Organofluorlne Chemistry Principles and Commercial Applications TOPICS in APPLIED CHEMISTRY Series Editors: Alan R

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Organofluorlne Chemistry Principles and Commercial Applications TOPICS IN APPLIED CHEMISTRY Series Editors: Alan R. Katritzky, FRS Kenan Professor of Chemistry University of Florida, Gainesville, Florida Gebran J. Sabongi Laboratory Manager, Encapsulation Technology Center, 3M St. Paul, Minnesota

BIOCATALYSTS FOR INDUSTRY Edited by Jonathan S. Dordick CHEMICAL TRIGGERING Reactions of Potential Utility in Industrial Processes Gebran J. Sabongi THE CHEMISTRY AND APPLICATION OF DYES Edited by David R. Waring and Geoffrey Hallas HIGH-TECHNOLOGY APPLICATIONS OF ORGANIC COLORANTS Peter Gregory INFRARED ABSORBING DYES Edited by Masaru Matsuoka LEAD-BASED PAINT HANDBOOK Jan W. Gooch ORGANOFLUORINE CHEMISTRY Principles and Commercial Applications Edited by R. E. Banks, B. E. Smart, and J. C. Tatlow POLY(ETHYLENE GLYCOL) CHEMISTRY Biotechnical and Biomedical Applications Edited by J. Milton Harris RADIATION CURING Science and Technology Edited by S. Peter Pappas RESORCINOL Its Uses and Derivatives Hans Dressler STRUCTURAL ADHESIVES Edited by S. R. Hartshorn TARGET SITES FOR HERBICIDE ACTION Edited by Ralph C. Kirkwood

A Continuation Order Plan is available for this series. A continuation order will bring delivery of each new volume immediately upon publication. Volumes are billed only upon actual shipment. For further information please contact the publisher. Organofluorine Chemistry Principles and Commercial Applications

Edited by R. E. Banks The University of Manchester Institute of Science and Technology (UMIST) Manchester, United Kingdom B. E. Smart DuPont Central Research & Development Wilmington, Delaware and J. C. Tatlow Editorial Office of the Journal of Fluorine Chemistry Birmingham, United Kingdom

Springer Science+ Business Media, LLC Library of Congress Cata1oging-in-Publication Data

Organofluorine chemistry : principles and commercial applications / edited by R.E. Banks, B.E. Smart, and J.C. Tatlow. p. cm. — (Topics 1n applied chemistry) Includes bibliographical references and Index. ISBN 978-1-4899-1204-6 1. Organofluorine compounds. I. Banks, R. E. (Ronald Eric), 1932- . II. Smart, B. E. (Bruce E.) III. Tatlow, J. C. IV. Series. QD305.H15074 1994 661' .891—dc20 94-26835 CIP

10 98765432

ISBN 978-1-4899-1204-6 ISBN 978-1-4899-1202-2 (eBook) DOI 10.1007/978-1-4899-1202-2

No part of this book may be reproduced, stored in a retrieval system, or transmitted in any form or by any means, electronic, mechanical, photocopying, microfilming, recording, or otherwise, without written permission from the Publisher Contributors

Y. W. Alsmeyer, Fluorochemical Process Technology Center, 3M Company, St. Paul, Minnesota 55144-1000

Madhu Anand, Air Products and Chemicals, Inc., Allentown, Pennsylvania 18195- 1501

Wolfgang K. Appel, Hauptlaboratorium, Hoechst AG, D-6230 Frankfurt-am-Main 80, Germany

Bruce E. Baker, DuPont Speciality Chemicals, Jackson Laboratory, Chambers Works, Deepwater, New Jersey 08023

R. E. Banks, Department of Chemistry, The University of Manchester Institute of Science and Technology, Manchester M60 lQD, England

BemdA. Bloch, RLMTC, Hoechst Celanese Corporation, Summit, New Jersey 07901

Ian J. Brass, Air Products PLC, Walton-on-Thames, Surrey KT12 4RZ, England

David Cartwright, Zeneca Agrochemicals, Jeallott's Hill Research Station, Brack• nell, Berkshire RG 12 6EY, England

W. V. Childs, Fluorochemical Process Technology Center, 3M Company, St. Paul, Minnesota 55144-1000

Richard A. Du Boisson, PeR Inc., Gainesville, Florida 32602

Philip Neil Edwards, Zeneca Pharmaceuticals, Aldedey Park, Macclesfield, Cheshire SKI04TG, England

Arthur J. Elliott, Halocarbon Products Corporation, North Augusta, South Carolina 29841-0369

A. Engel, Bayer AG, Research and Development-Dyes and Pigments, D-51368 Leverkusen 1, Germany

v vi Contributors

Andrew E. Feiring, DuPont Central Research & Development Department, Experi• mental Station, Wilmington, Delaware 19880-0328

Peter Field, PGF Associates Ltd., Buxton, Derbyshire SK17 6EW, England

R. M. Flynn, Fluorochemical Process Technology Center, 3M Company, St. Paul, Minnesota 55144-1000

S. W. Green, Rhone-Poulenc Chemicals Ltd., Avonmouth, Bristol BS11 9HP, England; present address: 69 South Road, Kingswood, Bristol BS 15 2JF, England

Donald F. Halpern, Ohmeda, P.P.D., Murray Hill, New Jersey 07076; present address: 44 Murray Hill Square, Murray Hill, New Jersey 07974.

K. J. Herd, Bayer AG, Research and Development-Dyes and Pigments, D-51368 Leverkusen 1, Germany

J. P. Hobbs, Air Products and Chemicals, Inc., Allentown, Pennsylvania 18195-1501

Takeshi Inoi, Technical Division, Chisso Corporation, Tokyo, Japan; present address: 8-8-6 Sugita, Isogo-ku, Yokohama-shi, Kanagawa-ken 236, Japan tNobuo Ishikawa, F & F Research Center, Shizushin Building, Minato-ku, Tokyo 107, Japan

Bernard Langlois, Laboratoire de Chimie Organique III, Universite Claude Bernard• Lyon I, 69622 Villeurbanne Cedex, France

Andre Lantz, Atochem, Centre de Recherche Rhone-Alpes, 69310 Pierre-Benite, France

Anestis L. Logothetis, DuPont Elastomers, Experimental Station, Wilmington, Dela• ware 19880-0328

Kenneth C. Lowe, Mammalian Physiology Unit, Life Science Department, Univer• sity of Nottingham, University Park, Nottingham NG7 2RD, England

Ganpat Mani, Allied-Signal Inc., Fluorine Products Division, Morristown, New Jersey 07962-1139

Guiseppe Marchionni, AusimontIMontefluos, MontedisonIMontefluos Group, 20021 Bollate, Milano, Italy

Harubisa Miyake, Research Center, Asahi Glass Co. Ltd., Kanagawa-ku, Yokohama 221, Japan tDeceased. Contributors vii

J. S. MoilIiet, Zeneca Agrochemicals, Huddersfield HD2 IFF, England; present address: BNFL Fluorochemicals, Springfields, Salwick, Preston PR4 OXJ, England

G. G. I. Moore, Fluorochemical Process Technology Center, 3M Company, St. Paul, Minnesota 55144-1000

Yohnosuke Ohsaka, Daikin Industries, Ltd., Chemical Division, 1-1 Nishi Hitotsuya, Settsu-shi, Osaka 566, Japan; present address: 1-16-5 Shirakawa, !baraki, Osaka, Japan

Ralph J. De Pasquale, AusimontiMontefluos, MontedisonIMontefluos Group, 20021 Bollate, Milano, Italy; present adddress: 5500 Atlantic View, St. Augustine, Florida 32084

Richard L. Powell, ICI Klea, Runcorn Technical Centre, Runcorn, Cheshire WA7 4QD, England

Nandakumar S. Rao, DuPont Speciality Chemicals, Jackson Laboratory, Chambers Works, Deepwater, New Jersey 08023 v. N. M. Rao, DuPont Central Research & Development, Experimental Station, Wilmington, Delaware 19880-0262

George A. Shia, Allied-Signal Inc., Fluorine Products Division, Buffalo Research Laboratory, Buffalo, New York 14210

Dario Sianesi, AusimontiMontefluos, MontedisonIMontefluos Group, 20021 Bollate, Milano, Italy

R. N. F. Simpson, RMne-Poulenc Chemicals Ltd., Avonmouth, Bristol BSll 9Hp, England; present address: Fluoro Systems Ltd., Abbots Leigh, Bristol BS8 3Rp, England

D. S. L. Slinn, RMne-Poulenc Chemicals Ltd., Avonmouth, Bristol BSll 9Hp, England; present address: Fluoro Systems Ltd., Abbots Leigh, Bristol BS8 3RP, England

Bruce E. Smart, DuPont Central Research & Development, Experimental Station, Wilmington, Delaware 19880-0328

J. C. Smeltzer, Fluorochemical Process Technology Center, 3M Company, St. Paul, Minnesota 55144-1000

J. Hugo Steven, ICI Klea, Runcorn Technical Centre, Runcorn, Cheshire WA7 4QD, England

Michael StObbe, Hauptlaboratorium, Hoechst AG, D-6230 Frankfurt-am-Main 80, Germany viii Contributors

J. C. Tatlow, Editorial Office of the Journal of Fluorine Chemistry, 30 Grassmoor Road, Kings Norton, Birmingham B38 8Bp, England

Claude Wakselman, CNRS-CERCOA, 94320 Thiais, France

A. J. Woytek, Air Products and Chemicals Inc., Industrial Gas Division, Allentown, Pennsylvania 18105

Masaaki Yamabe, Research Center, Asahi Glass Co. Ltd., Kanagawa-ku, Yokohama 221, Japan Preface

During the past fifteen years commercial interest in compounds containing carbon• fluorine bonds has burgeoned beyond all expectations, mainly owing to business opportunities arising from work on biologically active fluoroorganics-particularly agrochemicals, the relentless search for new markets for fluoropolymers and fluoro• carbon fluids, developments in the field of medical diagnostics, and the drive to find replacements for ozone-depleting CFCs and Halon fire-extinguishing agents. Judging the situation to warrant the publication of a comprehensive collection of up-to-date reviews dealing with commercial organofluorine compounds within a single volume of manageable size (and hence reasonable cost), we were delighted to be invited by Plenum Publishing Corporation to produce a suitable book. In order to provide an authentic and wide-ranging account of current commercial applications of fluoroorganic materials, it clearly was necessary to assemble a sizeable team of knowledgeable contributing authors selected almost entirely from industry. Through their efforts we have been able to produce an almost complete coverage of the modem organofluorochemicals business in a manner designed to attract a reader• ship ranging from experts in the field, through chemists and technologists currently unaware of the extent of industrial involvement with fluoroorganics, to students of applied chemistry. Promised chapters dedicated to perfluoroolefin oxides and 18F labeling of radiopharmaceuticals failed to materialize. This is somewhat unfortunate in view of our aim to achieve comprehensive coverage of the subject. However, not only do other chapters touch on these topics, but an excellent 149-page review, Fluorine-I8 Labeling of Radiopharmaceuticals (National Academy Press, Washing• ton DC, 1990) by Michael R. Kilbourn is available gratis from The Board on Chemical Sciences and Technology, National Research Council, 2101 Constitution Avenue NW, Washington, D.C. 20418, U.S.A. Finally we must emphasize that the production of this book has been a team effort and our sincere thanks go to all those who have contributed: librarians, typists, the staff at Plenum, co-workers and colleagues of authors, and-preeminently-the collaborating authors themselves. Sadly, one of our authors, Professor Nobuo Ishikawa, died in 1991, and we respectfully dedicate this book to his memory. Employment of such a large number of contributing authors, coupled with the busy lives they lead and the need to have manuscripts cleared for publication by the

ix x Preface companies involved, has resulted in an unusually wide range of receipt dates for typescripts. In fact, chapters started to arrive in the summer of 1990 and continued to appear until February 1992! Not wishing to leave too many gaps, we just held on as long as seemed reasonable. Our apologies for the delay in publication are offered to those authors who were within six months of the original deadline. Our own efforts toward the completion of this book are dedicated severally to our wives, who seem to possess endless patience.

R. E. Banks Manchester, England Bruce Smart Wilmington, Delaware 1. C. Tatlow Birmingham, England Contents

1. Organotluorine Chemistry: Nomenclature and Historical Landmarks

R. E. Banks and J. C. Tatlow 1.1. Preamble ...... 1 1.2. Nomenclature...... 2 1.2.1. Highly Fluorinated Compounds. 2 1.2.2. Fluorocarbon Code Numbers 4 1.3. Historical Landmarks...... 5 1.3.1. The HF Problem ...... 5 1.3.2. Synthesis of C-F Bonds . . . 6 1.3.3. Aliphatic Fluorides Go Commercial .12 1.3.4. Perfluorocarbons ...... 14 1.3.5. Wartime Advances: The Manhattan Project . . .17 1.3.6. Postwar Progress. .17 1.4. References ...... 21

2. Synthesis of Organotluorine Compounds

R. E. Banks and J. C. Tatlow 2.1. Introduction ...... 25 2.2. Synthesis Methodology...... 26 2.2.1. The Building-Block Approach .27 2.2.2. The Formation of Carbon-Fluorine Bonds .27 2.3. The Current Position ...... 29 2.4. Tabular Summary of Fluorination Methods and Reagents . .29 2.5. References ...... 53

xi xii Contents

3. Characteristics of C-F Systems Bruce E. Smart 3.1. Introduction . 57 3.2. Physical Properties 58 3.2.1. General ... 58 3.2.2. Solvent Polarity 64 3.2.3. Lipophilicity .... 66 3.2.4. Acidity and Basicity 67 3.2.5. Hydrogen Bonding. 69 3.3. Chemical Properties . . . . 70 3.3.1. Bond Strengths and Reactivity. 70 3.3.2. Reactive Intermediates . 74 3.3.3. Steric Effects 80 3.4. References ...... 82

4. PerOuorocarbon Fluids

S. W. Green, D. S. L. Slinn, R. N. R Simpson, and A. J. Woytek 4.1. Introduction ...... 89 4.1.1. Perfluorocarbon Gases . . 89 4.1.2. Perfluorocarbon Liquids . 90 4.2. Production of Perfluorocarbons . 91 4.2.1. Processes for Perfluorocarbon Gases 91 4.2.2. Processes for Perfluorocarbon Liquids . 92 4.3. Physical Properties ...... 93 4.4. Applications of Perfluorocarbons ...... 95 4.4.1. Perfluorocarbon Gases as Etchants. . . 95 4.4.2. Perfluorocarbon Liquids as Alternatives to Chlorofluorocarbons . 97 4.4.3. Perfluorocarbon Liquids as Heat Transfer Agents. . . . . 104 4.4.4. Miscellaneous Applications of Perfluorocarbon Liquids . 114 4.5. References...... 118

5. Electrochemical Fluorination and Its Applications Y. W. Alsmeyer. W. V. Childs, R. M. Flynn, G. G. I. Moore, and J. C. Smeltzer 5.1. Coverage ...... 121 5.2. Simons Electrochemical Fluorination. . 121 5.2.1. Introduction ...... 121 Contents xiii

5.2.2. Experimental Technique ...... 122 5.2.3. Anode Film ...... 123 5.2.4. Mechanisms ...... 124 5.2.5. Scope ...... 126 5.2.6. Commercial Utility of ECF-Derived Materials ...... 129 5.3. Cave-Phillips Process for Electrochemical Fluorination ...... 133 5.3.1. Systems ...... 133 5.3.2. Feeds ...... 135 5.3.3. Nonwetting Behavior ...... 135 5.3.4. Polarization ...... 137 5.3.5. Brief History of an Anode ...... 138 5.3.6. Fluorination Results ...... 138 5.3.7. Summary of the CAVE ECF Process ...... 140 5.4. References ...... 140

6. Chlorofluorocarbons

Arthur J. Elliott 6.1. Introduction .... 145 6.2. Production ...... 147 6.2.1. Halogen Exchange...... 147 6.2.2. Chlorotrifluoroethylene Telomerization ...... 149 6.3. Properties and Specifications...... 150 6.4. Applications ...... 151 6.4.1. General...... 151 6.4.2. Declining Applications ...... 151 6.4.3. Continuing Applications...... 153 6.5. References ...... 156

7. Alternatives to Chlorofluorocarbons (CFCs)

V. N. M. Rao 7.1. Introduction ...... 159 7.2. Synthesis ...... 162 7.2.1. 1,1,1, 2-Tetrafluoroethane, CF3CH:zF (HFC-134a) ...... 162 7.2.2. 2,2-Dichloro-1,1,1-trifluoroethane, CF3CHCh (HCFC-123) ..... 165 7.2.3. 2-Chloro-l,I,I,2-tetrafluoroethane, CF3CHFCI (HCFC-124) .... 167 7.2.4. Pentafluoroethane, CF3CHF2(HFC-125) ...... 168 7.2.5. 1,1-Dichloro-1-fluoroethane, CFChCH3 (HCFC-141 b) . 169 7.2.6. 1,I-Difluoroethane, CHF2CH3(HFC-152a) ...... 169 xiv Contents

7.2.7. Dichloropentafluoropropanes 170 7.3. Commercial Aspects . 171 7.4. Properties ...... 171 7.5. Applications .... . 172 7.5.1. Refrigeration .. 172 7.5.2. Foaming Agents 172 7.5.3. Solvents 173 7.6. References ...... 173

8. Pertluoroalkyl Bromides and Iodides

Claude Wakselman and Andre Lantz 8.1. Introduction . 177 8.2. Preparation ...... 178 8.3. Reactions ...... 178 8.3.1. "Classical" Radical Reactions. 178 8.3.2. Reactions with Nucleophiles . 180 8.3.3. Reactions with Metals . . . . . 183 8.3.4. Reactions with Acidic Reagents . 184 8.3.5. Electrochemical Transformations 185 8.4. Applications ...... 185 8.4.1. Halons ...... 185 8.4.2. Perfluoroalkyl Iodides . 188 8.5. References ...... 190

9. Industrial Routes to Ring-Fluorinated Aromatic Compounds

J. S. Moilliet 9.1. Introduction . 195 9.2. "Halex" Fluorinations .... 196 9.2.1. General Considerations 196 9.2.2. Examples. . . . . 198 9.2.3. Fluoride Sources ... . 199 9.2.4. Solvents ...... 200 9.2.5. Procedure for the Halex Process. 201 9.3. Diazotization Methods ...... 203 9.3.1. The Balz-Schiemann Reaction .. 203 9.3 .2. HF-DiazotizationIDediazoniation . 207 9.4. Other Fluorination Methods ...... 211 Contents xv

9.4.1. Cobalt Fluoride Fluorination 211 9.4.2. Using Hydrogen Fluoride .. 212 9.4.3. Direct Fluorination ..... 213 9.5. Comparison of the Three Principal Methods . 213 9.6. The Industrial Scene ...... 214 9.6.1. HF-DiazotizationIDediazoniation . 214 9.6.2. Halex Fluorination ...... 217 9.6.3. Balz-Schiemann Methodology 217 9.7. Concluding Remarks 217 9.8. References ...... 218

10. Side-Chain Fluorinated Aromatic Compounds Routes to Benzotrifluorides

Bernard Langlois 10.1. Introduction . . 221 10.2. Synthesis of Benzotrifluorides from the Corresponding Toluenes: Liquid-Phase Methods . 222 10.2.1. General Considerations ...... 222 10.2.2. Fluorination of Benzotrichlorides . . . 224 10.3. Vapor-Phase Routes to Benzotrifluorides and (Trifluoromethyl)pyridines ...... 225 10.4. Synthetic Manipulation of Benzotrifluorides . 225 10.4.1. Electrophilic Substitution ...... 225 10.4.2. Nucleophilic Displacement of Nuclear Halogen from 4-Halogenobenzotrifluorides ...... 227 10.4.3. Hydrolysis of Trifluoromethyl Groups . . 228 10.5. Newer Commercially Interesting Methods for the Trifluoromethylation of Aromatic Compounds. 229 10.5.1. Electrophilic Trifluoromethylation . 229 10.5.2. "Nucleophilic" Trifluoromethylation 230 10.5.3. Radical Trifluoromethylation 230 10.6. Concluding Remarks 232 10.7. References ...... 232

11. Recent Developments in Fluorine-Containing Agrochemicals

David Cartwright 11.1. Introduction . . 237 11.2. Occurrence of Fluorine in Agrochemicals 239 xvi Contents

11.3. Fluorine-Containing Herbicides ...... 240 11.3.1. Herbicides Containing an Aromatic-Type CF3 Group 240 11.3.2. Herbicides Containing a Fluoroaromatic Group: Pyridyloxyacetic Acids ...... 244 11.3.3. Herbicides Containing a Fluoroalkoxy Group: Sulfonylureas ...... 245 11.3.4. Herbicides Containing a Trifluoromethanelsulfonyl Group: Trifluoromethanesulfoanilides '" 245 11.4. Fluorine-Containing Insecticides ...... 246 11.4.1. Compounds Affecting Insect Growth 246 11.4.2. Pyrethroid Insecticides . 247 11.4.3. Others ...... 252 11.5. Fluorine-Containing Fungicides ... 252 11.5.1. Sterol Biosynthesis Inhibitors. 252 11.5.2. Amide Fungicides ...... 255 11.6. Fluorine-Containing Plant Growth Regulators . 255 11.6.1. Compounds that Interfere with Gibberellin Biosynthesis . 255 11.6.2. Benzylamine Derivatives 256 11.7. Rodenticides . 257 11.8. References ...... 257

12. Fluorinated Liquid Crystals

Takeshi lnoi 12.1. Introduction 263 12.2. Properties and Structural Classification of Liquid Crystals 263 12.3. Applications ...... 267 12.4. Molecular Design ...... 267 12.5. Fluorinated Liquid Crystals ... 270 12.5 .1. Semifluorinated Alkanes 271 12.5.2. Schiff Bases (Azomethines) . 271 12.5.3. Benzoates ...... 271 12.5.4. Biphenyls ...... 275 12.5.5. Cyclohexanecarboxylates .. 276 12.5.6. Liquid Crystals with Hybridized Structures and Multiring Systems . . 276 12.6. Ferroelectric Liquid Crystals 283 12.7. Conclusions 284 12.8. References ...... 285 Contents xvii

13. Fluorine.Containing Dyes A. Reactive Dyes

K. J. Herd 13A.1. Introduction 287 13A.2. Dyestuffs with One Reactive System ...... 288 13A.2.1. General Information on Reactive Dyes . 288 13A.2.2. Heterocyclic Carrier Systems with Fluorine as the Leaving Group . . . . . 289 13A.2.3. Preparation of the Reactive Compounds 297 13A.2A. Preparation of the Reactive Dyes . 299 13A.3. Dyes with Two or More Reactive Systems . 302 13A.3.1. Homobifunctional Reactive Dyes. 303 13A.3.2. Heterobifunctional Reactive Dyes 303 13A.3.3. Polyfunctional Reactive Dyes 306 13AA. Conclusion 307 13A.5. References ...... 307

13.B. Other Fluorinated Dyestuffs

A. Engel 13B.1. Introduction 315 13B.2. Properties of Fluorine-Containing Dyes 315 13B.3. Summary and Outlook 320 13B.4. References ...... 320

14. Textile Finishes and Fluorosurfactants

Nandakumar S. Rao and Bruce E. Baker 14.1. Textile Repellent Finishes ...... 321 14.1.1. Intrinsic Repellency and Fluorocarbon Structure. 321 14.1.2. Synthesis of Fluoroalkyl Intermediates . 325 14.1.3. Synthesis of Fluorochemical Repellents 329 14.1.4. Soil-Release Finishes 331 14.1.5. Future Developments .. 332 14.1.6. Major Manufacturers ., 332 14.2. Fluorosurfactants ...... 333 14.2.1. Fluorosurfactant Synthesis . 333 14.2.2. Aqueous Solutions of Fluorosurfactants 334 xviii Contents

14.2.3. Properties and Uses 336 14.3. R~ferences ...... 336

15. F1uoroplastics

Andrew E. Feiring

15.1. Introduction . . 339 15.2. Fluorinated Vinyl Monomers 341 15.3. Crystalline Perfluoroplastics 342 15.3.1. Poly(tetrafluoroethylene) (PTFE) . 342 15.3.2. Perfluorinated Copolymers (PEP and PFA) . 344 15.3.3. Properties of the Perfluoroplastics .. 346 15.3.4. Applications and Commercial Aspects 348 15.4. Amorphous Perfluoroplastics . 349 15.5. Poly(chlorotrifluoroethylene) . 350 15.5.1. Production ...... 351 15.5.2. Properties ...... 351 15.5.3. Applications and Commercial Aspects 352 15.6. Partially Fluorinated Plastics ...... 352 15.6.1. Ethylene-Tetrafluoroethylene Copolymer 352 15.6.2. Ethylene-Chlorotrifluoroethylene Copolymer 354 15.6.3. Poly(Vinylidene Fluoride) .. 356 15.6.4. Poly(Vinyl Fluoride) .... 358 15.7. Other Fluorine-Containing Plastics. 360 15.7.1. Addition Polymers ...... 360 15.7.2. Condensation Polymers .. . 362 15.7.3. Surface-Fluorinated Plastics. 363 15.8. Outlook and Conclusions 364 15.9. References ...... 364

16. Fluoroelastomers

Anestis L. Logothetis 16.1. Introduction ...... 373 16.1.1. Chemical Compositions . 374 16.1.2. Structural Considerations 374 16.2. Fluoroelastomers Based On Vinylidene Fluoride Copolymers. 376 16.2.1. General Description 376 16.2.2. Production ...... 377 Contents xix

16.2.3. Curing (Vulcanization) of Fluoroelastomers Containing Vinylidene Fluoride 380 16.2.4. Properties ...... 383 16.2.5. Processing ...... 385 16.3. Fluoroelastomers Based on TetrafluoroethylenelPropylene Copolymers 387 16.3.1. Introduction ...... 387 16.3.2. Polymerizations ...... 387 16.3.3. Curing Chemistry and Properties 388 16.3.4. Processing ...... 388 16.4. Perfluoroelastomers Based on TetrafluoroethylenelPerfluoro(alkyl vinyl ether) Copolymers. 389 16.4.1. Polymer Description . 389 16.4.2. Polymerizations . 390 16.4.3. Curing Chemistry 390 16.4.4. Properties .... 392 16.4.5. Processing . . . . 393 16.5. Uses of Fluorinated Elastomers. 393 16.6. References...... 394 16.6.1. General References 394 16.6.2. Specific References . 394

17. Fluoropolymer Coatings

Masaaki Yamabe • 17.1. Introduction ...... 397 17.2. Thermoplastic Fluoropolymer Coatings 397 17.2.1. Tetrafluoroethylene Polymers . 397 17.2.2. Poly(Vinylidene Fluoride) . 398 17.3. Curable Fluoropolymer Coatings . 399 17.4. References ...... 401

18. Fluorinated Membranes

Masaaki Yamabe and Haruhisa Miyake

18.1. Introduction ...... · 403 18.2. Structure and Properties. .404 18.3. Preparation ...... · 405 18.4. Applications ...... · 407 18.4.1. Chlor-Alkali Process · 407 18.4.2. Outlook .409 18.5. References ...... 410 Contents

19. Monomers and Polymers from Hexafluoroacetone

Wolfgang K. Appel, Bernd A. Blech, and Michael Stobbe 19.1. Introduction ...... 413 19.2. Synthesis of Hexafluoroacetone (HFA). . . 413 19.3. Synthesis of Intennediates Containing the Hexafluoroisopropylidene Group ...... 414 19.3.1. The Overall Reaction Sequence. . . 414 19.3.2. Fonnation of Arylbis(trifluoromethyl)carbinols . 414 19.3.3. Properties of Arylbis(trifluoromethyl)carbinols . 417 19.3.4. Fonnation of Diphenylhexafluoropropanes .. . 418 19.4. Directly Accessible HFIP-Bridged Monomers and Intennediates . 419 19.5. Polymers Containing Hexafluoroisopropylidene Groups . . 421 19.5.1. Aromatic 6F-Polyesters . . 421 19.5.2. Aromatic 6F-Polyamides . 422 19.5.3. Aromatic 6F-Polyimides . 423 19.6. Conclusion . 427 19.7. References...... 427

20. PerOuoropolyetbers (PFPEs) from PerOuorooletin Photooxidation: Fomblin® and Galden® Fluids

Dario Sianesi, Guiseppe Marchionni, and Ralph J. De Pasquale 20.1. Introduction ...... 431 20.2. The Photooxidation Route to Neutral PFPEs ...... 432 20.2.1. Oxidative Photopolymerization of Fluoroolefins . . 432 20.2.2. Removal of Peroxide Linkages ...... 435 20.2.3. End-Group Modification to Give Neutral PFPEs . . 437 20.3. Mechanism of HFP and TFE Oxidative Photopolymerization . . 438 20.4. Chemical and Physical Properties of Fomblin® and Galden® Fluids ...... 440 20.4.1. Chemical Properties and Solubilities . . . . . 440 20.4.2. Thennal Properties-Influence of Metals . . . 442 20.4.3. Oxidative Stability, Radiation Resistance, and Bioinertness 443 20.4.4. Physical Properties . . 443 20.4.5. Greases . . 446 20.4.6. Tribology ...... 446 20.4.7. Rheology ...... 448 20.5. Functional PFPEs from Photooxidation . 450 20.6. Applications of PFPEs ...... 453 20.6.1. Testing of Electronic Devices and Equipment . 453 20.6.2. Polymer Curing . 454 20.6.3. Lubrication ...... 454 Contents

20.6.4. Surfactants, Emulsions, and Cosmetics . · 454 20.6.5. Polymer Modification . · 455 20.6.6. Conductive Films ...... · 455 20.6.7. Mass Spectrometry ...... · 455 20.6.8. Environmental Applications . · 456 20.7. Future Prospects . · 456 20.8. References ...... · 457

21. PerDuoropolyetber Fluids (Demnum®) Based on Oxetanes

Yohnosuke Ohsaka 21.1. Introduction ...... 463 21.2. Preparation ... · . 463 21.2.1. Monomers · . 463 21.2.2.0ligomers .464 21.3. Properties .... .464 21.3.1. General . .464 21.3.2. Toxicity . · 465 21.3.3. Comparative PFPE Properties. · 465 21.4. Applications ...... · 466 21.4.1. Base Oil for Greases ...... · 466 21.4.2. Semiconductor Manufacturing · 466 21.4.3. Miscellaneous · 467 21.5. References ...... 467

22. Surface Fluorination of Polymers

Madhu Anand, J. P. Hobbs, and Ian J. Brass

22.1. Introduction ...... 469 22.2. Reactions of Elemental Fluorine with Organic Polymers '" .469 22.3. Properties and Applications of Surface-Fluorinated Polymers . · . 471 22.3.1. Barrier Properties ...... · . 471 22.3.2. Adhesion and Surface Energy ...... · 473 22.3.3. Other Properties of Fluorinated Surfaces ...... · 474 22.4. Techniques for the Direct Fluorination of Polymer Surfaces . · 475 22.4.1. Post-Treatment...... · 475 22.4.2. In Situ Treatment ...... 477 22.5. Safety and Environmental Concerns .. · ...... 478 22.6. Conclusions ...... · ...... 479 22.7. References ...... · ...... 479 xxii Contents

23. Fluorinated Carbon

George A. Shia and Ganpat Mani

23.1. Introduction . . . . . · 483 23.2. Physical Properties . · 484 23.3. Chemical Properties. · 488 23.4. Manufacture .. · 489 23.5. Applications ...... 490 23.5.1. Batteries .. . 490 23.5.2. Lubrication . · 492 23.5.3. Imaging ... .494 23.6. Fluorine Intercalation Compounds of Graphite · 495 23.7. Health/Safety ...... · 495 23.7.1. Toxicity ...... 495 23.7.2. Dermal and Ocular Effects .. . .496 23.7.3. Cytotoxicity ...... 496 23.7.4. Handling of Fluorinated Carbons 496 23.8. References ...... 496

24. Uses of Fluorine in Chemotherapy

Philip Neil Edwards 24.1. General Introduction · 501 24.2. Fluoroquinolone Antibacterial Agents . · 502 24.2.1. Introduction ...... 502 24.2.2. Early 6-Fluoro-7 -piperazino-quinolones 503 24.2.3. Mode of Action ...... 505 24.2.4. New Structural Types ...... 506 24.3. Electronegativity and Its Consequences .... 509 24.3.1. What Is Electronegativity and Can "It" Be Quantified? 509 24.4. Dipole Moments and Electron Density Distributions in Halogeno Compounds...... 511 24.5. Fluorine Substitution in Acid-Sensitive Compounds .. 512 24.6. Hydrogen Bonding in Fluoro Compounds . . 514 24.6.1. Fluorine as Hydrogen-Bond Acceptor .... 515 24.6.2. Halogeno-Substituent Effects on Hydrogen-Bond Donor and Acceptor Ability. 520 24.7. Fluoroketone Enzyme Inhibitors ...... 525 24.8. Inhibition of Pyridoxal-Dependent Enzymes . . . . . 527 24.9. Drug Absorption and Distribution ...... 530 24.9.1. Fluorine Substitution in Relation to log Poctanol Values 531 Contents xxiii

24.9.2. Solubility Effects . 532 24.10. Fluorination Effects on Metabolism and Elimination 533 24.11. The Size and Shape of Fluoro Substituents 536 24.12. References ...... 539

25. Fluorinated Inhalation Anesthetics Donald F. Halpern 25.1. Introduction . . 543 25.2. The Fluorine Revolution 544 25.2.1. Halothane . . . 546 25.2.2. Methoxyflurane 546 25.2.3. Enflurane .. 547 25.2.4.Isoflurane .. 547 25.2.5. Sevoflurane . 550 25.2.6. Desflurane .. 551 25.3. Conclusions and Acknowledgments 552 25.4. References ...... 553

26. Properties and Biomedical Applications of Perlluorochemicals and Their Emulsions Kenneth C. Lowe 26.1. Introduction . . 555 26.2. Properties of PFCs " 556 26.3. Synthesis of PFCs . . . 558 26.4. Emulsification of PFCs 558 26.4.1. "First-Generation" Emulsions . 558 26.4.2. Improved Emulsions . 560 26.4.3. Surfactants ...... 561 26.5. Biocompatibility Assessment. . . . 562 26.5.1. Tissue Uptake and Excretion 563 26.5.2. Effects on Lymphoid Tissues and the Reticuloendothelial System 563 26.5.3. Effects on Immunological Competence. . . . 563 26.5.4. Effects on Tissue Biochemistry . . 565 26.5.5. Other in vivo Responses 565 26.5.6. Cellular Effects in vitro 566 26.5.7. Effects of Surfactant(s) 567 26.6. Biomedical Applications . . . 568 xxiv Contents

26.6.1. Microcirculatory Support in Ischemic Tissues 568 26.6.2. Coronary Angioplasty ...... 569 26.6.3. Cancer Therapy ...... 570 26.6.4. Contrast Media and Diagnostic Imaging 570 26.6.5. Respiratory Distress Syndrome ... . 570 26.6.6. Decompression Sickness ...... 571 26.6.7. Lung Damage and Respiratory Failure 571 26.6.8. Blood Diseases ...... 572 26.6.9. Applications in Ophthalmology . . . 572 26.6.10. Organ Perfusion and Preservation . 572 26.6.11. Cell Culture Studies 572 26.7. Concluding Remarks 573 26.8. References...... 573

27. The Fluorochemical Industry A. The Fluorochemical Industry in the United States Richard A. Du Boisson 27A.l. The Manufacture of Hydrogen Fluoride in the United States .. 579 27A.l.l. Industrial Preparation of Hydrogen Fluoride. 579 27A.1.2. U.S. Manufacturers of Hydrogen Fluoride 580 27A.1.3. Hydrogen Fluoride Production Statistics. 580 27A.2. Industrial Uses of Hydrogen Fluoride ...... 582 27 A.2.1. Introduction ...... 582 27 A.2.2. Chlorofluorocarbons and Related Halogenoalkanes 583 27 A.2.3. Aluminum Production. . . . 590 27 A.2.4. Petroleum Alkylation ...... 590 27 A.2.5. Aqueous Hydrofluoric Acid. . . 591 27A.2.6. Fluorine ...... 591 27A.2.7. Uranium ...... 591 27 A.2.8. Chemical Intermediates . 592 27A.3. References ...... 592

27. B. Organotluorine Products and Companies in Western Europe Peter Field 27B.1. Introduction ...... 595 27B.2. Fluoroaliphatics ...... 595 27B.2.1. Fluorocarbons .. 595 27B.2.2. Halogenofluorocarbons 596 27B.2.3. Trifluoroacetic Acid and Its Derivatives 597 27B.2.4. Trifluoromethanesulfonic Acid and Its Derivatives 598 Contents XXV

27B.2.5. Higher (>C2) Fluoroalkane Derivatives. 599 27B.3. Fluoroaromatics ...... 600 27B.3.1. General Comments ...... 600 27B.3.2. Nuclear-Fluorinated Aromatics . . . . . 601 27B.3.3. Production of Nuclear-Fluorinated Aromatics in Europe. 604 27B.3.4. Side-Chain Fluorinated Aromatics ...... 605 27B.4. Fluoropolymers ...... 607 27B.5. Note Added in Proof: Developments Concerning Companies 607 27B.6. References...... 608

27.C. Manufacturers of Organic Fluoro Compounds in Japan ...... 609

Nobuo Ishikawa

28. CFCs and the Environment: Further Observations

Richard L. Powell and 1. Hugo Steven 28.1. Introduction ...... 617 28.2. Refrigeration ...... 618 28.3. The Ozone Layer Problem ... . 621 28.4. Replacements for the Chlorofluorocarbons . 622 28.5. Discovery of Antarctic Ozone Depletion .. 624 28.6 The Montreal Protocol ...... 625 28.7. Replacements for the Chlorofluorocarbons: A Second Look. 626 28.8. Commercial Production of Chlorofluorocarbon Replacements: The Third Period of Refrigeration 629 28.9. References ...... 629

Index ...... 631