Document b52X2n7MKZvjYEZxbkKQEzrz0

AKAS6- 267 FlUO RIIW ED SDREAC1ANTS AND REPELLENTS RovSiseocdonadndEEdxitpioannded Erik Kissa W ilmiCngotnosnu, lDtaenltaware MARCEL OEKKER Marcel Dekker, In c. N ew York Basel First edition published as Fluonnated Surfactants, by E. Kissa, Marcel Dekker, Inc., NY, 1994. Antron, Atsurf, Fluorad, Fluosol, Fluowet, Forafac, Lodyne, Monflor, Oxydent, Pluronic, Quilon, Scotchban, Stainmaster, Surflon, Teflon, and Zonyl are registered trademarks. ISBN: 0-8247-0472-X This book is printed on acid-free paper. Headquarters Marcel Dekker, Inc. 270 Madison Avenue, New York, NY 10016 tel: 212-696-9000; fax: 212-685-4540 Eastern Hemisphere Distribution Marcel Dekker AG Hutgasse 4, Postfach 812, CH-4001 Basel, Switzerland tel: 41-61-261-8482; fax: 41-61-261-8896 World Wide Web http://www.dekker.com The publisher offers discounts on this book when ordered in bulk quantities. For more information, write to Special Sales/Professional Marketing at the headquarters address above. Copyright 2001 by Marcel Dekker, Inc. All Rights Reserved. Neither this book nor any part may be reproduced or transmitted in any form or by any means, electronic or mechanical, including photocopying, microfilming, and recording, or by any information storage and retrieval system, without permission in writing from the publisher. Current printing (last digit): 10 9 8 7 6 5 4 3 2 1 PRINTED IN THE UNITED STATES OF AMERICA Contents PREFACE TO THE SECOND EDITION PREFACE TO THE FIRST EDITION PART A. FLUORINATED SURFACTANTS 1. STRUCTURE OF FLUORINATED SURFACTANTS 1.1 Introduction 1.2 Structural Features of Fluorinated Surfactants. The Hydrophobe 1.3 Anionic Fluorinated Surfactants 1.4 Cationic Surfactants 1.5 Amphoteric Surfactants 1.6 Nonionic Surfactants 1.7 Silicon-Containing Fluorinated Surfactants 1.8 Fluorinated Surfactants Without a Hydrophile 1.9 Polymeric Fluorinated Surfactants References 2. SYNTHESIS 2.1 Starting Materials 2.2 Electrochemical Fluorination 2.3 Telomerization 2.4 Oligomerization of Tetrafluoroethylene iii V 1 1 3 4 7 8 10 11 14 15 21 29 29 31 36 40 vii I/ Contents 2.5 Miscellaneous Reactions 2.6 Anionic Fluorinated Surfactants 2.7 Cationic Surfactants 2.8 Amphoteric Surfactants 2.9 Nonionic Surfactants References PHYSICAL AND CHEMICAL PROPERTIES 3.1 Chemical Properties 3.2 Melting Points 3.3 Boiling Points 3.4 Density 3.5 Refractive Index References LIQUID-VAPOR AND LIQUID-LIQUID BOUNDARIES. SURFACE TENSION 4.1 Theory of Surface Tension 4.2 Adsorption at Liquid-Vapor Boundary 4.3 Surface Tension in Water. Surfactant Structure 4.4 Kinetics of Adsorption 4.5 Surface Tension in Acids and Alkali 4.6 Surface Tension in Organic Liquids 4.7 Liquid-Liquid Interface 4.8 Emulsions 4.9 Foams References SOLID-LIQUID INTERFACE 5.1 Adsorption from Solution 5.2 Adsorption of Mixed Surfactants References FLUORINATED SURFACTANTS IN SOLUTION 6.1 Solubility 6.2 Micelle Formation 6.3 Krafft Point 6.4 Cloud Point 6.5 Thermodynamics of Micellization 6.6 Critical Micelle Concentration 43 44 56 59 64 70 80 80 90 94 99 100 101 103 103 108 124 133 139 145 155 160 166 169 175 175 190 194 198 198 202 210 217 220 228 4 i. \X X Contents 10. TOXICOLOGY AND ENVIRONMENTAL ASPECTS 10.1 Toxicology 10.2 Environmental Aspects 10.3 Physiology: Sorption, Metabolism, and Excretion 10.4 Fluorochemical Emulsions for Biomedical Oxygen Transport 10.5 Drug Delivery and Other Pharmaceutical Applications References 451 451 456 461 467 486 487 PART B. FLUORINATED REPELLENTS AND SOIL RETARDANTS II. THEORY OF REPELLENCY 11.1 Definitions 11.2 Wetting 11.3 The Equilibrium Contact Angle 11.4 Contact Angles in Real Systems 11.5 Critical Surface Tension and Surface Energy 11.6 Kinetics of Wetting 11.7 Repellency of Fabrics References 12. FLUORINATED REPELLENTS 12.1 Repellents with Hydrocarbon Hydrophobes 12.2 Silicones (Polysiloxanes) 12.3 Fluorochemical Repellents 12.4 Repellent Finishing with Fluoropolymers 12.5 Repellency Tests 12.6 Future References 494 494 495 498 499 501 506 510 513 516 516 525 530 541 543 551 551 13. FLUORINATED SOIL RETARDANTS 13.1 Soils 13.2 Soiling Mechanisms 13.3 Theory of Soil Retardation 13.4 Fluorinated Soil Retardants 13.5 Soil-Resistance Tests 13.6 Fluorinated Soil-Release Agents References 557 557 558 560 565 568 574 579 Contents 6.7 Solubilization 6.8 Association with Cyclodextrins References 7. STRUCTURE OF MICELLES AND MESOPHASES 7.1 Structure of Micelles 7.2 Theory for Mixed Micelles 7.3 Surfactant Mixtures 7.4 Mesophases and Liquid Crystals 7.5 Hybrid Surfactants References 8. APPLICATIONS 8.1 Performance Characteristics of Fluorinated Surfactants 8.2 Selection of Fluorinated Surfactants 8.3 Specific Applications References 9. ANALYSIS OF FLUORINATED SURFACTANTS 9.1 Determination and Characterization of Fluorinated Surfactants 9.2 Elemental Analysis 9.3 Volumetric Methods and Ion-Pair Spectroscopy 9.4 Chromatography 9.5 Ultraviolet and Infrared Spectroscopy 9.6 Mass Spectrometry 9.7 Nuclear Magnetic Resonance 9.8 Electron Spin Resonance 9.9 Chemical Relaxation Methods 9.10 Small-Angle Scattering Methods 9.11 Light Scattering 9.12 Luminescence Probing Methods 9.13 X-Ray Photoelectron Spectroscopy 9.14 Electrochemical Methods 9.15 Ultrafiltration 9.16 Surface Tension 9.17 Fluorinated Surfactants in Biological Systems 9.18 Fluorinated Surfactants in the Environment References ix 256 269 269 277 277 288 299 330 340 342 349 349 350 352 379 390 390 390 393 394 396 399 405 409 410 413 415 416 419 422 426 427 434 436 437 1 l<+ Contents 14. STAIN-RESISTANT CARPETS 14.1 Soiling and Staining 14.2 Carpet Fibers 14.3 Stains 14.4 Coffee Stains on Nylon 14.5 Theories for Stain Resistance 14.6 Stain-Resist Agents 14.7 Stain-Resistance Tests References INDEX xi 582 582 582 584 587 589 592 598 602 607