Utilized for the Self-Assembly of NPs in Nanopolymers

7.06.3 Properties of 1D Nanostructures

7.06.4 Applications of 1D Assemblies of NPs

7.06.5 Outlook

REFERENCES

7.07. Hybrid Polymer–Inorganic Nanostructures

7.07.1 Introduction

7.07.2 Block Copolymer Self-Assembly

7.07.3 Nanostructured Diblock Copolymer–Aluminosilicate Nanoparticle Composites: A Model System

7.07.4 Moving from Amorphous to Crystalline Inorganic Materials

7.07.5 Potential Applications of Nanostructured Block Copolymer-Derived Hybrids

7.07.6 Conclusions and Outlook

REFERENCES

7.08. Peptide–Polymer Conjugates Toward Functional Hybrid Biomaterials

7.08.1 Introduction

7.08.2 Peptides/Proteins

7.08.3 Advantages of Peptide–Polymer Conjugates

7.08.4 Synthesis

7.08.5 Self-Assembly of Peptide–Polymer Conjugates

7.08.6 Perspectives and Outlook

7.08.7 Conclusion

REFERENCES

7.09. Layer-by-Layer Assembly of Multifunctional Hybrid Materials and Nanoscale Devices

7.09.1 Introduction

7.09.2 Types of Interactions and Corresponding Materials Used for LbL

7.09.3 Substrates

7.09.4 LbL Deposition Techniques

7.09.5 Characterization Methods

7.09.6 Applications

7.09.7 Conclusion and Perspective

REFERENCES

7.10. Nanostructured Electrospun Fibers

7.10.1 Introduction

7.10.2 Formation of Fibers

7.10.3 Beaded Fibers

7.10.4 Core–shell and Hollow Fibers

7.10.5 Porous and Wrinkled Fibers

7.10.6 Block Copolymer Fibers

7.10.7 Applications of Electrospun Fibers

7.10.8 Conclusions and Perspectives

REFERENCES

7.11. Soft Lithographic Approaches to Nanofabrication

7.11.1 Introduction

7.11.2 Materials and Methods

7.11.3 Printing

7.11.4 Molding

7.11.5 2D and 3D Fabrication using Optical Soft Lithography

7.11.6 Nanoskiving

7.11.7 Conclusions

REFERENCES

7.12. Block Copolymer Thin Films on Patterned Substrates

7.12.1 Introduction

7.12.2 Block Copolymer Thin films on Topographical Prepatterns

7.12.3 Block Copolymer Thin Films on Chemical Prepatterns

7.12.4 Theory and Simulation of Block Copolymer Thin Films on Patterned Substrates

7.12.5 Future Issues for Block Copolymer Thin Films on Pattern Substrates

REFERENCES

7.13. Nanoimprint Lithography of Polymers

7.13.1 Introduction

7.13.2 Major Accomplishments of Nanoimprint Lithography

7.13.3 Technical Issues of Nanoimprint Lithography

7.13.4 Applications

7.13.5 Conclusions and Outlook

REFERENCES

7.14. Modeling Mixtures of Nanorods and Polymers

7.14.1 Introduction

7.14.2 Nanorod Polymer Composites

7.14.3 Mechanical Properties

7.14.4 Electrical Properties

7.14.5 Photovoltaic Properties

7.14.6 Conclusions

REFERENCES

7.15. Sterically Stabilized Nanoparticles in Solutions and at Interfaces

7.15.1 Introduction – Sterically Stabilized Nanoparticles: Synthesis and the Role of Surface-Bound Ligands

7.15.2 Synthesis of Ligand-Stabilized Nanoparticles

7.15.3 Nanoparticles at the Air–Liquid Interface

7.15.4 Sterically Stabilized Nanoparticles at Liquid–Liquid Interfaces: From Particle-Stabilized Emulsions to Robust Materials

7.15.5 Controlling Miscibility with Bijels: From Simulation to Experiments

7.15.6 Sterically Stabilized Nanoparticles in Polymer Matrices – From Dispersion to Interfacial Pinning

REFERENCES

7.16. Quasi-One-Component Polymer Nanocomposites Based on Particle Brush Assembly

7.16.1 Introduction

7.16.2 Structure of Particle Brush Systems

7.16.3 Particle Brush-Based Quasi-One-Component Nanocomposites

7.16.4 Conclusion

REFERENCES

7.17. Electrical Conductivity of Polymer Nanocomposites

7.17.1 Introduction

7.17.2 Applications of Electrically Conductive Polymer Nanocomposites

7.17.3 Percolation Theory and Simulation

7.17.4 Mechanisms of Electrical Transport

7.17.5 Filler Effects

7.17.6 Effects of Matrix Properties

7.17.7 Dispersion/Microstructure

7.17.8 Concluding Remarks and Future Directions

REFERENCES

7.18. Polymer Dynamics in Constrained Geometries

7.18.1 Introduction

7.18.2 The Nature of Confinement

7.18.3 Techniques to Quantify Dynamics

7.18.4 Physical Mechanisms of Confinement

REFERENCES

7.19. Polymer Nanomechanics

7.19.1 Introduction

7.19.2 Preliminary Mechanics Concepts

7.19.3 Contact Mechanics

7.19.4 Alternatives to Hertzian Mechanics

7.19.5 Single-Molecule Extension Mechanics

7.19.6 Summary

REFERENCES

VOLUME 8. Polymers for Advanced Functional Materials

8.01. Introduction – Applications of Polymers

8.01.1 Synopsis of Chapters

8.01.2 Closing Remarks

8.02. Top-Down versus Bottom-Up Patterning of Polymers

8.02.1 Block Copolymer Self-Assembly for Patterning Applications

8.02.2 Block Copolymer Phase Behavior

8.02.3 Block Copolymer Templates

8.02.4 The Intersection of Block Copolymer Self-Assembly with Photolithography

8.02.5 Outlook and Summary

REFERENCES

8.03. Photoresists and Advanced Patterning

8.03.1 Introduction

8.03.2 Basic Properties and Requirements of Photoresists

8.03.3 Classification of Resists

8.03.4 Introduction to Early Optical Photoresists: Cyclized Rubber and DNQ–Novolac Resists

8.03.5 Introduction to Chemically Amplified Photoresists

8.03.6 Photochemical Acid Generators

8.03.7 Polymeric Materials and Mechanisms for CARs

8.03.8 e-Beam Resists

8.03.9 Conclusions

REFERENCES

8.04. Rapid Prototyping

8.04.1 Basic Principles of Rapid Prototyping

8.04.2 Photopolymerization-Based RP Technologies

8.04.3 Extrusion-Based RP Processes

8.04.4 Powder-Based RP Processes

8.04.5 Laminated Object Manufacturing

8.04.6 Conclusions

REFERENCES

8.05. Polymer-Based Sensors

8.05.1 Polymers in Organic Electronics

8.05.2 Gas-Phase Sensing

8.05.3 Liquid-Phase Sensing

8.05.4 Conclusions

REFERENCES

8.06. Electroactive Liquid Crystalline Polymers

8.06.1 Introduction

8.06.2 Semiconductive Polymers

8.06.3 Electrooptical Switching of LC Polymers

8.06.4 Actuators

8.06.5 Conclusion

REFERENCES

8.07. Ink-Jet Printing of Functional Polymers for Advanced Applications

8.07.1 Ink-Jet Printing and Its Fundamental Properties

8.07.2 Ink-Jet Printing Functional Materials

8.07.3 Applications of Ink-Jet Printing

8.07.4 Conclusions and Outlook

REFERENCES

8.08. Nanocomposites and Hybrid Materials

8.08.1 Introduction

8.08.2 Nanoscaled Fillers

8.08.3 Nanocomposite Preparation

8.08.4 Applications

8.08.5 Summary

REFERENCES

8.09. Polymer Photonics

8.09.1 Introduction

8.09.2 Second-Order NLO Polymers

8.09.3 Third-Order NLO Polymers

8.09.4 Summary and Outlook

REFERENCES

8.10. Polymer-Based LEDs and Solar Cells

8.10.1 Introduction

8.10.2 Device Issues in Electroluminescent Materials and Full-Color Displays

8.10.3 Material Classes

8.10.4 Hybrid Solar Cells

8.10.5 Conclusions and Outlook

REFERENCES

8.11. Optical Fibers

8.11.1 Introduction

8.11.2 Fundamentals of Fiber Optics

8.11.3 Plastic Optical Fibers

8.11.4 Transmission Properties

8.11.5 Materials

8.11.6 Conclusions

REFERENCES

8.12. Adhesives and Sealants

8.12.1 Adhesives

8.12.2 Adhesive Testing

8.12.3 Pressure-Sensitive Adhesives

8.12.4 Rubber-Based Adhesives

8.12.5 Hot Melt Adhesives

8.12.6 Natural Product-Based Adhesives

8.12.7 Structural Adhesives

8.12.8 Sealants

8.12.9 Future of Adhesives and Sealants

REFERENCES

8.13. Polymer Membranes

8.13.1 Introduction and Historical Background

8.13.2 Membrane Variants and Their Utility

8.13.3 Membrane Formation

8.13.4 Membranes in Gas and Liquid Separations

8.13.5 Barrier Polymers

8.13.6 Membranes in Water Purification Processes

8.13.7 Membranes in Emerging Technologies

REFERENCES

8.14. Polymer Additives

8.14.1 Introduction

8.14.2 Thermo-Oxidative Degradation

8.14.3 Requirements for Polymer Stabilizers

8.14.4 Stabilization against Thermo-Oxidative Degradation

8.14.5 Stabilization of Polymers against Degradation under the Impact of Light

8.14.6 Multifunctional Additive for Engineering Polymers

8.14.7 Metal Ion Deactivators

8.14.8 Acid Scavengers

8.14.9 Analysis of Stabilizers in the Polymer Matrix

REFERENCES

8.15. Stimuli-Responsive Polymer Systems

8.15.1 What Are ‘Responsive Polymers’?

8.15.2 Stimuli-Responsive Polymers

8.15.3 Special Structures of Responsive Polymers

8.15.4 Properties of Responsive Polymers

8.15.5 Responsive Polymers and Their Applications

REFERENCES

8.16. Graphene and Its Synthesis

8.16.1 Introduction and Physical Properties of Graphene

8.16.2 Graphene Synthesis and Characterization

8.16.3 Graphene Nanoribbons

8.16.4 Bottom-Up Organic Synthesis of Graphene Nanostructures

8.16.5 Conclusions

REFERENCES

8.17. Functionalized Carbon Nanotubes and Their Enhanced Polymers

8.17.1 Introduction

8.17.2 CNT Synthesis Techniques

8.17.3 Functionalization of CNTs

8.17.4 CNT–Polymer Nanocomposites

REFERENCES

VOLUME 9. Polymers in Biology and Medicine

9.01. Introduction and Overview

9.01.1 Introduction

9.01.2 Overview

9.02. Lifelike but Not Living

9.02.1 Introduction

9.02.2 Basic Aspects of DNA and RNA Polymers

9.02.3 Three Discoveries That Transformed Nucleic Acid Chemistry

9.02.4 Upper Limits of a Degenerate DNA Synthesis – A Cap on Outcome

9.02.5 Catalytic RNA Cleavage by Ribozymes and DNAzymes

9.02.6 DNAzymes – Deoxyribozymes

9.02.7 M2+-Independent RNA-Cleaving DNAs

9.02.8 RNase A-Catalyzed RNA Cleavage – M2+-Independent Catalytic Perfection

9.02.9 Early Attempts at Expanding the Catalytic Repertoire of Nucleic Acids

9.02.10 Simultaneous Incorporation of Imidazoles and Amines – Selection of M2+-Independent RNase A Mimics

9.02.11 A Comparison of Two Selected M2+-Independent DNAzyme RNase A Mimics

9.02.12 M2+-Independent RNA-Cleaving DNAzymes with Three Modified Nucleosides

9.02.13 Nucleic Acid Diels–Alderases – Modified and Unmodified

9.02.14 Nanoparticle Templation by Modified RNAs

9.02.15 Other Reports of Modified rNTPs and dNTPs for Potential Selection

9.02.16 Non-Nucleobase Modifications – Altered Phosphodiester and Sugar Portions

9.02.17 Nucleobase-Modified Aptamers

9.02.18 Evolving Polymerases

9.02.19 Conclusions

REFERENCES

9.03. Collagen

9.03.1 Introduction

9.03.2 The Collagen Fibril – A Building Block of Extracellular Tissues

9.03.3 Examples of Collagen-Based Natural Tissues

9.03.4 Collagen as Biomaterial

REFERENCES

9.04. Silks

9.04.1 Introduction

9.04.2 Types of Silk Fibers

9.04.3 Material Properties

9.04.4 Composition

9.04.5 Structure

9.04.6 Silk Processing

9.04.7 The Future

REFERENCES

9.05. Elastins

9.05.1 Introduction

9.05.2 Native Elastin Derivatives: Sequence, Structure, and Function

9.05.3 Elastin-Mimetic Polypeptides: Synthesis and Applications

9.05.4 Comparison between Native and Synthetic Elastins

REFERENCES

9.06. Resilin in the Engineering of Elastomeric Biomaterials

9.06.1 Introduction

9.06.2 Native Resilin

9.06.3 Recombinant Resilin-Like Polypeptides

9.06.4 Conclusions and Perspectives

REFERENCES

9.07. Artificial Proteins

9.07.1 Introduction

9.07.2 Protein Biosynthesis and Genetic Engineering of Protein Polymers

9.07.3 Bioinspired Artificial Protein Polymers

9.07.4 Biosynthesis of De Novo-Designed Protein Polymers

9.07.5 Expanding the Scope of Protein Chemistry: Noncanonical Amino Acids

REFERENCES

9.08. Polysaccharides

9.08.1 Introduction

9.08.2 The Chemistry of Carbohydrates

9.08.3 Glycopolymers

9.08.4 Conclusions

REFERENCES

9.09. Poly(hydroxyalkanoate)s

9.09.1 General Introduction

9.09.2 Biosynthesis of PHAs

9.09.3 Structure and Properties of PHAs

9.09.4 Biodegradability of PHAs

9.09.5 Industrial Production of P(3HB) and Its Copolymers

REFERENCES

9.10. Polymers of the Cytoskeleton

9.10.1 Introduction

9.10.2 Cytoskeletal Filament Subunits

9.10.3 Cytoskeletal Assembly

9.10.4 Cytoskeletal-Binding Proteins

9.10.5 Polyelectrolyte Properties: Counterion Cross-Linking

9.10.6 Mechanical Properties of the Cytoskeleton

9.10.7 Active, Nonequilibrium Gels

9.10.8 Conclusions

REFERENCES

9.11. Mechanical Interactions between Cells and Tissues

9.11.1 Introduction

9.11.2 Elasticity of Physiological Microenvironments

9.11.3 Cell-Induced Matrix Deformations

9.11.4 How Deeply Do Cells ‘Feel’? – Experiments

9.11.5 How Deeply Do Cells ‘Feel’? – Computations

9.11.6 Matrix-Mediated Cell–Cell Interactions

9.11.7 Cell Morphology and Cytoskeletal Forces Are Directed by Extracellular Mechanical Cues

9.11.8 Molecular Mechanics in Mechanism: From Forced Unfolding to ‘Heat Shock’ Proteins

9.11.9 Putting It All Together: Microenvironment Elasticity, Cytoskeletal Stress, and Gene Organization

9.11.10 Conclusion

REFERENCES

9.12. Biological Adhesion

9.12.1 Introduction

9.12.2 Bioinspired Fibrillar Adhesives

9.12.3 Bioinspired Wet Adhesives

9.12.4 Other Biological Adhesives as Future Targets of Biomimetic Systems

9.12.5 Conclusion

REFERENCES

9.13. Viral Packaging of Nucleic Acids

9.13.1 Introduction

9.13.2 Physical Models of dsDNA, ssDNA, and RNA

9.13.3 Internal Organization of a Viral Genome

9.13.4 Thermodynamic Forces in the Packaging in Bacteriophages

9.13.5 Electrostatic Dominance in the Assembly of ssRNA Viruses

9.13.6 Ejection Forces and Dynamics

REFERENCES

9.14. Making New Materials from Viral Capsids

9.14.1 Introduction

9.14.2 Capsid-Based Templates for the Generation of Inorganic Materials

9.14.3 Chemical Methods for the Covalent Modification of Viral Capsids

9.14.4 Capsid-Based Materials for Drug Delivery, Diagnostics, and Tissue Engineering

9.14.5 Capsid-Based Materials for Optical and Catalytic Applications

9.14.6 Summary and Future Challenges

REFERENCES

9.15. Peptoid Oligomers

9.15.1 Background

9.15.2 Peptoid-Based Polymers

9.15.3 Applications of Peptoid Polymers

9.15.4 Antimicrobial Peptoids

9.15.5 Concluding Remarks

REFERENCES

9.16. Polymer–Membrane Interactions

9.16.1 Polymer–Membrane Interactions

9.16.2 Neutral Polymers

9.16.3 Zwitterionic Polymers

9.16.4 Anionic Polymers

9.16.5 Cationic Polymers

9.16.6 Conclusion

REFERENCES

9.17. Protein–Polymer Conjugates

9.17.1 Introduction

9.17.2 Grafting To

9.17.3 Grafting From

9.17.4 Conclusions and Outlook

REFERENCES

9.18. Biomimetic Polymers (for Biomedical Applications)

9.18.1 Introduction

9.18.2 Interaction of Cells with their Environment: Potential of Biomaterial Design

9.18.3 Biomimetic Strategies Applied for Polymeric Materials

9.18.4 Polymers Used for Biomedical Applications: Biomimetic Modification Techniques

9.18.5 Examples of Biomedical Applications for Biomimetic Polymers

9.18.6 Characterization of Biomimetic Polymer Properties and of the Resulting Interactions with the Biological Environment

9.18.7 Conclusion and Outlook

REFERENCES

9.19. Biocompatibility

9.19.1 Introduction

9.19.2 Biocompatibility

9.19.3 Materials for Medical Devices

9.19.4 In Vitro Tests for Biocompatibility

9.19.5 In Vivo Tests for Biocompatibility

9.19.6 Inflammation, Wound Healing, and the Foreign Body Response

9.19.7 Hemocompatibility

9.19.8 Immune Responses

9.19.9 Summary and Conclusion

REFERENCES

9.20. Hydrogels

9.20.1 Introduction

9.20.2 Gel Swelling and Solute Transport

9.20.3 ‘Intelligent’ Hydrogels

9.20.4 Conclusions

REFERENCES

9.21. Polymeric Implants

9.21.1 Introduction

9.21.2 Properties of Biomedical Polymers

9.21.3 Key Polymers Used in Today’s Medical Devices

9.21.4 Perspectives and Opportunities

REFERENCES

9.22. Photopolymerizable Systems

9.22.1 Introduction

9.22.2 Photopolymerization Reactions

9.22.3 Applications

9.22.4 Conclusion

REFERENCES

9.23. Patterning of Polymeric Materials for Biological Applications

9.23.1 Introduction

9.23.2 Top-Down Polymer Patterning Techniques

9.23.3 Bottom-Up Patterning Techniques

9.23.4 Integration of ‘Top-Down’ and ‘Bottom-Up’ Techniques

9.23.5 Biological Applications of Patterned Polymers

9.23.6 Summary

REFERENCES

9.24. High-Throughput Approaches

9.24.1 Introduction

9.24.2 Polyarylates

9.24.3 Cationic Polymers

9.24.4 Organic Coatings

9.24.5 Polyolefin Catalyst Discovery

9.24.6 Polymers Generated through Radical Polymerization

9.24.7 Ring-Opening Polymerizations

9.24.8 Microarray Approaches

9.24.9 Other High-Throughput Screening Approaches

REFERENCES

9.25. Programming Cells with Synthetic Polymers

9.25.1 Introduction

9.25.2 Extracellular Matrix as a Model for Materials to Program Cells

9.25.3 Recruiting Host Cells

9.25.4 Programming Cells via Adhesive Interactions

9.25.5 Regulating Cell Dispersal

9.25.6 Bringing All Three Steps Together: Regulating Dendritic Cell Recruitment, Activation, and Dispersion

REFERENCES

9.26. Nucleic Acid Delivery via Polymer Vehicles

9.26.1 Introduction

9.26.2 Polymer Vehicles for Nucleic Acid Delivery

9.26.3 Polyplex Characterization

9.26.4 Polymer Structure–Nucleic Acid Delivery Relationships from In Vitro Studies

9.26.5 Introduction to In Vivo Nucleic Acid Delivery with Polymers

9.26.6 Polymer–Nucleic Acid Therapeutics in Human Clinical Trials

REFERENCES

9.27. Polymeric Imaging Agents

9.27.1 Introduction

9.27.2 X-Ray Imaging Contrast Agents

9.27.3 Magnetic Resonance Imaging Contrast Agents

9.27.4 Ultrasound Contrast Agents

9.27.5 Radionucleotide Imaging Agents

9.27.6 Optical Imaging Agents

9.27.7 Conclusions

REFERENCES

9.28. Biodegradation of Polymers

9.28.1 Introduction

9.28.2 Polyesters

9.28.3 Polyanhydrides

9.28.4 Polyorthoesters

9.28.5 Polyketals

REFERENCES

VOLUME 10. Polymers for a Sustainable Environment and Green Energy

10.01. Introduction

10.01.1 Introduction

REFERENCES

10.02. Green Chemistry and Green Polymer Chemistry

10.02.1 Introduction

10.02.2 Green Chemistry

10.02.3 Green Polymer Chemistry

10.02.4 Biopolymer Definitions

REFERENCES

Lipids

10.03. Lipid-Based Polymer Building Blocks and Polymers

10.03.1 Introduction

10.03.2 Natural Fats and Oils as Polymer Building Blocks

10.03.3 Oleochemical Polymer Building Blocks

10.03.4 Glycerol

10.03.5 Summary

REFERENCES

Carbohydrate-Based Polymer Building Blocks & Biopolymers

10.04. Mono-, Di-, and Oligosaccharides as Precursors for Polymer Synthesis

10.04.1 Introduction

10.04.2 Mono-, Di-, and Oligosaccharide-Based Platforms and Building Blocks

10.04.3 Carbohydrate-Based Polymers

10.04.4 Conclusions

REFERENCES

10.05. Celluloses and Polyoses/Hemicelluloses

10.05.1 Introduction

10.05.2 Cellulose Sources and Isolation

10.05.3 Structure and Superstructure of Cellulose: Methods for Analysis

10.05.4 Cellulose Solvents

10.05.5 Cellulose Regeneration

10.05.6 Cellulose Esters

10.05.7 Cellulose Ethers

10.05.8 Deoxy Celluloses

10.05.9 Oxidation of Cellulose

10.05.10 Grafting Reactions

10.05.11 Hemicelluloses

REFERENCES

10.06. Nanochitins and Nanochitosans, Paving the Way to Eco-Friendly and Energy-Saving Exploitation of Marine Resources

10.06.1 Structural Characteristics of Chitins In Vivo

10.06.2 β-Chitin: The Simplest 2D Hydrogen-Bonded Polymorph

10.06.3 α-Chitin: The 3D Hydrogen-Bonded Polymorph

10.06.4 Oxychitin

10.06.5 Simplified Preparation of Chitin Nanofibrils

10.06.6 Electrospinning

10.06.7 Conclusion

REFERENCES

10.07. Starch-Based Biopolymers in Paper, Corrugating, and Other Industrial Applications

10.07.1 Starch Basics

10.07.2 Markets

10.07.3 Starch Modification

10.07.4 Starch Handling and Cooking

10.07.5 Industrial Applications

10.07.6 Pharmaceutical and Chemical Applications

10.07.7 Outlook

REFERENCES

10.08. Guar and Guar Derivatives

10.08.1 Introduction

10.08.2 From the Green Beans to Guar Splits and Guar Powders

10.08.3 Chemical Structure and Resulting Physicochemical Properties and Comparison with Other Polysaccharides

10.08.4 Guar Derivatives

10.08.5 Major Applications of Guars

10.08.6 Conclusions and Outlooks

REFERENCES

10.09. Acacia Gum

10.09.1 Origin

10.09.2 Acacia Gum and Sustainable Environment

10.09.3 Chemical Structure

10.09.4 Applications

10.09.5 Conclusion

REFERENCES

10.10. Alginates

10.10.1 Introduction

10.10.2 Sources and Production

10.10.3 Chemical Composition and Conformation

10.10.4 Properties

10.10.5 Tailoring of Alginates by In Vitro Modification

10.10.6 Technical Applications

10.10.7 Applications of Alginates in Medicine and Biotechnology

10.10.8 Conclusions

REFERENCES

10.11. Xanthan

10.11.1 Introduction

10.11.2 Chemical Structure and Biosynthesis

10.11.3 Production Process and Xanthan Modifications

10.11.4 Physicochemical Properties

10.11.5 Applications

10.11.6 Perspectives

REFERENCES

10.12. Polylactic Acid

10.12.1 Introduction

10.12.2 Nondepleting Properties of PLA

10.12.3 Market Potential of PLA

10.12.4 Process Routes to PLA

10.12.5 Processing of PLA

10.12.6 Properties of PLA

10.12.7 Perspective

10.12.8 LA as Raw Material of PLA

REFERENCES

Amino Acid Based Polymer-Building Blocks and Proteins as Biopolymers

10.13. Gelatin

10.13.1 Gelatin

10.13.2 Chemical Composition

10.13.3 Physical and Chemical Properties

10.13.4 Manufacture and Processing

10.13.5 Economic Aspects

10.13.6 Analytical Test Methods and Quality Standards

10.13.7 Uses

REFERENCES

10.14. Processing Soy Protein Concentrate as Plastic in Polymer Blends

10.14.1 Introduction

10.14.2 Soy Protein Products and Fractionation

10.14.3 Plastic Application of Soy Protein

10.14.4 General Extrusion Compounding for Processing SPC as a Plastic in Blending

10.14.5 Properties of PBAT/SPC Blends

10.14.6 Conclusions

REFERENCES

Lignin

10.15. Lignin as Building Unit for Polymers

10.15.1 Constitution and Structure of Lignin from Renewable Resources

10.15.2 Important Isolation Methods and Their Influence on the Properties of Lignin

10.15.3 Current Applications and Future Aspects of the Utilization of Lignin

10.15.4 Outlook

REFERENCES

Sustainable Use of Biomass

10.16. Natural Fibers

10.16.1 Generalities

10.16.2 Fiber Structure

10.16.3 Fiber Morphology

10.16.4 Fiber Sourcing

10.16.5 Summary of the Proprieties of Natural Fibers

10.16.6 Processing of Natural Fibers

10.16.7 Conclusions

REFERENCES

10.17. Natural Rubber

10.17.1 Introduction and History

10.17.2 Challenge Facing the Supply Chain

10.17.3 The Biosynthesis of Poly(cis-1,4-isoprene)

10.17.4 Nonisoprene Components of Natural Rubber (NR)

10.17.5 NR Structure

10.17.6 NR in the Manufacture of Antivibration Parts

10.17.7 General Aspects of NR Applications in Tires

10.17.8 Conclusion

REFERENCES

10.18. Biocomposites

10.18.1 Introduction

10.18.2 Matrix Systems for NF-Reinforced Composites

10.18.3 Natural Fibers for Composites

10.18.4 Natural Composites and Biocomposites

10.18.5 Manual of Typical Challenges for Selected Applications

10.18.6 Conclusions

10.18.7 Outlook

REFERENCES

Polymer Processing: Environmentally Benign & Safe

10.19. Performance Profile of Biopolymers Compared to Conventional Plastics

10.19.1 Introduction

10.19.2 Property Profiles of the Most Important Biopolymers

10.19.3 Properties in Comparison with Conventional Plastics

REFERENCES

10.20. Processing of Plastics into Structural Components

10.20.1 Introduction

10.20.2 Procedures for Serial Production of Plastics Products

REFERENCES

10.21. Processing and Performance Additives for Plastics

10.21.1 Introduction

10.21.2 Radical Generation

10.21.3 Surface Active Additives

10.21.4 Additives for Polymer Processing

10.21.5 Additives for Polymer Properties and Performance

10.21.6 Stabilization against Polymer Degradation

REFERENCES

10.22. Processing and Performance Additives for Coatings

10.22.1 Introduction

10.22.2 Emulsification, Stabilization, and Dispersion

10.22.3 Foam Control

10.22.4 Rheology, Thickening, and Flow

10.22.5 Coalescence and Film Formation

10.22.6 Preservation

10.22.7 Coating Performance

REFERENCES

Sustainable Manufacturing, Processing and Applications for Polymers and Polymer Systems

10.23. Paper

10.23.1 Introduction

10.23.2 Paper History

10.23.3 Paper Applications and Trends

10.23.4 Paper Manufacturing Basics

10.23.5 Cell Structure of Wood

10.23.6 Lignin and Cellulose Chemistry

10.23.7 Sustainable Forestry

REFERENCES

10.24. Polyurethanes

10.24.1 General Description and Basic Reactions

10.24.2 Foams and Elastomers

10.24.3 Coatings and Adhesives

REFERENCES

10.25. Polysiloxanes

10.25.1 Introduction: Siloxanes and their Environmental Characteristics

10.25.2 How Siloxanes Contribute to Sustainable Manufacturing and Resource Conservation

10.25.3 New Applications with Polysiloxanes as Key Substances for Environmentally Important Processes

10.25.4 Conclusion and Outlook

REFERENCES

10.26. Lubricant and Fuel Additives Based on Polyalkylmethacrylates

10.26.1 Synthesis of Polyalkylmethacrylates

10.26.2 The Chemistry of Polyalkylmethacrylates

10.26.3 Applications of PAMAs

REFERENCES

10.27. Aqueous Emulsion Polymers

10.27.1 Introduction

10.27.2 Emulsion Polymerization and Powder Production

10.27.3 Introduction on Dry Mortars

10.27.4 Function of Dispersible Polymer Powders in Dry Mortars

10.27.5 Environmental Aspects of Using Polymer-Modified Dry Mortars

10.27.6 Applications of Polymer-Modified Dry Mortars

10.27.7 Summary on Polymers in Dry Mortars

10.27.8 Polymer Dispersions in Paper Manufacturing

10.27.9 Polymer Dispersions in Adhesives

10.27.10 Polymer Dispersions in Architectural Coatings

10.27.11 Nonwoven Fabrics

10.27.12 Summary and Outlook

REFERENCES

10.28. Water-Based Epoxy Systems

10.28.1 Introduction

10.28.2 Definition

10.28.3 Classification of Waterborne Epoxy Technologies

10.28.4 Comparison of Waterborne and Solvent-Borne Epoxy Coatings

10.28.5 Waterborne Amine Hardeners: General Structural Requirements

10.28.6 Type I Waterborne Epoxy Technologies

10.28.7 Type II Waterborne Epoxy Technologies

10.28.8 Deep Penetrating and Green Concrete Primer

10.28.9 Water Vapor Permeable Floor Systems

10.28.10 Concrete Coating Systems

10.28.11 Waterborne Epoxy Curing Agent Systems

10.28.12 Self-Leveling Floor Formulation

10.28.13 Self-Leveler

10.28.14 Low-Emission Industrial Floorings

10.28.15 Path to Low-Emission Floorings

10.28.16 Water-Based Low-Emission Formulation

10.28.17 Time Is Money

10.28.18 Conclusions

REFERENCES

10.29. Powder Coatings

10.29.1 Introduction

10.29.2 General Concepts

10.29.3 Material Saving

10.29.4 Raw Materials

10.29.5 Production of Powder Coatings

10.29.6 Application of Powder Coatings

10.29.7 In-Use Considerations

10.29.8 Future Trends

REFERENCES

10.30. Radiation-Curing Polymer Systems

10.30.1 Introduction

10.30.2 Technology

10.30.3 Formulations and Raw Materials

10.30.4 Network Formation and Characterization

10.30.5 Structure–Property Relationship

10.30.6 Applications

10.30.7 Perspectives

REFERENCES

Plastics after Use

10.31. Sustainable Management of Material and Energy Resources

10.31.1 Introduction

10.31.2 Waste Management

10.31.3 Regulatory Framework for Waste Management in Europe

10.31.4 Plastics Waste in Europe

10.31.5 Plastics Waste Recovery

10.31.6 Plastics Waste Recovery and Sustainability

10.31.7 Outlook 2020+

REFERENCES

Polymers in Energy Applications

10.32. Polymers in Energy Applications

10.32.1 Introduction

10.32.2 Chapter Summaries

10.33. Poly(Perfluorosulfonic Acid) Membranes

10.33.1 Introduction

10.33.2 Membrane Manufacturing

10.33.3 Morphology

10.33.4 Durability and Lifetime

10.33.5 New Chemistry

10.33.6 Summary

REFERENCES

10.34. Alternative Hydrocarbon Membranes by Step Growth

10.34.1 Introduction

10.34.2 Alternative Hydrocarbon Ionomer Membranes

10.34.3 Recent Trends in Hydrocarbon Ionomer Membranes

10.34.4 Application to Fuel Cells

10.34.5 Prospects

REFERENCES

10.35. Alternative Proton Exchange Membranes by Chain-Growth Polymerization

10.35.1 Introduction

10.35.2 Chain-Growth Polymerization

10.35.3 Chain-Growth Polymerization Applied to PEM Materials

10.35.4 Conclusions and Future Directions

REFERENCES

10.36. Polymers in Membrane Electrode Assemblies

10.36.1 Introduction

10.36.2 Polymer Electrolyte Membranes

10.36.3 Polymer Electrolyte Ionomers in the Electrode

10.36.4 Summary

REFERENCES

10.37. Morphology of Proton Exchange Membranes

10.37.1 Introduction

10.37.2 Perfluorosulfonate Ionomers as the Benchmark Materials for Proton Exchange Membranes

10.37.3 Alternative Membrane Materials

10.37.4 Evolution of Morphological Models for Nafion®

10.37.5 Morphology–Property Relationships in Ion-Containing Polymers

10.37.6 Development and Manipulation of Morphological Features in Proton Exchange Membranes

10.37.7 Computational Modeling/Simulation of Proton Exchange Membrane Morphology

10.37.8 Conclusions

REFERENCES

10.38. Polymer Electrolyte Membrane Degradation

10.38.1 Introduction

10.38.2 Mechanical Degradation of Polymer Electrolyte Membranes

10.38.3 Chemical Degradation of Polymer Electrolyte Membranes

10.38.4 Summary

REFERENCES

10.39. Molecular and Mesoscale Modeling of Proton Exchange Membranes

10.39.1 Introduction

10.39.2 Simulations of PEMs

10.39.3 Future Directions

REFERENCES

10.40. Polymers for Thin Film Capacitors

10.40.1 Capacitor Fundamentals

10.40.2 Dielectric Polymers

10.40.3 Biaxially Oriented PP Film Capacitors

10.40.4 Ferroelectric Poly(vinylidene fluoride)-Based Film Capacitors

10.40.5 High-Temperature Polymer Capacitors

10.40.6 Polymer Nanocomposite Capacitors

10.40.7 Conclusions

REFERENCES

10.41. Aromatic Poly(amides) for Reverse Osmosis

10.41.1 Introduction

10.41.2 RO Theory

10.41.3 Real-World Design Considerations

10.41.4 RO History

10.41.5 Thin-Film Composites

10.41.6 Polyamide Thin-Film Composites

10.41.7 FT-30 Polymer Analogies

10.41.8 Conclusions

REFERENCES

10.42. Electrolyzer Membranes

10.42.1 Introduction

10.42.2 Development of Polymer Electrolyte Membranes for Electrolysis

10.42.3 Polymer Membranes in the Chlor-Alkali Industry

10.42.4 Polymer Membranes in Gas Generators

10.42.5 Polymer Membranes in Early Regenerative Fuel Cells

10.42.6 Polymer Membrane Performance and Degradation

10.42.7 Performance Fundamentals

10.42.8 Electrolysis and Thermochemical Cycles

10.42.9 Status of Nuclear Power Technology

10.42.10 Review of the Hybrid Sulfur Electrolyzer

10.42.11 Hybrid Sulfur Electrolyzer Performance

10.42.12 Conclusions

REFERENCES

Subject Index

Authors

Life Sciences

Physical Sciences & Engineering

Social Sciences & Humanities

Health

Polymer Science: A Comprehensive Reference

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Martin Moeller

Krzysztof Matyjaszewski

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