Handbook of Fluoropolymer Science and Technology -- Contents -- Foreword -- In Memoriam -- Preface -- Contributors -- About the Editors -- 1 Fluorinated Polyphosphazenes -- 1.1 BACKGROUND -- 1.2 SYNTHESIS METHODS AND PROPERTY DEVELOPMENT -- 1.3 THE ROLE OF FLUORINE IN POLYPHOSPHAZENE SYNTHESIS CHEMISTRY -- 1.3.1 Facilitation of Chlorine Replacement by Fluorinated Nucleophiles -- 1.3.2 Enhancement of the Hydrolytic Stability and Resistance to Other Reagents When Fluorine Is Present in the Organic Side Groups -- 1.3.3 Influence by the Structure of the Fluorinated Alkoxide Nucleophile -- 1.3.4 Fluoroaryloxy Side Groups -- 1.3.5 Fluorinated Alkylamino Side Groups -- 1.3.6 Poly(difluorophosphazene) and Derivatives as Alternatives to Poly(dichlorophosphazene) -- 1.3.7 Block Copolymers and Micelles -- 1.4 PROPERTIES OF FLUORINATED POLYPHOSPHAZENES -- 1.4.1 Solubility as a Function of Side Group Structure -- 1.4.2 Solid State Properties -- 1.4.3 Surface Properties -- 1.4.4 Thermal and Thermo-Oxidative Stability -- 1.5 EXISTING AND EMERGING APPLICATIONS FOR FLUORINATED POLYPHOSPHAZENES -- 1.5.1 Fibers and Nanofibers -- 1.5.2 Impact-Absorbing Elastomers -- 1.5.3 Surface Coatings -- 1.5.4 Radiation Resistant Polymers -- 1.5.5 Membranes -- 1.5.6 Micelles -- 1.5.7 Uses for Fluorophosphazene Oligomers -- REFERENCES -- 2 Mn2(CO)10-Visible Light Photomediated, Controlled Radical Polymerization of Main Chain Fluorinated Monomers and Synthesis of Block Copolymers Thereof -- 2.1 INTRODUCTION -- 2.2 VDF PHOTOPOLYMERIZATION CATALYST SELECTION -- 2.3 EFFECT OF REACTION PARAMETERS AND MECHANISTIC CONSIDERATIONS -- 2.3.1 Effect of Temperature and Light -- 2.3.2 Solvent Effect -- 2.3.3 Polymerization Mechanism and Initiator Evaluation -- 2.4 SYNTHESIS OF WELL-DEFINED BLOCK COPOLYMERS FROM PVDF-I AND I-PVDF-I CHAIN ENDS -- 2.5 CONCLUSIONS -- REFERENCES.

3 Interfacial Response of Semifluorinated Multi-Block Copolymers -- 3.1 Introduction -- 3.2 Simulation Model and Methodology -- 3.3 Results and Discussion -- 3.4 Conclusions -- ACKNOWLEDGMENTS -- REFERENCES -- 4 FLUOROPOLYMER NANOCOMPOSITES -- 4.1 Introduction and Overview -- 4.2 Preparation of Fluoroalkyl End-Capped Oligomers -- 4.3 Preparation and Thermal Stability of Fluoroalkyl End-Capped Oligomers/Silica Nanocomposites -- 4.4 Preparation and Properties of Fluoroalkyl End-Capped Oligomers/Titanium Oxide Nanocomposites -- 4.5 Preparation and Properties of Fluoroalkyl End-Capped Oligomers/Calcium Carbonate Nanocomposites -- 4.6 Preparation and Properties of Fluoroalkyl End-Capped Oligomeric Nanocomposites-Encapsulated Organic Guest Molecules -- REFERENCES -- 5 Thermal Degradation and Pyrolysis of Polytetrafluoroethylene -- 5.1 Introduction -- 5.2 Ptfe Pyrolysis -- 5.2.1 Overview of Methods -- 5.2.2 Mechanism of Pyrolysis -- 5.3 Autogenous Reactions of Pyrolysis Products -- 5.3.1 Mechanism of TFE Formation -- 5.3.2 Mechanism of OFCB Formation -- 5.3.3 Mechanism of Hexafluoropropylene Formation -- 5.3.4 Mechanism of Formation of Perfluorobutenes -- 5.3.5 Toxicity and Safe Handling of Pyrolysis Products -- 5.4 Catalytic Reactions of Pyrolysis Products -- 5.4.1 Catalytic Reformation of TFE -- 5.4.2 Reactions of TFE With Species Containing Hetero-Atoms -- 5.4.3 Mechanism of Catalysis -- NOMENCLATURE -- REFERENCES -- 6 Molecular Simulation of Fluoropolymers -- 6.1 Introduction -- 6.2 Overview of Computational Methods -- 6.2.1 Quantum Calculation Methods -- 6.2.2 Atomistic Methods -- 6.3 Polymerization -- 6.3.1 Telomerization -- 6.3.2 Initiators -- 6.4 Force Fields for Fluoropolymers -- 6.4.1 Force Fields for PTFE -- 6.4.2 Force Fields for PVDF -- 6.4.3 Specific Force Fields in Explosive Materials -- 6.4.4 Current Status -- 6.5 Studies on PVDF.

6.5.1 Electric Properties -- 6.5.2 Polymorphism in Crystalline PVDF -- 6.5.3 Presence of Defects -- 6.6 Applications -- 6.6.1 Characterization Tool -- 6.6.2 Environment -- 6.6.3 Fuel Cells -- 6.6.4 Coatings -- REFERENCES -- 7 VAPOR DEPOSITION OF FLUOROPOLYMER SURFACES -- 7.1 Introduction -- 7.2 Polytetrafluoroethylene (PTFE) -- 7.3 Poly(Vinylidene Fluoride) -- 7.4 Poly(1H,1H,2H,2H-Perfluorodecyl Acrylate) -- 7.5 Copolymerization of Fluorinated Monomers -- 7.5.1 Copolymers with 1H,1H,2H,2H-Perfluorodecyl Acrylate (PFDA) -- 7.5.2 Copolymers with Pentafluorophenyl Methacrylate (PFM) -- 7.5.3 Copolymers with 2,2,3,3,4,4,5,5,6,6,7,7-Dodecafluoroheptyl Acrylate (DFHA) and (Perfluoroalkyl)Ethyl Methacrylate (PFEMA) -- 7.5.4 Copolymers with Organosilicons -- 7.6 Summary -- Acknowledgments -- REFERENCES -- 8 Functionalized and Functionalizable Fluoropolymer Membranes -- 8.1 Introduction -- 8.2 Preparation of Fluoropolymer Membranes -- 8.2.1 Phase Inversion -- 8.2.2 Track Etching -- 8.2.3 Sintering -- 8.2.4 Electrospinning -- 8.3 Functionalization of Fluoropolymer Membranes -- 8.3.1 Modification by Blending -- 8.3.2 Modification by Graft Copolymerization -- 8.3.3 Surface Modification and Functionalization of Fluoropolymer Membranes -- 8.4 Summary -- REFERENCES -- 9 POLY[METHYL(3,3,3-TRIFLUOROPROPYL)SILOXANE] -- 9.1 Introduction -- 9.2 Manufacture -- 9.3 Properties -- 9.3.1 Liquid Surface Tension -- 9.3.2 Solid Surface Tension -- 9.3.3 Polymer/Water Interface -- 9.3.4 X-Ray Photoelectron Spectra -- 9.4 OTHER PROPERTIES -- 9.4.1 Swelling Resistance -- 9.4.2 Glass Transition Temperature -- 9.4.3 Viscosity -- 9.4.4 Permeability -- 9.4.5 Electrical Properties -- 9.4.6 Lubrication -- 9.5 CONCLUDING REMARKS -- REFERENCES -- 10 Functional Fluorous Copolyoxetane Polymer Surface Modifiers -- 10.1 Introduction.

10.2 Different Nanoscale Phase Separation and Wetting Behavior for Random versus Block P[A-co-B] Soft Blocks -- 10.3 U-P[AB] WHEREIN A COPOLYMER EFFECT ENHANCES HYDROPHOBICITY -- 10.4 Surfaces that are Reversibly Hydrophilic When Dry and Hydrophobic When Wet, or "Contraphilic" -- 10.5 Introducing Surface Charge via P[AB] Soft Block Polyurethanes with Alkylammonium B Side Chains -- 10.6 SUMMARY -- ACKNOWLEDGMENTS -- REFERENCES -- 11 Self-Organizing Semifluorinated Methacrylate Copolymers -- 11.1 Introduction and Overview -- 11.2 Synthesis Methods for Semifluorinated Copolymers -- 11.2.1 Overview -- 11.2.2 Semifluorinated Methacrylate Copolymers -- 11.3 Self-Organization Behavior of Semifluorinated Polymers in Bulk and in Thin Films -- 11.3.1 Methods to Observe Self-Organization -- 11.3.2 Overview about Self-Organized Semifluorinated Alkanes and Polymers -- 11.3.3 Self-Organization in Polymers with Long Semifluorinated Side Chains -- 11.3.4 Semifluorinated Methacrylate Copolymers -- 11.4 Consequences of Self-Organization for the Macroscopic Wetting Behavior -- 11.5 Possible Applications of Semifluorinated Methacrylates -- 11.6 Summary and Outlook -- ACKNOWLEDGMENTS -- REFERENCES -- 12 Synthesis of Fluoropolymers Using Borane-Mediated Control Radical Polymerization for Energy Storage Applications -- 12.1 Introduction -- 12.2 Borane Oxidation/Polymerization Mechanism -- 12.3 Fluoropolymer Dielectric for High Energy Density Capacitors -- 12.4 Functional Fluoropolymer for Proton Exchange Membranes -- 12.5 Functional Fluoropolymer for Proton-Conductive Composite Membranes -- 12.6 Conclusion -- ACKNOWLEDGMENT -- REFERENCES -- 13 Fluoropolymers in Supercritical Carbon Dioxide: Phase Behavior, Self-Assembly, and Stabilization of Water/Co2 Emulsions -- 13.1 Introduction and Overview -- 13.2 Solubility of (Co)Polymers in sc-CO2.

13.2.1 Interactions of CO2 with Fluorine Atoms -- 13.2.2 Phase Behavior of (CO)Polymers in CO2 -- 13.3 Self-Assembly of Amphiphilic Copolymers in sc-CO2 -- 13.3.1 Block Copolymers -- 13.3.2 Amphiphilic Gradient Copolymers -- 13.3.3 Double CO2-Philic Block Copolymers -- 13.3.4 Amphiphilic Graft and Comb Copolymers -- 13.3.5 Amphiphilic Hyperbranched Polymers and Dendrimers -- 13.4 Fluorinated Macromolecular Surfactants for Water/Carbon Dioxide Emulsions -- 13.4.1 Water/CO2 Macroemulsions -- 13.4.2 Water/CO2 Miniemulsions -- 13.4.3 Critical Flocculation Density -- 13.4.4 Water/CO2 Microemulsions -- 13.5 Conclusion -- REFERENCES -- 14 Semifluorinated Polymers from Trifluorovinyl Aromatic Ether Monomers -- 14.1 INTRODUCTION -- 14.2 SYNTHESIS OF TRIFLUOROVINYL AROMATIC ETHER -- 14.2.1 Classical Synthesis for Trifluorovinyl Aromatic Ether -- 14.2.2 The "Intermediate" Route to Trifluorovinyl Aromatic Ether -- 14.3 NMR CHARACTERIZATION OF TRIFLUOROVINYL AROMATICETHER -- 14.4 CYCLODIMERIZATION OF TRIFLUOROVINYL AROMATICETHER -- 14.5 POLYMER SYNTHESIS VIA [2+2] CYCLOADDITION OF ARYL TRIFLUOROVINYL ETHERS -- 14.6 CONCLUSIONS -- ACKNOWLEDGMENTS -- REFERENCES -- 15 Combustion Characterization of Energetic Fluoropolymer Composites -- 15.1 Introduction -- 15.2 SYNTHESIS OF COMPOSITES -- 15.2.1 Stoichiometry -- 15.2.2 Mixing -- 15.2.3 Powders Versus Pellets -- 15.3 EQUILIBRIUM KINETICS -- 15.3.1 Simultaneous Thermal Analysis -- 15.3.2 Molecular Structure -- 15.4 NONEQUILIBRIUM COMBUSTION CHARACTERIZATIONS -- 15.4.1 Energy Propagation -- 15.4.2 Ignition -- 15.5 CONCLUSION -- ACKNOWLEDGMENTS -- REFERENCES -- 16 Amorphous Perfluoropolymers -- 16.1 Introduction -- 16.2 Effect of the Polymer Structure on Tg -- 16.3 Copolymers With TFE-Teflon® AF AND Hyflon® AD -- 16.4 Poly(Perfluoro-4-Vinyloxy-1-Butene)-Cytop® -- 16.5 Syntheses of Teflon®, Hyflon®, and Cytop® Monomers.

16.6 Perfluoro-2-Methylene-1,3-Dioxolanes.