US006015838A United States Patent (19) 11 Patent Number: 6,015,838 Stern et al. (45) Date of Patent: *Jan. 18, 2000

54 AQUEOUS FILM-FORMING FOAM 4,555,556 11/1985 Beresniewicz ...... 526/212 COMPOSITIONS 4,576,869 3/1986 Malholtra ...... 428/502 4,749,526 6/1988 Flynn ...... 562/849 (75) Inventors: Richard M. Stern, Woodbury; 5,085,786 2/1992 Alm et al...... 252/8.05 Wei-Qiang Fan, Cottage Grove, both of 5,144,469 9/1992 Stern et al...... 562/556 Minn. 5,266,639 11/1993 Chapman, Jr. et al...... 525/200 5,362.919 11/1994 Costello et al...... 568/601 5,488,142 1/1996 Fall et al...... 560/227 73) Assignee: 3M Innovative Properties Company, 5,506,309 4/1996 Bierschenk et al...... 525/410 St. Paul, Minn. 5,539,059 7/1996 Bierschenk et al...... 525/331.6 5,756,000 5/1998 Hansen et al...... 252/3 Notice: This patent issued on a continued pros ecution application filed under 37 CFR FOREIGN PATENT DOCUMENTS 1.53(d), and is subject to the twenty year 0 267 828 5/1988 European Pat. Off...... CO7C 53/21 patent term provisions of 35 U.S.C. 0.375 610 6/1990 European Pat. Off...... CO7H 15/14 154(a)(2). 2015 296 4/1970 France ...... CO8F 1/OO This patent is Subject to a terminal dis 1216 116 5/1966 Germany. claimer. 1812 531 6/1970 Germany ...... A62D 1/OO 1632714 3/1991 U.S.S.R. . 1092141 11/1967 United Kingdom ...... CO7C 53/34 Appl. No.: 08/743,478 1302612 1/1973 United Kingdom ...... CO7C 135/02 Filed: Nov. 4, 1996 OTHER PUBLICATIONS Int. Cl." ...... B01F17/00; A62D 1/04 Database WPIDS on STN, week 9206, London: Derwent U.S. Cl...... 516/12; 516/915; 252/3; Publ., Inc., AN 92-046595, Class E16, SU 1632714 A1 544/173; 564/147; 564/297 (Voitovich et al.) abstract, 1992. Field of Search ...... 252/3; 54.4/170, Yuminov et al. “New Fluorine-Containing Emulsifiers,” 544/171, 172, 173; 546/245, 250; 564/147, International Polymer & Science Technology, vol. 6, No. 3, 209, 297; 516/12, 15,915 pp. 106–109 (1979). Gambaretto et al., “Perfluorinated Alyphatic C-Akyl Substi References Cited tuted Acids.” La Chemica e l’Industria, month unknown 1971, vol.53, pp. 1033–1038. U.S. PATENT DOCUMENTS Abe et al., “The Electrochemical Fluorination of C-Alkyl 2,519,983 8/1950 Simons ...... 205/430 Substituted Carboxylic Acids,” Journal of Fluorine Chem 2,567,011 9/1951 Diesslin et al. ... 560/227 istry, 1978, month unknown vol. 12, pp. 1-25. 2,592,069 4/1952 Reid ...... 526/245 Abe et al., “Preparation, Properties, and Industrial Applica 2,593,737 4/1952 Diesslin et al...... 562/507 tions of Organofluorine Compounds' Chpt. 1, Ellis Hor 2,642,416 6/1953 Ahlbrecht et al. ... 526/245 2,647.933 8/1953 Zerte et al...... 570/142 wood Ltd., Holsted Press (1982) month unknown pp. 19-43. 2,666,797 1/1954 Husted et al. ... 568/842 Abe et al., “Synthesis of Perfluorobicyclic Ethers,” Journal 2,668,864 2/1954 Hals et al...... 570/142 of Fluorine Chemistry, 1983, month unknown vol. 23, 2,713,593 7/1955 Brice et al...... 562/586 pp. 123-146. 2,746,997 5/1956 Reid et al...... 570/142 LaZerte et al., “Pyrolyses of the Salts of the Perfluoro 2,764,602 9/1956 Ahlbrecht ...... 554/55 Carboxylic Acids,” Journal of American Chemical Society, 2,764,603 9/1956 Ahlbrecht et al...... 554/55 1953, month unknown vol. 75, pp. 4525-4528. 2,795,615 6/1957 Husted et al...... 564/510 Goecke-Flora et al., “Influence of Carbon Chain Length on 2,803,615 8/1957 Ahlbrecht et al...... 252/79 the Hepatic Effects of Perfluorinated Fatty Acids,” Chem. 2,803,656 8/1957 Ahlbrecht et al...... 564/96 2,809,990 10/1957 Brown ...... 562/556 Res. Toxicol. 1996, month unknown vol. 9, pp. 689-695. 2,950,317 8/1960 Brown et al...... 562/829 Nagase, “Electrochemical Fluorination,” Fluorine Chemis 3,088,849 5/1963 Friedlander et al. . ... 428/422 try Reviews, 1967, month unknown vol. 1, pp. 77-106. 3,094,547 6/1963 Heine ...... 558/175 Fluorine Chemistry, edited by J.H. Simons, Academic Press, 3.232,970 2/1966 Hauptschein et al. ... 554/103 Inc., New York, N.Y., 1950, month unknown pp. 416-419. 3,271,341 9/1966 Garrison, Jr...... 524/777 3,274,239 9/1966 Selman ...... 562/503 Primary Examiner Richard D. Lovering 3,351,644 11/1967 Hauptschein et al...... 562/851 ASSistant Examiner-Daniel S. Metzmaier 3,398,182 8/1968 Guenthner et al...... 558/239 Attorney, Agent, or Firm-Kent S. Kokko 3,661,776 5/1972 Fletcher et al...... 252/3 3,721,638 3/1973 Sianesi et al...... 524/758 57 ABSTRACT 3,772,195 11/1973 Francen ...... 252/8.05 3,787,351 1/1974 Olson ...... 523/453 This invention provides acqueous film-forming foamable 3,828,085 8/1974 Price et al...... 252/3 (AFFF) compositions comprising one or more 3,896.251 7/1975 Landucci...... 442/80 environmentally-friendly C-branched fluoroalkylcarbonyl 3,957,657 5/1976 Chiesa, Jr. ... 252/3 group-containing Surfactants. 4,264,484 4/1981 Patel ...... 524/168 4,360,652 11/1982 Dohany ...... 526/210 5 Claims, No Drawings 6,015,838 1 2 AQUEOUS FILM-FORMING FOAM Straight-chained perfluorocarboxylic acids of the Struc COMPOSITIONS ture RCF.COOH and derivatives thereof are known not to degrade under aqueous environmental exposure and do not FIELD OF THE INVENTION thermally decarboxylate until at least 180–200° C. (J. Am. Chem. Soc., 1953, 75,4525-28). These compounds are very This invention relates to C.-branched fluoroalkylcarbonyl Stable and, therefore, also persist in the environment. It is fluoride compositions, their preparation, and their use. In also known that linear perfluorocarboxylic acids and their another aspect, this invention relates to the use of carboxylate Salts are moderately toxic, especially longer C.-branched fluoroalkylcarbonyl fluoride compositions to prepare C-branched fluoroalkylcarbonyl group-containing chain Salts Such as n-CFCOONH. (See, e.g., Goeche compositions. In yet another aspect, it relates to Flora et al., Chem. Res. Toxicol. 1996, 9, 689–95). While it is known that fluorochemical acids of the type intermediates, monomers, repellent treatments and coatings, (R)-CFCO.H, where R is a short chain such as CF, and Surfactants, emulsifiers, and aqueous film-forming foamable CFs, are unstable in aqueous Solution (See, e.g., Chim. Ind., Solutions. 1971, 53, 1033-8), these compounds generally possess poor BACKGROUND OF THE INVENTION 15 Surfactant properties. There are no known fluoroalkylcarbonyl fluoride deriva Classes of perfluoralkylcarbonyl fluorides containing tives that exhibit a combination of those properties that are Straight chain perfluoroalkyl groups, cyclic perfluoroalkyl favorable in today's chemical market. A highly desirable groups, and derivatives thereof are known. U.S. Pat. No. fluorochemical compound is one having Superior Surfactant 2,567,011 (Diesslin et al.), for example, describes fluoro properties when dissolved in a liquid (i.e., can reduce the carbon carbonyl fluorides, monocarboxylic acids, and their surface tension of the liquid to a value lower than 20 derivatives containing open-chain (i.e., non-cyclic) and dyneS/cm), is relatively non-toxic or is very low in toxicity, closed-chain (i.e., cyclic) perfluoroalkyl groups, and com and is non-persistent in the environment (i.e., can com binations of cyclic and non-cyclic fluorinated alkyl Sub pletely degrade biochemically, thermally, or photochemi radicals. All open chain Structures cited by Diesslin et al. are 25 cally under mild conditions Such as those encountered in the Straight chain structures (e.g., CF (CF), ); no branched environment under ambient conditions). open chain Structures are noted. U.S. Pat. No. 3,351,644 (Hauptschein et al.) describes SUMMARY OF THE INVENTION Straight-chain telomeric acid fluorides of the Structure Briefly, in one aspect, the present invention provides R(CFCF),COF, where R is a perfluoroalkyl or monochlo compositions of open-chain, C.-branched fluoroalkylcarbo roperfluoroalkyl group and where n is a Small number from nyl fluorides, and derivatives thereof, that can be represented 1 to about 8. generally by the formula: British Amended Patent 1,092,141 describes perfluoro alkylcarbonyl fluorides containing omega (co)-branched per fluoroalkyl chains, i.e. of the structure (CF)CF(CF)-. 35 These co-branched perfluoroalkylcarbonyl fluorides report edly are produced as a minor component during electro chemical fluorination of Straight chain hydrocarbon carbo nyl fluorides and derivatives. 40 U.S. Pat. No. 4,749,526 (Flynn) describes C.-branched perfluoropolyether carbonyl fluorides having the general wherein: formula RCF.OICF(CFA)CF.O.CF(CF)COF. Acids R, and R', are selected independently from one another as derived from these materials have been shown to be stable a fluorinated, preferably perfluorinated, group bonded to decarboxylation of the perfluoropolyether chain. 45 through carbon that may be substituted or Short-chain C.-branched perfluoroalkylcarbonyl fluorides unsubstituted, cyclic or acyclic, linear or branched (or and acids and certain classes of Short-chain cyclic group any combination thereof) and may optionally contain containing C-branched perfluoroalkylcarbonyl fluorides are one or more catenary heteroatoms Such as nitrogen, known. Gambaretto et al. (Chim. Ind., 1971, 53, 1033-8) Sulfur, or oxygen; R or R, may contain one or more reports the preparation of CFCF(CFs)COH and (CF) 50 hydrogen atoms or one or more other halogen atoms, CFCOH by electrochemical fluorination and the Subse e.g. chlorine, provided that at least 75%, and preferably quent decarboxylation of these acids. The electrochemical at least 90%, of the atoms attached to the carbon fluorination of O-alkyl-substituted acid chlorides and methyl backbone are fluorine atoms, esters to give perfluorooxolanes and perfluorooxanes as well p may be 1, 2, Several or many, equalling the Valency of as a Small amount, i.e. nine percent, of the corresponding 55 X; perfluoroalkanoyl fluorides (e.g. CFCF(CF)COF) also X is halogen, a hydroxyl group, or a moiety remaining has been reported. (Abe, T. et al., J. Fluorine Chem., 1978, after the reaction of an O-branched fluoroalkylcarbonyl 12, 1-25). In this article, Abe et al. also reports the existence fluoride with a reagent containing at least one active of CFCF(CF)COF. (i.e., acidic) hydrogen atom and after the elimination of Certain cycloalkyl group-terminated C-branched perfluo 60 hydrogen fluoride; and roalkylcarbonyl halides are known. c-CF, CFCF(CF) when X is fluorine or is a hydroxyl group, p is equal to 1, COF has been reported (T. Abe et al. in Chapter 1 of R, and R', are acyclic alkyl groups, at least one of said "Preparation, Properties, and Industrial Applications of RandR, contains at least 5 carbon atoms, and the Sum Organofluorine Compounds,” R. E. Banks, editor, Ellis of the carbon atoms in said R, and R', groups is greater Horwood Ltd., Holsted Press (1982)), and c-CFCF(CF) 65 than or equal to 7, preferably less than or equal to about COF and c-CFCF(CF)COCl (Abe, T. et al., J. Fluorine 24; preferably the ratio of carbon atoms in said R, and Chem., 1983, 23, 123-146) have been disclosed. R, moieties is at least 2to 1. 6,015,838 3 4 In another aspect, the present invention provides prepared through fluorination of a non-fluorinated organic C.-branched fluoroalkylcarbonyl group-containing com analogue (e.g., an alkylcarbonyl halide or an alkylcarbonyl pounds including derivatives of those compounds depicted ester). The fluorination reaction may be carried out either by by Formula I Supra. Such derivatives find utility, for electrochemical fluorination (“ECF), sometimes referred to example, as Surfactants and emulsifiers and as Soil, water, as the "Simons process,” with hydrogen fluoride as and oil-repellent compositions. In yet another aspect, this described, for example, by U.S. Pat. No. 2,519,983 invention provides aqueous film-forming foamable (AFFF) (Simons), or by direct fluorination with elemental fluorine as compositions comprising one or more a-branched fluoro described, for example, by U.S. Pat. No. 5,488,142 (Fall et alkylcarbonyl group-containing Surfactants. al.), both of whose descriptions are hereby incorporated by The C-branched fluoroalkylcarbonyl derivatives of this reference. Preferably, the reaction is carried out by electro invention are environmentally non-persistent and are much chemical fluorination. lower in toxicity than their linear and cyclic homologues. The “Simons process” or the “Simons electrochemical The O.-branched fluoroalkylcarboxylate Salt compositions fluorination process” is a known, commercially-practical provided herein are very low in toxicity, thermally degrade process for reacting anhydrous HF with certain classes of quickly at temperatures between about 80° C. and about organic compounds. A typical fluorination reaction using the 100° C. in aqueous media, and break down in the environ 15 Simons electrochemical fluorination to produce an ment to volatile, non-Surface active Species that are elimi C.-branched trifluoromethyl perfluoroalkylcarbonyl fluoride nated from the body of a transpiring organism. is given below: DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS IV In one aspect, this invention provides C.-branched fluo O O roalkylcarbonyl fluorides. A preferred class of these com ECF | pounds may be represented generally by the following He formula. CH CF 25 II An early patent describing this technology is U.S. Pat. No. 2,519,983 (Simons), which contains a drawing of a Simons cell and its appurtenances, and a description and photograph of laboratory and pilot plant cells appear at pages 416–418 of Vol. 1 of “Fluorine Chemistry”, edited by J. H. Simons, published in 1950 by Academic Press, Inc., New York. wherein: Electrochemical fluorination by the Simons process is also R, and R', are selected independently from one another as described by S. Nagase in Fluorine Chem. Rev., I (1)77-106 an acyclic fluorinated, preferably perfluorinated, group 35 (1967), and by T. Abe et al. in Chapter 1 of “Preparation, bonded through carbon that may be substituted or Properties, and Industrial Applications of Organofluorine unsubstituted, linear or branched (or any combination Compounds,” R. E. Banks, editor, Ellis Horwood Ltd., thereof) and may optionally contain one or more cat Holsted Press (1982). Other suitable feedstocks which can enary heteroatoms Such as nitrogen, Sulfur, or oxygen; be electrochemically fluorinated with HF include unsatur Rf or R, may contain one or more hydrogen atoms or 40 ated alkylcarbonyl fluorides (e.g., CH (CH)3CH=C(CH) one or more other halogen atoms, e.g. chlorine, pro COF), saturated methyl esters (e.g., CH(CH2)CH(CH) vided that at least 75%, and preferably at least 90%, of COCH), and acid chlorides (e.g., CHCH(CH)COCl). the atoms attached to the carbon backbone are fluorine Generally, in a relatively large-scale Setting, a Simons cell atoms, useful in the practice of this invention comprises a cell body, wherein at least one of said R and R, groups contain at 45 typically made of carbon Steel and usually provided with a least 5 carbon atoms and wherein the Sum of the carbon cooling jacket, in which is Suspended an electrode pack atoms in said RandR, moieties is greater than or equal comprising Series of alternating and closely-spaced cathode to 7, and preferably less than or equal to about 24, plates (typically made of iron, nickel, or nickel alloy) and preferably the ratio of carbon atoms in said R, and R, anode plates (typically made of nickel), the plates being moieties is at least 2 to 1. 50 immersed in the current-conductive Solution of the organic An especially preferred class of fluorinated X-Substituted Starting material in essentially anhydrous hydrogen fluoride. carbonyl fluorides can be represented by Formula III: Gaseous cell effluent comprising the Volatilized electro chemically fluorinated product and volatilized hydrogen III fluoride can be withdrawn from the cell as an overhead O 55 stream via a valved-outlet line. The cell is operated with the | conductive Solution containing a desired concentration of the organic starting material (the C-branched alkylcarbonyl precursor), typically between 5 and 30 percent, that will result in the production of the desired Saturated, fully 60 fluorinated, or partially-fluorinated product. wherein: The relative temperatures and preSSures under which the n is between 5 and about 18 inclusive; and cell is operated will be those conditions conducive to the m is between 0 and about 9 inclusive where preferably n production of the desired fluorinated product. Generally, by and m are chosen Such that the ratio of n+1) to (m+1) increasing the concentration of organic Starting material in is at least 2 to 1. 65 the conductive Solution (and thereby decreasing the concen Generally, C.-branched fluoroalkylcarbonyl fluorides, tration of the HF reactant), the hydrogen-content of the such as those depicted above by Formulas II and III, may be resulting fluorinated products is increased, the reaction mix 6,015,838 S 6 ture in a sense being “starved” for HF. Generally, the obtain the fluorinated product as the product of the process, temperature of the cell during the electrochemical fluorina or, if a fluorinated alkyl ester, can be easily converted to the tion can be in the range of 0° to 70° C., preferably 20° to 60° fluorinated carbonyl fluoride by treatment with potassium C. In operation, the cell can be run at a pressure in the range iodide in acetone. of 760 to 4000 torr, preferably in the range from 1000 to Other details of this preferred method of direct fluorina 3000 torr. The cell can be operated at cell voltages in the tion and details of other useful methods of direct fluorination range of 4 to 9 volts and current densities in the range of 10 are omitted in the interest of brevity, as those details are to 100, preferably 20 to 80, mAmp/cm of active anode well-known and established in the art. Surface (where the electrolysis takes place). The cell can be Yields of the C-branched carbonyl derivatives of this operated either at constant current or constant Voltage. invention obtained using electrochemical fluorination typi The reactor gaseous effluent, comprising the fluorinated cally range from about 20 to about 50 percent (compared to adduct, hydrogen fluoride, hydrogen, and other gaseous yields of only around 15% with isomeric straight chain products, can be withdrawn from the top of the reactor and carbonyl derivatives), while typical yields using direct fluo passed to a condenser System, as described Supra. The rination reach as high as 60-80%. The choice of a preferred fluorination product can be removed from the cell as part of 15 fluorination method will of course be governed by a com the gaseous effluent. The effluent can be cooled to condense bination of any given Set of busineSS and technical concerns. and collect or recover the aforementioned Saturated and Electrochemical fluorination yields of the a-branched com partially- or fully-fluorinated a-branched fluoroalkylcarbo positions taught herein are Surprisingly high. One would nyl fluorides. Any unreacted HF or by-products can also be expect a high degree of degradation or isomerization to condensed and recycled to the cell. linear compounds, yet instead, ECF yields are much Other details of the Simons electrochemical fluorination improved over yields obtained for linear analogues of the process and cell will be omitted here in the interest of C.-branched compositions. brevity, and the disclosure of Such technology in the above In a Second aspect of this invention, derivatives of cited references to Such technology can be referred to for C.-branched fluoroalkylcarbonyl fluorides are provided. descriptions of Such detail, whose descriptions are herein 25 Among the many and varied classes of useful derivatives incorporated for Such purpose. that may be prepared from the C-branched fluoroalkyl C-Branched fluoroalkylcarbonyl fluoride precursors may carbonyl fluorides described herein are carboxylate Salts, also be prepared by direct fluorination with excess elemental ester derivatives (e.g., acrylates and methacrylates), amide fluorine using known methods. A typical direct fluorination derivatives, and dihydrofluoroalkyl derivatives. Classes of reaction with elemental fluorine to produce an O-branched oligomers and polymerS may also be obtained. fluoroalkylcarbonyl derivative is shown below: Generally, the most useful C.-branched fluoroalkylcarbo nyl fluoride derivatives will be those prepared by the reac V tion of an O-branched fluoroalkylcarbonyl fluoride with a reagent containing at least one active hydrogen atom. 35 Generally, the simplest of these compounds are those that chctlycott + 22F -> may be represented by the following general Formula VI CH where a Single C.-branched fluoroalkylcarbonyl moiety is bonded to the residue of the active hydrogen-containing f reagent existing after the elimination of hydrogen fluoride. CFCF),CFOCF, + 22HF acetOne- CFCF), FCOF 40 CF VI

Other Suitable feedstocks useful in the methods of direct fluorination heretofore described include branched esters 45 (e.g., CH (CH),CH(CH)CHOCOCH) and unsaturated esters (e.g., CH(CH-)-CH=C(CH2)COOCH). U.S. Pat. No. 5,488,142 (Fall et al.), whose description is wherein: incorporated herein by reference, describes a useful direct R, and R', are selected independently from one another as fluorination method. According to this method, a diluted 50 a fluorinated, preferably perfluorinated, group bonded Solution of the organic precursor material (typically a short through carbon that may be substituted or chain alkyl ester of an C.-branched carboxylic acid) in a unsubstituted, cyclic or acyclic, linear or branched (or normally liquid, inert medium (e.g., perfluoromethyl any combination thereof) and may optionally contain morpholine) is directly contacted with a Stoichiometric one or more catenary heteroatoms Such as nitrogen, excess of fluorine gas, F, which preferably is diluted with 55 Sulfur, or oxygen; R or R, may contain one or more an inert gas Such as nitrogen, in a temperature-controlled, hydrogen atoms or one or more other halogen atoms, turbulent, tubular flow-style reactor to fluorinate the precur e.g. chlorine, provided that at least 75%, and preferably Sor material at a temperature and a flow rate of inert gas (if at least 90%, of the atoms attached to the carbon used) Sufficient to volatilize by-product hydrogen fluoride, backbone are fluorine atoms; preferably the ratio of HF. The hydrogen fluoride is removed from the reactor as it 60 carbon atoms in said R, and R, moieties is at least 2 to is produced (and is not recycled) So that the fluorination is 1; and Substantially carried out in a hydrogen fluoride-free envi X is chlorine or bromine or is a group of the formula ronment. The resultant Solution of fluorinated organic Sub —N(R')(R), —OR" -YQOR, -YQN(R')(R), stance (typically a perfluorinated short chain alkyl ester of -YQZ, or -O 1/qM'" (q=valency of M) where R", an O-branched carboxylic acid) is then removed from the 65 is a fluorinated alkyl group and R, R', and R are, reactor. The fluorinated product, using this method, can be independently from one another, Selected as hydrogen, Separated from the inert medium, e.g. by distillation, to or an alkyl, aryl, alkaryl, aralkyl (or any combination 6,015,838 7 8 thereof) group that may be Substituted or unsubstituted, a quaternary ammonium Salt, as described in U.S. Pat. No. Saturated, linear or branched, cyclic or acyclic, and may 2,764,602 (Ahlbrecht); it can be oxidized with hydrogen contain one or more catenary heteroatoms Such as peroxide to form an amine oxide, as described in British oxygen or nitrogen; where present, R and R together Specification 1,302,612; it can be reacted with a chloroalky with the depicted nitrogen can form a heterocyclic ring, 5 lcarboxylate Salt or a chloroalkylsulfonate Salt to form a Such as a piperidino or morpholino group; Y is O, S, or betaine or a Sultaine amphoteric Surfactant respectively; it NR, where R is as defined Supra; Q is a substituted or can be reacted with acrylic acid to form the Michael adduct to the amine nitrogen, as described in U.S. Pat. No. 5,144, unsubstituted divalent organic group; M is a cation 069 (Stern et al.); or it can be reacted with B-propiolactone Selected from the group consisting of H'(i.e., the free to form a carboxyethyl amphoteric Surfactant, as described carboxylic acid), metal cation (e.g., Na', K", Li", Ca", in U.S. Pat. No. 3,661,776 (Fletcher et al.). While esters and Mg, Fe", Al" or Zn), ammonium cation (i.e., amides of linear fluorocarboxylic acids are unstable to HN), Substituted ammonium cation (e.g., H.N. hydrolysis, esters and amides of C.-branched fluorocarboxy (CH), HN(CH3), HN (CHOH), lic acids are more Stable to hydrolysis. (CH)N" or (CH)N"), and polyammonium cation The fluoroalkylcarbonyl fluoride may also be reacted with (e.g., HN (CH-NH). CH-NH), and Z is an 15 aminoalcohols Such as (N-methyl)-2-aminoethanol and anionic, cationic, nonionic or amphoteric water (N-ethyl)-2-aminoethanol as described in U.S. Pat. No. Solubilizing group (e.g., Sulfonate, Sulfate, ether 2,803,656 (Ahlbrecht et al.), replacing the Sulfate, phosphate, quaternary ammonium, betaine, Sul n-perfluorooctanecarbonyl fluoride of Ahlbrecht’s Example fobetaine or polyoxyethylene) or is an ethylenically 1 with C.-branched fluoroalkylcarbonyl fluoride, to produce unsaturated group (e.g., -OC(O)CH=CH and -OC useful fluorinated amidoalcohols. The resulting amidoalco (O)C(CH)=CH-). hols can be ethoxylated (as described for example in U.S. A preferred subclass of these C-substituted fluoroalkyl Pat. No. 2,567,011 (Diesslin et al.)), Sulfated (as described carbonyl fluoride derivatives is that represented below by for example in U.S. Pat. No. 2,803,656 (Ahlbrecht et al.)) or Formula VII: phosphated (as described in U.S. Pat No. 3,094,547 (Heine)) 25 to prepare nonionic or anionic degradable fluoroaliphatic VII Surfactants. Useful oil and water repellent treatments may be O produced from these fluorinated amido alcohols: for | example, (1) by reaction with acrylic or methacrylic acid or CF (CF). CFCX acryloyl or methacryloyl chloride to form an acrylate or methacrylate monomer and then polymerizing or copoly merizing the monomer using a Standard free radical initiator to form a repellent polymer (see, e.g., U.S. Pat. No. 2,803, 615 (Ahlbrecht et al.); (2) by reaction with isocyanates to wherein: form repellent fluoroaliphatic urethanes, ureas, or carbodi n is between 4 and about 18 inclusive; imides (see, e.g., U.S. Pat. Nos. 3,398,182 (Guenthner et al.) m is between 0 and about 9 inclusive where preferably n 35 and 3,896,251 (Landucci)); or (3) by reaction with carboxy and m are chosen Such that the ratio of (n+1) to (m+1) lic acids (or derivatives thereof) to form repellent esters (see, is at least 2 to 1; and e.g., U.S. Pat. No. 4,264,484 (Patel)). X is as described Supra by Formula VI. Another novel class of compositions provided by this Acid derivatives of C-substituted fluoroalkylcarbonyl invention are C.-branched 1,1-dihydrofluoroalkyl deriva fluorides can be synthesized readily from the C-branched 40 tives. Such compositions, which may be prepared by reduc fluoroalkylcarbonyl fluorides. To form the fluoroalkylcarbo ing C-branched fluoroalkylcarbonyl fluorides, can be repre nyl chloride, the carbonyl fluoride can reacted with hydra sented by Formula VIII below: Zine followed by chlorine using, for example, the procedure described in U.S. Pat. No. 2,950,317 (Brown et al.). Fluo VIII rocarboxylic acids may be obtained by reacting the carbonyl 45 RCFCH2X fluoride or chloride with water, preferably also in the pres ence of acid, and the carboxylate Salts are most conveniently made by reacting either the carbonyl fluoride or the car boxylic acid with a base, preferably in water. Esters can be wherein: made by reacting the carbonyl fluoride or chloride with a 50 R, and R', are selected independently from one another as primary, Secondary, or tertiary alcohol. These reactions a fluorinated, preferably perfluorinated, group bonded involving fluorocarboxylic acids can be run as described in through carbon that may be substituted or U.S. Pat. No. 2,567,011 (Diesslin et al). unsubstituted, cyclic or acyclic, linear or branched (or Amides are particularly useful intermediates that can be any combination thereof) and may optionally contain prepared by reacting the fluoroalkylcarbonyl fluoride with 55 one or more catenary heteroatoms Such as nitrogen, ammonia, a primary amine or a Secondary amine. Primary Sulfur, or oxygen; R or R, may contain one or more amides may be made as instructed in U.S. Pat. No. 2,567, hydrogen atoms or one or more other halogen atoms, 011. The primary amides can further be derivatized, for e.g. chlorine, provided that at least 75%, and preferably example, by reaction with a glycol ester followed by Saponi at least 90%, of the atoms attached to the carbon fication to form carboxylate Salts as described, for example, 60 backbone are fluorine atoms; preferably the ratio of in U.S. Pat. No. 2,809,990 (Brown). Of particular interest is carbon atoms in said R, and R', moieties is at least 2 to the reaction with N,N-dimethylaminopropyl amine to form 1; and the tertiary amidoamine intermediate, which can be prepared X is -OR, —OSOR, —OCOR, -N(R')(R), -SR, as described in U.S. Pat. No. 2,764,603 (Ahlbrecht). The halogen, or an ethylenically unsaturated moiety (e.g., amidoamine can in turn be reacted in a number of ways to 65 acrylate, methacrylate, allyl, Vinyl ether, Vinyl form a variety of cationic and amphoteric Surfactants: for benzyloxy) where R, R and Rare as defined supra in example, it can be quaternized with an alkyl halide to form Formula VI. 6,015,838 9 10 A preferred class of these above-described C.-branched cation (i.e., HN), Substituted ammonium cation (e.g., 1,1-dihydrofluoroalkyl derivatives include the 1,1- HN"(CH), HN+(CH3), HN"(CHOH) dihydrofluoroalkyl derivatives represented by Formula IX , (CH)N" or (CHo)N), and polyammonium cat below: ion (e.g., H.N"(CHNH)-CHNH); and 5 q is equal to the Valency of M. A preferred class of these above-described C.-branched fluorocarboxylate salts is that represented by Formula XI below:

1O wherein: n is between 4 and about 18 inclusive; m is between 0 and about 9 inclusive where preferably n and m are chosen Such that the ratio of n+1) to (m+1) is at least 2 to 1; and 15 X is as defined supra by Formula VIII. The C.-branched fluoroalkylcarbonyl fluoride derivatives wherein: often exhibit Superior water Solubility, Superior Surface n is between 4 and about 18 inclusive; tension VS. concentration profiles, and critical micelle con m is between 0 and about 9 inclusive where preferably n centrations (CMCs) that are comparable to their isomeric and m are chosen Such that the ratio of (n+1) to (m+1) linear fluoroalkylcarbonyl fluoride derivatives with the same is at least 2 to 1; and carbon number. Thus, they are excellent candidates as emul M and q are as defined supra by Formula X. sifiers and Surfactants in applications where environmental In their dry state, the C-branched fluorocarboxylate salts persistence is of concern. Such applications include fluo decarboxylate at temperatures of approximately 140-190 ropolymer emulsions, cleaning Solutions, aqueous film 25 C. to form mostly internal fluoroolefins Such as depicted forming foams, coating additives, plating baths, wetting below for an exemplary Species: agents, floor polish levelling agents, dispersion aids, oil well Stimulation chemicals, and photographic coupling agents. C-F-CFCOO NH, PC Typically, those C.-branched fluoroalkylcarbonyl fluoride derivatives exhibiting the most favorable surface activity characteristics will be those having a long fluorinated alkyl group (i.e., having 5 or more carbon atoms) and a short C.-branched alkyl group (i.e., perfluoromethyl or perfluoroethyl). C-Branched fluoroalkylcarbonyl fluoride derivatives 35 CF15CFHCF (10%). especially preferred as emulsifiers for preparing Stable fluo ropolymer emulsions, latexes, and Suspensions, e.g., poly The Straight chain isomers (also in dry state) decompose at tetrafluoroethylene and polyvinylidene fluoride emulsions, a slightly higher temperature of approximately 180-200 C. (including those methods described by U.S. Pat. No. 4,360, in a sealed tube to form terminal fluoroolefins: 652 (Dohany), which is incorporated herein by reference) 40 are C-branched fluorocarboxylate Salts that may be repre sented generally by Formula X below. CFCOO. NH' 18O-2OO C. CFCFFCF (J. Am. Chem. Soc., 1953, 75, 4525-28).

45 In acqueous Solution the C-branched fluorocarboxylate Salts readily undergo decarboxylation at temperatures of 60-100° C. or lower to give a mixture consisting of roughly 85% monohydride and 15% olefin, isolatable and recover 50 able by azeotropic distillation. The Straight chain isomers, wherein: however, will not decompose in water at a temperature of R, and R', are selected independently from one another as less than 100° C. (e.g., in refluxing water). In water, the pH a fluorinated, preferably perfluorinated, group bonded and the initial concentration of the a-branched Salts also through carbon that may be substituted or greatly affect the rate of thermal decarboxylation, as the unsubstituted, cyclic or acyclic, linear or branched (or 55 decarboxylation reaction Slows in more acidic aqueous any combination thereof) and may optionally contain Solution or at higher emulsifier concentration. Changing the one or more catenary heteroatoms Such as nitrogen, nature of the cation, e.g., from Sodium to ammonium, does Sulfur, or oxygen; R or R, may contain one or more not, however, greatly affect the rate of thermal degradation hydrogen atoms or one or more other halogen atoms, in the environment. e.g. chlorine, provided that at least 75%, and preferably 60 While not wanting to be held to any particular theory, it at least 90%, of the atoms attached to the carbon is believed that the degradation of C.-branched fluorocar backbone are fluorine atoms; preferably the ratio of boxylic acids and their derivatives occurs via the decarboxy carbon atoms in said R, and R, moieties is at least 2 to lation of the C-branched fluorocarboxylate anion (often 1, created from hydrolysis and/or oxidation) to form volatile, M is a cation Selected from the group consisting of H" 65 non-atmospherically-persistent fluorocarbon Species, Such (i.e., the free carboxylic acid), metal cation (e.g., Na', as olefins and monohydrides. The carboxylate anion can be K", Li, Ca, Mg, Fe, Al" or Zn), ammonium formed from hydrolysis and/or oxidation of other 6,015,838 11 12 C.-branched derivatives. If ingested by a transpiring organism, the a-branched fluorocarboxylic acids and their XII derivatives degrade to the above-mentioned volatile mate O rials that are readily eliminated from the body, unlike their R-CFCNHCHN(R") linear acid analogs which are retained unchanged in the body for long periods of time. Organisms will also promote the degradation of C.-branched materials to volatile materials that are readily eliminated by the organism. AS the degra wherein: dation mechanism appears to be independent of a biochemi 1O R, and R', are selected independently from one another as cal mechanism, degradation and elimination should occur in a fluorinated, preferably perfluorinated, group bonded all transpiring organisms (rodents and primates). The Salts of through carbon that may be substituted or C.-branched fluorocarboxylic acids cannot therefore persist unsubstituted, cyclic or acyclic, linear or branched (or indefinitely in the body of the organism as do some of their any combination thereof) and may optionally contain 15 one or more catenary heteroatoms Such as nitrogen, linear analogs. The esters and amides of C.-branched fluo Sulfur, or oxygen; R or R, may contain one or more rocarboxylic acids are, however, much more hydrolytically hydrogen atoms or one or more other halogen atoms, Stable than their linear analogues. e.g. chlorine, provided that at least 75%, and preferably Removal and recycling of fluorinated emulsifiers from at least 90%, of the atoms attached to the carbon fluoropolymer water emulsions during emulsion polymer backbone are fluorine atoms; preferably the ratio of ization processes have become critical from environmental, carbon atoms in said R, and R', moieties is at least 2 to economic, and performance Standpoints. C-Branched fluo 1, rocarboxylic acid ammonium Salts are particularly useful as k is between 2 and 6; and Such fluorinated emulsifiers. Generally in practice of emul R" is a lower alkyl group having from 1 to 4 carbon atoms, 25 preferably methyl, or N(R") may be a heterocyclic Sion polymerization, the emulsifier and free radical initiator ring (Such as a pyridyl, piperidino, or morpholino are first added to water following which is added the group). fluoromonomers as is described in more detail by U.S. Pat. A preferred class of these above-described a-branched 4.576,869 (Malholtra), whose description is incorporated tertiary amidoamine intermediates is that represented by herein by reference. Typically utilized free radical initiators Formula XIII below: include diisopropyl peroxydicarbonate and permanganate compounds of the formula XMnO, where X is hydrogen, XIII ammonium, alkali earth metal, or alkaline earth metal. One O or more chain transfer agents, Such as isopropyl alcohol, | may also be used to control the molecular weight of the 35 polymer. Useful fluoromonomers include any ethylenically unsaturated fluorinated compounds Such as, for example, tetrafluoroethylene, vinylidene fluoride, trifluoroethylene, chlorotrifluoroethylene, hexafluoropropene, Vinyl fluoride, wherein: and pentafluoropropene. Polymerization may be effected by 40 k and R" are as defined supra by Formula XII; mixing the foregoing ingredients in aqueous media at a n is between 4 and about 18 inclusive, and temperature typically between about 50 and 125 C. and a m is between 0 and about 9 inclusive where preferably n and m are chosen Such that the ratio of(n+1) to (m+1) pressure typically between about 15 and 40 kg/cm and is at least 2 to 1. generally is carried out in a gently stirred autoclave. Other 45 The amidoamine intermediates depicted by Formula XIII details of emulsion polymerization techniques will be omit Supra may Subsequently: (1) be either protonated with an ted in the interest of brevity, as such details are well inorganic halogen acid (e.g., HCl or HBr), a Sulfur documented and understood in the art and reference may be containing inorganic acid (e.g., Sulfuric acid),an organic made to the cited documents for Such teaching. After the carboxylic acid (e.g., CHCOOH), or an organic Sulfonic fluoropolymer polymerization is complete, the O.-branched 50 acid (e.g., benzene Sulfonic acid) or be quaternized with an ammonium Salt can be easily destroyed by Simple azeotropic alkylating agent (e.g., an alkyl halide, dialkyl Sulfate, or distillation to give the volatile monohydride and fluoroolefin alkyl Sulfonate) to form a cationic fluoroaliphatic Surfactant; as product, which can be recovered and derivatized for other (2) be reacted with a Sultone (e.g., gamma-propane Sultone), applications. a lactone (e.g., gamma-butyrolactone), an acrylic acid (e.g. According to recent tests, the Salts of a-branched fluoro 55 acrylic acid), a Sulfonato-functional acrylamide (e.g., N-(3- carboxylic acids have acute toxicities an order of magnitude Sulfo-2,2-dimethylpropyl)acrylamide) or a similar com pound to form an amphoteric Zwitterionic fluoroaliphatic less (i.e. LDso levels are ten times higher) than the linear Surfactant; or (3) be reacted with an oxidizing agent (e.g., (non C.-branched) analogues. For instance, the linear long hydrogen peroxide) to form the most preferred amphoteric chain ammonium carboxylate salt, CFCOOTNH, is 60 amine oxide Surfactant. The details of Such reactions are moderately toxic, where its C.-branched isomer, C7FCF well-known and established in the art. (CF)COONH", exhibits relatively low toxicity. Some pyridinium oxides and pyridinium Salts with ester Another class of preferred (X-substituted fluoroalkylcar linkages are similarly prepared from the fluoroalkylcarbonyl bonyl fluoride derivatives are tertiary amidoamine interme fluorides by reaction with for instance 2-(2-hydroxyethyl) diates that are useful in the preparation of degradable 65 pyridine or N-(2-hydroxyethyl)isonicotinamide. fluoroaliphatic Surfactants. This class of compositions may Among the many classes of Surfactants that can be SO be represented generally by Formula XII below. prepared are tertiary amidoamine oxide Surfactants and 6,015,838 13 14 quaternary ammonium Surfactants. Preferred members of CFCF(CF)COF the former class include those according to Formula XIV below. CFCF(CF)COF CoFCF(CoF)COF XIV O CFCF(CF)CFCF(CF)COF Rt-CFCNHCHN (R").O CFCF(CF)COF

1O Acids and Salts wherein: Re, R., k, and R", are as defined supra by Formula XII. Preferred quaternary ammonium Surfactants can be rep resented by Formula XV below. 15

XV O | Rt-CFCNHCHN (R").R" A

wherein: Re, R., k, and R" are as defined sierra by Formula XII; 25 R" is hydrogen or a substituted or unsubstituted monova lent organic group; and A is an anion which is the residue of the alkylating agent R"A or the acid HA. Preferred amphoteric Surfactants which can be prepared O F NCFCFCOOHN from C.-branched tertiary amidoamine intermediates are those isomers represented by Formulas XVI and XVII CF below:

XVI 35 RCF(R')CON(R)(CH), COOH and sodium salts, O where: R is CF (CF), (n=4-9), R", is CF (CF), (m=0-1), and 40 R is CH or H 1,1-Dihydroalcohols

45 C.F.CF(CF)CHOH CFCF(CF)CH-OH wherein: Re, R., k, and R" are as defined supra by Formula XII; CFCF(CF)CH-OH Q is as defined Supra by Formula VI; and 50 CFCF(CF)CH-OH X" is either -SO or -COO. Examples of C-branched fluoroalkylcarbonyl fluorides CF, CF(CF)CHOH and derivatives of this invention are given below. The R CFCF(CFCF)CH-OH group (CF-) group in each formula is primarily nor CFCF(CFCF)CH-OH mal (i.e., unbranched). 55 Carbonyl Fluorides Amides CFCF(CF)COF CFCF(CF)COF C.F.CF(CF)CONH, CFCF(CF)COF 60 CF, CF(CF)CONH(CH)N(CH), CFCF(CF)COF CFCF(CF)COF CFCF(CF)CONH(CH)N(CH) CFCF(CF)COF CFCF(CF)CONH(CH)N(CH) CFCF(CF)COF 65 CFCF(CF)COF CFCF(CF)CONH(CH)N(CH) CFCF(CF)COF CFCF(CF)CONH(CH)N(CH)

6,015,838 17 18 -continued CFCF(CFCF)CHOCOC(CH)=CH, O O CFCF(CFCF)CHOCH=CH, Ill/ \ The C-branched fluoroaliphatic Surfactants made in accor CFCFCOCHNHC N'-CH, I dance with this invention may be used for any application requiring a Surface active agent, including uses as protective CF coatings and Similar applications. Those Surfactants detailed O O herein find particular utility in the formulation of aqueous Ill/ \ film-forming foam (AFFF) concentrates such as those used CF15CFCOCHNHC N-CH, I to extinguish hydrocarbon and other flammable liquid fires. CF o Concentrated aqueous fluoroaliphatic Surfactant-containing Solutions (commonly referred to as “concentrates') that i produce an aqueous film-forming foam upon dilution to C-FisCFNHC.H.N.I O OOCCH premix Solutions (typically called “premixes”) and aeration, CF must possess a combination of critical properties to be O 15 effective in extinguishing flammable liquid fires. These | / \ . concentrates typically are designated as 1%, 3%, or 6% CF15CFCNHCHN O Cl concentrates and are diluted with 99%, 97%, or 94% fresh or Sea water respectively to form the premix. Upon dilution, CF the premix must exhibit Superior foaming characteristics to produce a thick foam blanket that achieves rapid knock down, control, extinguishment, and resistance to reignition of the fire and persists for a significant time after the fire's Nonionic Surfactants extinguishment. Aqueous Solutions comprising the fluoro CFCF(CF)CO(OCH2CH), OH chemical Surfactants detailed Supra are useful as concen 25 trates for producing a film-forming foam. Because of the CFCF(CF)CO(OCH2CH)OCH remarkably low Surface tensions achieved by these CF, CF(CF)CO(OCH2CH)OCH C.-branched fluoroaliphatic Surfactants, the Surface tension Amphoteric Surfactants of these aqueous Solutions is depressed well below the Surface tension of a flammable liquid So that a vapor-Sealing CFCF(CF)CONH(CH)N(CH)(CHCOO) film draining from their foam readily spreads over the CFCF(CF)CON(CHSO)(CH-)-N'-(CH4)H flammable liquid. As a consequence, films produced by these Solutions have a strong tendency to reform if disturbed CFCF(CF)CONH(CH)N(CH)-CHSO or broken thereby reducing the tendency of a fire to reignite O where the film has been disturbed, for example, by wind 35 blowing over the surface of the foam. cricketsch, In practice of the aqueous film-forming foam concentrates, water delivered through a fire hose under CF CHOO preSSure educts typically three percent by Volume of a 3% O concentrate into the hose line by venturi effect to form a / V 40 premixture (or “premix”) of the concentrate diluted with CF15CFCNHCHN\ /O water. The premix becomes aerated to produce a foam by use CF CHOO of an air-aspirating nozzle located at the outlet end of the hose. The foam is applied to a body of burning fuel or other flammable liquid and Spreads quickly as a thick but mobile 45 blanket on the Surface for rapid extinguishment. AS the foam Ethylenically Unsaturated Monomers on the Surface of the flammable liquid drains, an aqueous film is formed which, if disturbed or broken, tends to reform CFCF(CFCF)COOCHCHOCOC(CH.)=CH, to Seal hot vapors and prevents reignition of the fire. The CF, CF(CF)COOCHCHOCOCH=CH, concentrates of the invention are considered highly Storage CF, CF(CF)COOCHCHOCOC(CH.)=CH, 50 stable, passing the U.S. Government specification (MIL-F- CFCF(CF)COOCHCHOCOCH=CH, 24385F) requiring that foaming and film-forming properties CFCF(CF)COOCHCHOCOC(CH.)=CH, of concentrates not be adversely affected if the concentrate and its fresh and Sea water premixes (i.e., the concentrate CFCF(CF)COOCHCHOCOC(CH.)=CH, diluted with water) are stored at 65° C. for 10 days, designed CFCF(CF)COOCHCHOCOCH=CH, 55 to Simulate a room temperature Storage period of approxi CFCF(CF)COOCHCHOCOCH=CH, mately 10 years. CFCF(CF)COOCHCHOCOC(CH.)=CH, The aqueous film-forming foamable Solutions (i.e., CF, CF(CF)COOCHCHOCOCH=CH, concentrates) of the invention comprise an aqueous Solution CF, CF(CF)COOCHCHOCOC(CH)=CH, of one or more a-branched fluoroaliphatic Surfactants of this CF, CF(CF)CHOCOCH=CH, 60 invention and one or more water-Soluble Substantially fluorine-free surfactants. While any of the a-branched fluo CFCF(CF)CHOCOCH=CH, roaliphatic Surfactants described herein may be employed in CFCF(CF)CHOCOCH=CH, the AFFF concentrates of the invention, amphoteric CFCF(CF)CHOCOC(CH)=CH C.-branched fluoroaliphatic Surfactants are preferred, the CF, CF(CF)CHOCOCH=CH, 65 amphoteric amine oxide Surfactants being particularly pre CFCF(CF)CHOCH=CH, ferred. One or more additional fluoroaliphatic amphoteric CF, CF(CF)CHOCHCH-CH=CH, and/or anionic Surfactants, Such as a fluorinated aminocar 6,015,838 19 20 boxylate or a perfluoroalkane Sulfonate, may also be added Surfactants, including ethylene glycol, glycerol, butyl to the formulation. Such additional Surfactants are described Carbitol', dipropylene glycol mono-n-propyl ether, dipro in U.S. Pat. No. 5,085,786 (Almet al.), whose description is pylene glycol monomethyl ether, and hexylene glycol. These also incorporated herein by reference. Solvents may also act as foam Stabilizers and freeze Usefull fluorine-free Surfactants include (1) nonionic Sur protection agents. Additional components, Such as Stabiliz factants that have a hydrophilic-lipophilic balance (HLB) erS and thickeners, can be incorporated into the concentrates value of greater than or equal to about 10, (2) anionic of the invention to enhance the foam stability property of the Surfactants having a carbon chain length containing inclu foam produced after aeration of the premix. Examples of sively from about 6 to about 16 carbon atoms and (3) Stabilizers and thickeners include partially hydrolyzed amphoteric Surfactants, used either individually or as blends. protein, Starches, polyvinyl resins (e.g., polyvinyl alcohol, Representative nonionic fluorine-free Surfactants include polyvinyl pyrolidone, polyacrylamides, carboxyvinyl ethylene oxide-based nonionic Surfactants Such as CH polymers), alkanolamide Surfactants, long chain alkanols, 1O(CHO), H where n is an integer between about 8 and 18 poly(oxyethylene)-glycol, guar gum and locust bean gum. In and m is greater than or equal to about 10, ethoxylated particular, polysaccharide resins, Such as Xanthan gum and alkylphenols Such as 15 other biogums, can be incorporated as foam Stabilizers in concentrates intended to be used on polar Solvent fires Such as alcohols, ketones, and ethers. Other useful resins for improving polar Solvent resistance are fluorochemically modified acrylates or polymers. Corrosion inhibitors, call-O-octor buffers, antimicrobial or other preservative agents, and diva lention Salts may also be employed. Additional components where p is an integer between about 4 and about 12 and Z is that may be added to the AFFF formulations of the invention greater than or equal to about 10, and block copolymers of are detailed in U.S. Pat. Nos. 5,085,786 (Alm et al.) and ethylene oxide and propylene oxide such as PluronicTM F-77 3,772,195 (Francen), both of whose descriptions are incor surfactant (containing at least about 30 wt.% ethylene 25 porated herein by reference for Such purpose. oxide) available from BASF Corp., Wyandotte, Mich. Typically, between 1 and 10 percent by weight of the Representative Short chain anionic fluorine-free Surfac fluorochemical Surfactant or Surfactants and between 1 and tants include alkyl Sulfates, Such as Sodium octyl Sulfate 30 percent by weight of the fluorine-free surfactant or (e.g., SipexTM OLS, commerically available from Rhone surfactants will be employed to make the AFFF concentrate. Poulenc Corp., Cranberry, N.J.) and sodium decyl sulfate The total amount of Solids attributable to other additive (e.g., PolystepTM B-25, commercially available from Stepan components, if Such components are present, should be Such Co., Northfield, Ill., alkyl ether Sulfates Such as CH that the premix maintains its foamability and Such that the (OCH)OSONa, where 6sns 10 (e.g., Witcolate"M 7093, density of the foam prepared therefrom is less than about 1 commerically available from Witco Corp., Chicago, Ill.); g/cc. Generally, the amount of Solids in the concentrate and alkyl Sulfonates Such as CHSO Na, where 35 attributable to Said optional components will be less than 6s ns 10. about 50 weight percent, preferably less than about 30 Representative amphoteric Surfactants include amine weight percent, of the concentrate. The amount of Solvent oxides, aminopropionates, Sultaines, alkyl betaines, used in the concentrate typically is between 5 and 40 percent alkylamidobetaines, dihydroxyethylglycinates, imadazoline by weight of the concentrate. Generally, the amount of Solids acetates, imidazoline propionates, and imidazoline Sul 40 (i.e. nonvolatiles) attributable to non-Surfactant and non fonates. Preferred amphoteric Surfactants include: Salts of Solvent components Such as Stabilizers, thickeners, corro n-octyl amine di-propionic acid, e.g., CH7N Sion inhibitors, buffers, antimicrobial agents, and divalent (CH-CHCOOM) where M is sodium or potassium; ion salts will be less than about 20 percent by weight, MirataineTM H2C-HA (sodium laurimino dipropionate), preferably less than about 10 weight percent of the concen MiranolTM C2M-SF Conc. (sodium cocoampho propionate), 45 trate. MirataineTM CB (cocamidopropyl betaine), Mirataine"M The following examples are offered to aid in a better CBS (cocamidopropyl hydroxysultaine), and MiranolTM JS understanding of the present invention. These examples are Conc. (Sodium caprylampho hydroxypropyl Sultaine), all not to be construed as an exhaustive compilation of all commerically available from Rhone-Poulenc Corp.; and embodiments of the present invention and are not to be those imidazole-based Surfactants described in U.S. Pat. No. 50 unnecessarily construed as limiting the Scope of this inven 3,957,657 (Chiesa, Jr.), whose description is hereby incor tion. porated by reference. The abovementioned preferred amphoteric Surfactants are EXAMPLES especially useful in combination with the fluorinated Test Methods C.-branched fluoroalkylcarbonyl amidoamine oxide Surfac 55 tants of this invention to formulate Superior AFFF agents. The following test methods and procedures were used to Not only is the foamability of the agents excellent, but the evaluate the performance of the fluorinated emulsifiers, Surface tensions of the premixes made from the concentrates surfactants and AFFF agents made therefrom: are very low, for example, below about 17 dyneS/cm, and the Surface Tension (ST): Surface tensions of aqueous Sur interfacial tension at about 2.5 dyneS/cm is optimal for film 60 factant solutions and 3% AFFF premixes were measured in formation. This allows the premixes to form thick and stable units of dyneS/cm using a K-12 Processor Tensiometer and non-emulsified acqueous films which spread over the fuel or 665 Dosimat'TM measuring method with Software K 122, other flammable liquid, leading to excellent fire-fighting available from Kriss GmbH, Hamburg Germany. The sur performance. face tension should be as low as possible for the premix to Additional components may optionally be added to the 65 have its maximum film-forming effectiveness. AFFF concentrates Such as water Soluble solvents used to Interfacial Tension (IT): Interfacial tensions (in dynes/cm) facilitate solubilization of the fluoroaliphatic Surfactant or of the interface formed between 3% premixes and n-heptane 6,015,838 21 22 (>99% purity, Surface tension=20.4 dynes/cm) were mea According to this procedure, 3.0 gallons of a 3.0% (vol) sured using a K-12 Processor Tensiometer. The interfacial premix is made by mixing 3 volumes of a 3% concentrate tension should be as high as possible to produce thick, Stable with 97 volumes of synthetic sea water (the sea water being films and to avoid emulsification of the fuel, yet should be made in accordance with ASTM D1141). The premix is Sufficiently low to allow for a positive spreading coefficient. poured into a tank with attached hose and foam nozzle, and the filled tank is pressurized. Then 15 gallons (57 L) of Spreading Coefficient (SC): The Spreading Coefficient (in automotive gasoline is poured onto a water base contained dyneS/cm), is calculated from the Surface and interfacial in a 50 ft (4.7 mi) circular pit. After the gasoline is ignited tension values measured with the premixes as follows: and allowed to preburn for 10 Seconds, an operator aggres Sively attacks the fire using foam generated from the premix SC-STfuel-ST(premix)+Tcpremix fell by passing the premix through a National Foam System air-aspirating nozzle at a flow rate of 2.0 gal/min. The A positive Spreading Coefficient is a minimum requirement percent extinguishment of the fire is recorded at every 10 for the premix to form a vapor Sealing aqueous film on the Second mark until the fire is fully extinguished. Also, the Surface of the fuel. exact extinguishment time is recorded. The efficiency of fire Critical Micelle Concentration (CMC): The critical 15 extinguishment is quantified as the “40 Second Summation,” micelle concentration is defined as the concentration at which is defined as the Sum of the percent extinguishment which further surface tension is no longer lowered with values recorded at the 10, 20, 30 and 40 second marks. After increasing levels of Surfactant. To determine CMC, surface extinguishment, the foam is continually applied to the pit tension is measured as a function of Surfactant concentration until the 90 second mark, at which time the premix solution using a K-12 Processor Tensiometer in conjunction with a is exhausted. 665 Dosimat automatic Surfactant injection device (also Within 60 seconds after extinguishment, a one foot diam commercially available from Kriss GmbH). Surface tension eter circular pan containing burning gasoline is placed at the is then plotted VS. log concentration and the data points are center of the circular pit. The time for 25% (12.5 ft, or 1.16 connected. The resulting curve has a nearly horizontal flat m) of the foam-covered area to become reinvolved in portion at concentrations above the CMC and has a negative 25 flames is measured and is recorded as the "25% burnback steep slope at concentrations below the CMC. The CMC is time.” defined as the lowest Surfactant concentration in the hori EXAMPLES Zontal flat portion of the curve. A. Synthesis of C.-Branched Fluoroalkylcarbonyl Foam Expansion and Drain Time: Foam expansion, Fluorides defined as the volume of foam produced divided by the Volume of liquid used to produce the foam, is determined as Example A1 described in U.S. Government Military Specification MIL CFCF(CF)COF, an O-branched perfluoroalkylcarbo F-24335, Revision F. In this test, a standard National Foam nyl fluoride, was prepared using the following electrochemi System 2 gal/min (7.6 L/min) nozzle is used to generate cal fluorination procedure. foam from a 3% premix (i.e., 3 parts by volume of concen 35 Using an electrochemical fluorination cell of the type trate mixed with 97 parts by volume of fresh or sea water) described in U.S. Pat. No. 2,713,593 (Brice et al.), a mixture contained in a stainless Steel pressurized tank. The foam is of 94% (wt) CHCH(CH)COCl (275.4 g) and 6% (wt) deflected off a 45 backstop into a 1-L tared graduated dimethyldisulfide (DMDS) (17.6 g) was electrochemically cylinder, and the weight of the cylinder plus foam is fluorinated in boiling HF at 1380 torr and 38 C. contained recorded in grams. The foam expansion is calculated by 40 in a 750 mL cell equipped with a 0.037 m nickel anode for dividing the actual volume (mL) (i.e., not the nominal 1-L a total time of 300 hours using an average current of 7.74 Volume) of the graduate by the weight (g) of the foam. ampS and average conductivity of 6.8 volts during the The 25% drain time for the foam, also described in U.S. electrofluorination. The production rate of crude perfluori Government Military Specification MIL-F-24385, Revision nated carbonyl fluoride increased throughout the run to a F, is defined as the amount of time after foam collection for 45 peak level of 20.0 g/50 amp-hours. Yield of functional 25% of the weight (i.e., volume) of foam to drain to the perfluoroalkylcarbonyl fluorides produced was about 17% bottom of the graduate (read as milliliters in the graduated of theoretical based on cell crude, according to a GC/FTIR cylinder, assuming a specific gravity of 1.0). analysis of an aliquot derivatized into the methyl ester. Film-Forming and Sealing: The Film-Forming and Seal Subsequent analysis of the functional perfluoroalkylcarbo ing Test determines whether an AFFF premix is capable of 50 nyl fluoride mixture using GC/MS showed 21% to be forming a stable film on n-heptane. In this test, an inverted C.F.CF(CF)COF. No. 8 flathead screw is placed in the center of a 10 cm The following a-branched perfluoroalkylcarbonyl fluo diameter glass petri dish containing 40 mL of n-heptane rides (Examples A2-A3) were synthesized from their unflu (>99% purity, Surface tension=20.4 dyneS/cm). An aqueous orinated carbonyl chloride analogues using the essentially film is generated on the n-heptane Surface by gently apply 55 the same electrochemical fluorination procedure as ing dropwise 0.75 mL of test premix solution from a 1 mL described in Example A1. disposable Syringe to the tip of the inverted Screw over an approximately 30 to 60 second time period. Two minutes after applying the first drop of premix Solution, a Small flame Ex. is moved approximately 0.5 inch (1.3 cm) over the 60 A2. CFCF(CF)COF n-heptane Surface for about 10 Seconds. For a good vapor A3. CFCF(CFCF)COF Seal, no Sustained ignition shall result, though a Small intermittent flash is permitted. Fire Extinguishment and Burnback Test: The fire test Synthesis of Methyl Ester Intermediates. By Direct Fluorination procedure used to evaluate AFFF agents in the examples is 65 outlined in the U.S. Department of Defense Military Speci CFCF(CF)COOCF was prepared from CHCH fication No. MIL-F-24385, Revision F, Section 4.7.13.2. (CH)COOCH using the following direct fluorination pro 6,015,838 23 24 cedure. A direct fluorination run was made using a reactor Examples A5-A13 system similar to the one described in U.S. Pat. No. 5,488, The following fluoroalkylcarbonyl fluorides were pre 142.6449 g of 3M Brand PF-5052 Performance Fluid was pared from their perfluorinated methyl ester analogues using charged to the gas-liquid Separator of the reactor System and, the same KI reaction procedure as described in Example A4. using a circulating pump, was circulated through the reactor 5 System at a rate of 11.8 kg/min. Nitrogen was introduced into the circulating stream of PF-5052 at a rate of 2007 Ex. Percent Yield cm/min, and the temperature of the circulating stream was A5. CF, CF(CF)COF 79 maintained at 28 C., maintaining the temperatures of the A6. CFCF(CF.)COF 84 A7. CF,CF(CF.)COF 92 two overhead condensers at 10 C. and -32 C. respectively. A8. CF, CF(CF)COF 88 After Sufficient nitrogen had purged the vapor Space to drop A9. CFCF(CF)COF N/R the oxygen concentration to below 0.1% (as measured in the A10. CFCF(CFS)COF 84 gas stream exiting the System), fluorine was introduced into A11. CFCF(C.F.)COF N/R 15 A12. C.F.CF(C.F.)COF 85 the tubular reactor at 538 cm/min. A feed of 464 g of A13. CFCF(CF)COF N/R CHCH(CH)COOCH was gradually introduced into the PF-5052 in the mixing Zone to react with the fluorine over a period of 59 hours. After all of the organic feed had been B. Synthesis of a-Branched added, the diluted fluorine addition was continued until the Perfluoroalkylcarboxamides oxygen gas content of the gaseous effluent of alumina columns used as Scrubbers rose to greater than 5% (i.e., the Example B1 alumina reacts with fluorine and releases oxygen). The C.F.CF(CF)CONH(CH)N(CH) was prepared by fluorine Supply was shut off and the nitrogen Supply was reacting C.F.CF(CF)COF (from Example A1) with N,N- continued until unreacted fluorine was purged from the 25 dimethylaminopropylamine using the following procedure. System, after which the circulating pump was shut off. 1084 g (2.1 mol) of CFCF(CF)COF was added dropwise Percent yield of CFCF(CF)COOCF was 72%. The to a mixture of 320 g (3.1 mol) of N,N- product was purified by distillation. dimethylaminopropylamine and 1200 mL of tetrahydrofuran (THF) at room temperature over a period of approximately The following fluorinated ester derivatives were prepared 2 hours. After addition was completed, the mixture was from their hydrocarbon analogues using an analogous direct refluxed for 3 hours. After being allowed to cool, the THF fluorination procedure to that described immediately above. Solution was washed twice with an aqueous Solution of NaHCO, then was washed twice with deionized water. The 35 aqueous portion was extracted twice with 150 mL aliquots Ex. Percent Yield of chloroform, the chloroform solutions were combined with the THF solution, and the resulting combined solution was C.F.CF(CF)COOCF, 86 C.F.CF(CF)COOCF, 85 dried over anhydrous MgSO. Solvent was removed under CF, CF(CF)COOCF, 91 reduced preSSure and the residue was distilled under reduced CF, CF(CF)COOCF, 76 pressure to give 1025 g (82% yield) of the desired product, CFCF(CF)COOCF, Not Recorded (NIR) 40 whose structure was confirmed by IR spectra and by H, °C CFCF(CFs)COOCF, 72 CFCF(C.F.)COOCF, N/R and 'F NMR spectra. C.F.CF(C.F.)COOCF, 82 The following a-branched perfluoroalkylcarbonamidoam CFCF(CF)COOCF, N/R ine and perfluoroalkylcarbonamide intermediates (Examples 45 B2-B 15) were synthesized by reacting their C.-branched perfluoroalkylcarbonyl fluoride analogues shown in Examples A1-A13 with N,N-dimethylaminopropylamine, Example A4 dimethylaminopropanol or primary mono- or diamines using the same reaction procedure as described in Example 50 B1, keeping the molar ratio of carbonyl fluoride to active In Example A4, CFCF(CF)COF was prepared from hydrogen-containing amine the same. In Some examples, CFCF(CF)COOCF. To 4500 g (7.73 mol) of CFCF diisopropyl ether (IPE) was used as the solvent instead of (CF)COOCF in 1700 mL of acetone was added 200 g (1.2 THF. mol) of KI in one portion at room temperature. The mixture was Stirred for 2 hours at room temperature and then for 55 another 2 hours at 40 C. The inorganic salt by-product was Ex. Amine Used filtered off, and the bottom layer, containing the desired B2. CFCF(CF)CONH(CH)N(CH), HN(CH2)N(CH), B3. CFCF(CF)CONH(CH)N(CH), HN(CH2)N(CH), product, was recovered by distillation at 142-147 C. (3598 B4. CF, CF(CF)CONH(CH)N(CH), HN(CH2)N(CH), g, 90.2% yield). The structure of the desired product, B5. CFCF(CF)CONH(CH.)N(CH), HN(CH2)N(CH), C.F.CF(CF)COF, was confirmed by analysis of IR and 60 B6. CFCF(CFCF)CONH(CH)N(CH), HN(CH2)N(CH), 'F NMR spectra. B7. C.F.CF(CFCFCF)CONH(CH)N(CH), H.N(CH)N(CH), B8. CFCF(CF)CONH(CH2)CH, H.N(CH2)CH, B9. C.F.CF(CF)CONH(CH2)CH, H.N(CH2)CH, B10. CFCF(CF)CONH(CH)N(CH), HN(CH2)N(CH), (By word of Caution to the reader: Running this size B11. C.F.CF(CF)CONHCHCH, HNCHCH reaction generates Significant concentrations of hazardous 65 B12. CF, CF(CF)CONHCHCH, HNCHCH carbonyl fluoride (COF), and care must be taken to remove B13. CFCF(CF)CONHCHCH, HNCHCH the COF2 by Suitable absorption in aqueous alkali.) 6,015,838 26 -continued lowing procedure. 155 g (0.3 mol) CFCF(CF)COF (from Example A1) was added dropwise at room tempera Ex. Amine Used ture to a mixture of 41 g (0.35 mol) of 2-hydroxyethylacrylate, 31 g (0.3 mol) of triethylamine, and 350 mL of THF. After addition was complete, the resulting B14. O mixture was allowed to react by heating to 50° C. with CF15CFCNH(CH2)N O H2NCH2)3N O stirring for 3 hours. The reaction mixture was washed 3 times with deionized water, the resulting aqueous Solutions CF were poured together and extracted with chloroform, the resulting chloroform Solution was combined with the reac tion mixture, and reaction mixture/chloroform combination Example B15 was dried over anhydrous MgSO. The solvent was then removed and the residue was distilled at 95-102 C. and 3 C.F.CF(CF)CONCCHN(CH) was prepared by mm Hg to yield 130 g of desired product, whose structure reacting CFCF(CF)COF (from Example A1) with was confirmed using IR and NMR analysis. HNI(CH6N(CH) using the following procedure. 25.8 g. 15 The following acrylates, methacrylates and alkyl-, aryl-, (0.05 mol) of CFCF(CF)COF was added to a mixture of Substituted alkyl- and Substituted aryl esters (Examples 18.7 g (0.10 mole) of HN(CH, N(CH) and 50.5g of D2-D31) were Synthesized using the same procedure as diisopropyl ether in a 3-necked round bottom flask equipped described in Example D1. with Stirrer, heater, thermometer and reflux condensor, and the resulting mixture was refluxed for 3 hours and was allowed to cool. Then 150 g of deionized water was added Ex. and the contents of the flask were stirred vigorously. The pH D2. CF,CF(CF.)COOCHCHOCOCH=CH, of the contents was adjusted downward from 10 to 9 using D3. C.F.CF(CF.)COOCHCHOCOC(CH)=CH, acetic acid, resulting in the formation of two distinct phases. D4. CF,CF(CF.)COOCHCHOCOC(CH)=CH, The lower aqueous phase was drained, Saving the upper 25 D5. CFCF(CF)COOCHCHOCOCH=CH, D6. CFCF(CF.)COOCHCHOCOC(CH)=CH, organic phase. The organic phase was then washed with 50 D7. C.F.CF(CF)COOCHCHOCOCH=CH, g of water (readjusting the pH of the contents to 9), and the D8. C.F.CF(CF)COOCHCHOCOC(CH)=CH, water phase was again drained. The washed organic phase D9. CF, CF(CF)COOCHCHOCOCH=CH, was dried over anhydrous MgSO, was filtered, and was D10. CF, CF(CF)COOCHCHOCOC(CH)=CH, D11. CFCF(CFCF)COOCHCHOCOC(CH)=CH, evaporated to dryneSS in a vacuum oven, resulting in 30.0g D12. C.F.CF(CF)COOCHCHCHCH, of an amber oil which was the desired product (as confirmed D13. CFCF(CF)COOCHCHCHCH by IR and H NMR analysis). D14. C.F.CF(CF.)COOCHCHCHCH D15. CF,CF(CF)COOCHCHCHCH, C. Synthesis of C-Branched Perfluorocarboxylic D16. CF, CF(CF)COOCHCHCHCH, Acid Methyl Esters D17. CFCF(CFCF)COOCHCHCHCH, 35 D18. C.F.CF(CF)COOCHs Example C1 D19. C.F.CF(CF)COOCH-p-OCH D2O. CFCF(CF)COOCH-p-NO, The methyl ester, C.F.CF(CF)COOCH, was prepared D21. CFCF(CFCF)COOCHCH-NHCO-4-Py D22. C.F.CF(CF.)COOCHCH-NHCO-4-Py using the following procedure. CFCF(CF)COOCF was D23. CFCF(CF.)COOCHCH-NHCO-4-Py mixed with a Stoichiometric excess of methanol, and the 40 D24. CF, CF(CF)COOCHCH-NHCO-4-Py mixture was refluxed with stirring for 2 hours. The unreacted D25. CF,CF(CF.)COOCHCH-2-Py methanol was distilled off and the desired methyl ester, D26. C.F.CF(CF.)COOCHCH-2-Py D27. CFCF(CF.)COOCHCH-2-Py CFCF(CF)COOCH, was washed with deionized water, D28. CF, CF(CF)COOCHCH-2-Py was dried over anhydrous MgSO, and was purified by D29. C.F.CF(CF.)COOCHCHCHN distillation. 45 D3O. C.F.CF(CF.)COOCH(CHN)CHOCH, The following methyl esters ( Examples C2-C9) were D31. C.F.CF(CF.)COOCH(CHN)CHOCHN Synthesized using the same procedure as described in D32. CFCF(CF)COOCH(COOCH)(CH.) D33. C.F.CF(CF.)COOCHCH.)CHN(CH), Example C1. D34. CF,CF(CF.)COOCHCH.)CHN(CH), D35. CSF, CF(CF)COO(CH)N(CH), 50 Ex. (where Py = pyridyl) C2. C.F.CF(CFCFCF)COOCH, The acrylate and methacrylate esters from Examples C3. CFCF(CF)COOCH, D1-D11 were fully recoverable with essentially no degra C4. CFCF(CFCF)COOCH, C5. CF, CF(CF)COOCH, dation after being Stirred with concentrated acqueous ammo C6. CF, CF(CF)COOCH, 55 nium hydroxide for a period of 2 days. Thus, C.-branched C7. CFCF(CF)COOCH, esters were shown to be hydrolytically stable, even in basic C8. CFCFCF(CF)CF(c-CF)COOCH, Solution, So that they may be polymerized using emulsion C9. (c-CF),CFCOOCH, polymerization. In contrast, Similar esters of a non-C.- branched perfluorocarboxylic acid, for example, *The cyclic perfluorinated methyl ester precursors to these methyl esters were 60 CFCOOCHCHOCOCH=CH, were readily hydro made according to the procedure described in Example A4 lyzed under comparable conditions. D. Synthesis of C-Branched Perfluorocarboxylic E. Synthesis of C-Branched Perfluoroalkylcarbonyl Acid (Meth)acrylates and Longer Chain Esters Amine Oxide Surfactants

Example D1 65 Example E1 The a cry late, C, F, CF (CF) CFCF(CF)CONH(CH)N(CH)O was prepared COOCHCHOCOCH=CH, was prepared using the fol by reacting CFCF(CF)CONH(CH)N(CH) (from 6,015,838 27 28 Example B1) with hydrogen peroxide using the following procedure. 12.0 g (0.02 mol) of CFCF(CF)CONH(CH) N(CH) and 12.0 g of ethanol were added to a 3-necked Ex. Amine Oxide round-bottom flask equipped with Stirrer, thermometer and E11 O O water condensor. To this stirred solution was added 5.7g (0.05 mol) of 30% aqueous H.O. over a 5 minute period, cercocystic|| || ( yN-O and Stirring was continued for 72 hours at ambient lab CF o temperature. The resulting Solution was refluxed for a 4-hour E12 period, 0.2 g of decolorizing/activated charcoal was added, 1O O and the mixture was gently refluxed for an additional 3 | hours. The reacted mixture was filtered through Celite TM CF13CFCOC2H4 N+ filter aid and the filtrate was evaporated to dryneSS at CF aspirator vacuum at 70° C. for 3 hours to produce a viscous O yellow oil. IR analysis and H and 'F NMR analysis were 15 consistent with the structure CFCF(CF)CONH(CH-)-N' E13 (CH)O. O CF15CFCOCH4 The following C-branched tertiary perfluoroalkylcarbon N+ amidoamine oxides (Examples E2-E9) were synthesized by CF reacting their ax-branched tertiary perfluoroalkylcarbonami O doamine analogues with hydrogen peroxide using the same reaction procedure as that described in Example E1, keeping the molar ratio of reactants the same: 25 Example E14 CFCF(CF)CONCCH)N(CH2)2O) was prepared Ex. Amine Oxide using the following procedure. To 10.0 g (0.0146 mol) of E2 C.F.CF(CF)CONH(CH.)N(CH).O. CF15CF(CF)CONICH6N(CH) (from Example B16) E3 CFCF(CF.)CONH(CH.)N(CH).O. was added 10.0 g of ethanol. 7.9 g (0.07 mol) of 30% E4 CF,CF(CF.)CONH(CH.)N(CH).O. aqueous HO was added, and the mixture was heated at 70 E5 CF, CF(CF)CONH(CH)N(CH)O C. for 5 hours, then was allowed to cool to room tempera E6 CFCF(CFS)CONH(CH)N(CH).O. E7 C, F, CF(C.F.)CONH(CH)N(CH).O. ture. After cooling, the mixture was refluxed for 1 hour, then E8 CFCF(CF)CON(CHOH)(CH)N(CH),O 0.2 g of activated carbon was added and the mixture was refluxed for an additional 3 hours. The Solution was filtered 35 E9 O and the solvent was removed at 70° C. and 25 torr to give | / V 10.7 g of the desired product, a yellow oil. CF festical O CF O F. Synthesis of C.-Branched Perfluoroalkylcarbonyl 40 Cationic Surfactants Example F1 Example E10 The pyridinium Salt, The perfluoroalkylcarbonyl pyridinium amine oxide, 45

CF15CFCOCHNHC / N-CH, I cercoolinico / N-O CF CF 50 was prepared using the following procedure. CFCF(CF) was prepared using the following procedure. A mixture of COOCHCH-NHCO-4-Py (from Example D22) was added 0.04 mol of CFCF(CF)COOCHCH-NHCO-4-Py (from to a slight stoichiometric excess of methyl iodide in THF, Example D23) and 0.1 mol of peracetic acid in 100 mL of 55 and the mixture was allowed to react by refluxing for 2 ethanol was allowed to react by refluxing for 9 hours. Then hours. The resultant orange Solid was filtered off, was 2 g of activated carbon was added and the mixture was washed with THF, and was recrystallized from ethanol as allowed to reflux for 3 additional hours. The mixture was yellow crystals. filtered and the solvent was removed from the filtrate to give the desired product. 60 Example F2 The following a-branched tertiary perfluoroalkylcarbonyl The following a-branched perfluoroalkylcarbonyl pyri pyridinium amine oxides (Examples E11-E13) were Syn dinium iodide was Synthesized by reacting the analogous thesized by reacting their C.-branched perfluoroalkylcarbo C.-branched perfluoroalkylcarbonyl pyridine (from Example nyl pyridine analogues with peracetic acid using the same 65 D23) with methyl iodide using the same reaction procedure reaction procedure as that described in Example E1I, keep as described in Example F1, keeping the molar ratio of ing the molar ratio of reactants the Same: reactants the Same: 6,015,838 29 30 round bottom flask and Stirred while warming until a clear O O solution was formed. The ethanol was evaporated off under reduced pressure and the resulting product was further dried cercoolinic|| || ( yN-CH, I in a vacuum oven at 70° C. and 25 torr for 4 hours to provide CF o the Surfactant citrate Salt. Analysis by IR spectroscopy confirmed the structure to be

Example F3 CF COOH 10.0 g (0.02 mol) of the amidoamine from Example B2 1O CsF1CFCOO(CH2)N(CH3)2H OOCCHCCHCOOH and 1.77 g (0.022 mol) of 2-chloroethanol were added to a OH round bottom flask. The mixture was heated and stirred at 70° C. for 24 hours and was cooled to give an amber resinous material. Using infrared spectroScopy, the Structure Example F9 of the product was confirmed to be the desired cationic 15 fluoroaliphatic Surfactant, The amine salt, CFCF(CF)CONCHN(CH)H) 2OOCCH), was prepared using the following procedure. CF 5.0 g of CFCF(CF)CONICHN(CH) (from Example B15) was mixed with 5.0 g of glacial acetic acid CI and 10.0 g of deionized water to form an aqueous Solution of the desired amine Salt. Example F4 G. Synthesis of C-Branched Perfluoroalkylcarbonyl Thioesters The following a-branched perfluoroalkylcarbonyl ami 25 doamines (Example F4-F6) were synthesized using a Syn Example G1 thetic procedure analogous to that described in Example F3 except that the amides of Examples B1, B14 and B15 The thioester, C.F.CF(CF)COSCHCHCHCH, was respectively were substituted for that from Example B2. prepared using the following procedure. A mixture consist ing of 0.02 mol C, FCF(CF)COF (from Example A1), 0.025 mol of 1-butanethiol, 0.025 mol of pyridine and 50 mL Ex. of THF was allowed to react by refluxing for 3 hours. Dilute aqueous HCl was added with mixing, producing two phases. F4. f C2H4OH After Separating the organic phase, the aqueous phase was C7F15CFONH(CH2)3.N(CH3)2 CI 35 extracted twice with 30 mL of chloroform and the two chloroform Solutions were combined with the organic phase. F3 O Solvent was then removed from the chloroform/organic / \ phase mixture and the residue was distilled to give the C7F15CFCNHCHN O Cl desired product having a boiling range of 202-205 C. CF 40 The following thioesters (Examples G2-G7) were syn C2H4OH thesized using the same procedure as described in Example G1. F6 i to: CF15CFCNHCHN(CH3)2 2Cl 45 Ex. CF G2. CF, CF(CF)COSCHCHCHCH, G3. CFCF(CF)COSCHCHCHCH, G4. C.F.CF(CF)COSCHCHCHCH, G5. C.F.CF(CF)COSCHCHCOOCH, Example F7 G6. C.F.CF(CF)COSCHCHCOOH 50 1.0 g (0.0016 mol) of the amidoamine from Example B14, G7. CFCF(CF)COSCHCHN(CH), 1.22 g (0.02 mol) of glacial acetic acid and 1.11 g of deionized water were combined in a round bottom flask and H. Synthesis of C-Branched 1,1- Stirred for 1 hour at ambient temperature to form a clear Dihydroperfluoroalkanols Solution of the desired Surfactant Salt, 55 Example H1 O | / \ The dihydroperfluoroalkanol, CFCF(CF)CH-OH, CF15CFCNHCHNH O OOCCH was prepared using the following procedure. 4 g of Sodium CF 60 borohydride was added in portions to a mixture of 25 g of CFCF(CF)COF (from Example A1) and 100 mL of THF at room temperature. The resulting mixture was stirred overnight at room temperature. Deionized water was then Example F8 added carefully to destroy the excess sodium borohydride 10.0 g (0.02 mol) of CFCF(CF)COO(CH)N(CH) 65 and hydrochloric acid was added to adjust the pH in a range (from Example D35), 3.84 g (0.02 mol) of citric acid of 7-8, thus producing a bottom organic and a top aqueous (>99.5% pure) and 10.0 g of ethanol were combined in a phase. The organic phase was Separated and distilled to give 6,015,838 31 32 19 g of the desired product, whose Structure was confirmed The data in Table 1 show that both the acrylate and by IR and NMR analysis. methacrylate hoimopolymers have relatively low glass tran The following dihydroperfluoroalkanols (Examples Sition temperatures. H2-H7) were Synthesized using the same procedure as described in Example H1. Examples I5-12 In Examples I5-I12, homopolymers were made from the acrylates and methacrylates from Examples D2, D3, D4, D5, D6, D8, D10 and D11 respectively using essentially the H2. C.F.CF(CF,CF,CF)CHOH Same procedure as was used to make the homopolymer from H3. CF, CF(CF.)CHOH 10 the monomer of Example D1. Each homopolymer was then H4.HS. CFCF(CF)CH-OH dissolvedissolved in trifluorotoltriluorotoluene, coatedted ontoont a glass1 cover Slip,li H6. CFCF(CF,CF)CHOH and allowed to air-dry. After drying, aach coated slip was HF. CFCF(CFCF)CHOH heat treated at 120° C. for 15 minutes to cure the polymer. Measurements of advancing contact angle with deionized I. Synthesis and Evaluation of Polymers containing 15 water and n-hexadecane were then made on each polymer C-Branched Perfluoroalkyl Acrylates and coated glass cover Slip using a Cahn Dynamic Contact Angle Methacrylates Analyzer, Model 322 (Wilhelmy balance and computer for Example I1 control and data processing), with a stage speed of 150 The homopolymer of C, F, CF (CF) microns per Second. Contact angles are reported in Table 2 COOCHCHOCOCH=CH was prepared using the fol- and are the average of 3 replicates.

TABLE 2 Mon. Contact Angle: Ex. Ref. Monomer Structure Water C15H34 I5. D2 CF, CF(CF)COOCHCHOCOCH=CH, 111° 78 I6. D3 C, F, CF(CF)COOCHCHOCOC(CH)=CH, 120° 720 I7. D4 CF,CF(CF)COOCHCHOCOC(CH)=CH, 112 74° 8. D5 CFCF(CF)COOCHCHOCOCH=CH, 119° 720 9. D6 CFCF(CF)COOCHCHOCOC(CH)=CH, 919 69 1O D8 C.F.CF(CF.)COOCHCHOCOC(CH)=CH, 113 700 11. D10 CFCF(CF)COOCHCHOCOC(CH)=CH, 69 68 I12. D11 CFCF(CFCF)COOCHCHOCOC(CH)=CH, 95° 69°

35 lowing procedure. A 100 mL 3-necked flask was charged The data in Table 2 show that excellent repellency to both with 1 O 9. of ne at C, F, CF (CF) aqueous and organic liquids is shown by each C-branched COOCHCHOCOCH=CH (the acrylate monomer from perfluoroalkyl-containing acrylate and methacrylate Example D1) and 0.2 g of azobis(isobutyronitrile) (AIBN). polymer, indicating that these polymers would be excellent The flask was evacuated of air and was purged with nitrogen. 40 repellents for fibrous Substrates Such as textiles, carpet and The contents of the flask were heated to 60° C. with stirring leather. for one hour to give the desired polyacrylate. Example I13 A polymeric Surfactant active in both organic Solvents and 45 water was made from C, F, CF (CF) COOCHCHOCOCH=CH, the acrylate monomer pre Examples I2-4 pared in Example D1, using the following procedure. To an 8 ounce (225 mL) narrow mouth bottle were added 6.0 g of monomer D1, 28 g of 50% (wt) PluronicTM L-44 diacrylate In Examples I2-14, homopolymers were made from the 50 in toluene (prepared as described in Example 1 of U.S. Pat. methacrylate monomers from Examples D8, D6 and D3 No. 3,787,351 (Olson)), 0.8 g of mercaptopropanediol, 0.4 respectively using essentially the same procedure as was g of t-butyl peroctoate, and 113 g of isopropanol. The bottle used to make the homopolymer from the monomer of with its contents was sealed and was tumbled at 90° C. for Example D1. The homopolymers were evaluated for their approximately 4–5 hours to polymerize the monomers. Then glass transition temperatures according to Test Method tumbling was ceased and the bottle was allowed to cool to ASTM E 1356-91, with results presented in Table 1. room temperature before opening and admitting air. The

TABLE 1. Mon. Tg ( C.) Tg ( C.) Ex. Ref Monomer Structure (bulk) (soln) 1. D1 CFCF(CF)COOCHCHOCOCH=CH, 3 -11 2. D8 C.F.CF(CF)COOCHCHOCOC(CH)=CH, 16 2 3. D6 CFCF(CF.)COOCHCHOCOC(CH)=CH, 7 -16 I4. D3 C.F.CF(CF.)COOCHCHOCOC(CH)=CH, -3 -22 6,015,838 33 34 resulting concentration of polymer was 15% by weight, as the amidoamine intermediate of Example B1 and 1.66 g determined by evaporating a Small weighed portion of the (0.023 mol) of acrylic acid were added to a round bottom Solution in a small dish in a forced air oven at 100° C. for flask, and the resulting mixture was stirred at room tem 1 hour. perature for 6 days to obtain a Viscous amber liquid. The completion of reaction was confirmed by dissolving 1% by The polymer solution was diluted to 0.5% (wt) solids in weight of the amber liquid in deionized water and adjusting both toluene and deionized water, and Surface tension values the pH of the resulting Solution to 8 using dilute aqueous of the diluted Solutions, as measured using a Fisher Model NaOH. The solution stayed clear with no precipitate of 20 duNuoy Tensiometer, were found to be 25.7 dynes/cm in amidoamine Starting material evident, indicating good toluene and 21.3 dyneS/cm in water. completion of reaction to form the desired product, C.F.CF(CF)CONH(CH.)N(CH), CHCOO. 1H Example I14 NMR spectroscopy was consistent with the desired product. A waterborne copolymer was prepared from an Example K2 C.-branched perfluoroalkylcarbonyl-derived acrylate by the 15 following procedure. To a 16 oz (225 mL) bottle was 21.9 g (0.04 mol) of the amidoamine intermediate of charged 36 9. of CF, CF (CF) Example B3 and 4.9 g (0.04 mol) of Y-propanesultone were COOCHCHOCOCH=CH (from Example D2), 15 g of added to a 3-necked round bottom flask equipped with a acrylic acid, 2.5g of CH=C(CH)COOCHCHSi(OCH) stirrer and thermometer. The mixture was heated to 80 C. 2, 40 g of isopropanol, 20g of N-methylpyrrolidinone and with stirring, when an exotherm to 135 C. occurred. The 0.40 g of AIBN. The charged bottle was purged with temperature was kept at 135 C. for 15 minutes, then the nitrogen for about 5 minutes, the bottle was Sealed, and the contents of the flask were allowed to cool at room tempera contents were allowed to polymerize at 80 C. for 5 hours. ture. Upon cooling, 26.8 g of a cream-colored Solid formed The polymer formed was transferred to a flask and isopro which was broken up with a spatula. The completion of panol was stripped at 70° C. under reduced pressure. The 25 reaction was confirmed by dissolving a Small amount of the polymer was then neutralized by dispersing into 150 g of Solid in deionized water and raising the pH of the resulting 2.4% (wt) aqueous ammonium hydroxide. The Solids con aqueous Solution to 8 using dilute aqueous NaOH. The tent of this solution was 16.2% by weight, measured by Solution stayed clear with no precipitate of the amidoamine evaporating a small Sample at 80 C. for 2 hours. intermediate evident, indicating good completion of reac tion. Analysis by infrared and "H NMR spectroscopy con To 50 g of the above-made solution was added 41 g of firmed the product to be primarily a mixture of the ampho CX-WS-300 crosslinker (a 10% aqueous dispersion of an oxazoline terpolymer made from 85% isoprope nyl teric Surfactants CFCF(CF)CON(CHSO)(CH)-N" oxazoline, 10% methyl methacrylate and 5% ethyl meth (CH4)H and CFCF (CF)CONH(CH)N(CH) acrylate; commercially available from Nippon Shokubai, CHSO Japan), and the pH of the formulation was adjusted to 7.5 by 35 The following acrylic acid adducts (Examples K3 and K4) the addition of a very Small amount of aqueous ammonia. were Synthesized using an analogous procedure as described This formulation was then aged for 1 week at room in Example K1, except that amidoamine of Examples B14 temperature, after which a Small Sample was coated into and B15 respectively were substituted for the amidoamine of clear polyethylene terephthalate (PET) film using a #15 Example B1. wire-wound rod. The coated PET film was cured for 10 40 minutes at 120° C., producing a transparent coating which Ex. caused dewetting of ink applied to the coated film from a blue Sharpie TM permanent marker. | / V J. Synthesis of Nonionic Surfactant Containing C.- 45 CF15CFCNHCHN O Branched Perfluoroalkyl Group CFl, /\ / CHOO Example J1 50 CF, CF(CF)CO(OCH2CH)OCH was prepared using the following procedure. An equimolar mixture of CF, CF(CF)COF (from Example A7) and CarbowaxTM CF CHCOO 750 methoxy-terminated diol (commercially available from Union Carbide Corp., Danbury, Conn.) were reacted for 5 hours in stirred refluxing tetrahydrofuran (THF). The THF 55 was then removed under reduced pressure to give the desired Evaluation of C-Branched Perfluoroalkyl nonionic Surfactant, whose Structure was confirmed using IR Surfactants analysis. The C-branched perfluoroalkyl Surfactants made in Sev 60 eral of the previous examples were dissolved in deionized K. Synthesis of Amphoteric Surfactants Containing water at various concentrations and the Surface tension of C-Branched Perfluoroalkyl Groups each resulting aqueous Surfactant Solution was measured using a K-12 Processor Tensiometer and 665 Dosimat"M Example K1 measuring method. Then the critical micelle concentration 65 (CMC) was determined for each surfactant. The CMC for CFCF(CF)CONHCCH)N(CH-)-CHCOO was each Surfactant and the corresponding Surface tension at the prepared using the following procedure. 12.0 g (0.02 mol) of CMC are presented in Table 3.

6,015,838

TABLE 3-continued

From Salt Surf Tens. CMC Ex.: Structure (dynes/cm) (ppm)

F2 O O 15.5 3O CFCFCOCHNHC / N-CH, I CF

F1 O O 15.O 500 CF15CFCOCHNHC / Ni-CH, I CF

F5 O 20.8 1OOO / V CF15CFCNHCHN O C

CF C2H4OH

K1 C.F.CF(CF)CONH(CH)N(CH),C.H.COO 16.6 125 K2 CFCF(CF)CON(CHSOs)(CH)N(CH).H 2O3 500

K3 O 19.2 1OOO / M C7F15CFCNHCHN O

CF CHCOO

K4 O 23.6 1OO effectical CF CHCOO

J1 CF,CF(CF)CO(OCH2CH)OCH 22 150

The data in Table 3 show that the C-branched perfluoro Film-Formation and Sealability, Surface Tension and Inter alkyl Surfactants exhibit good Surface tension reduction in facial Tension. Results from the 3% premix evaluations are water, with especially good results shown by the amine 40 presented in Table 4. oxides and pyridinium iodides. TABLE 4 L. Evaluation of C-Branched Test Method 3% tap 3% sea Spec. Perfluoroalkylcarbonyl Amine Oxide Surfactants in 45 AFFF Formulations Foam Expansion 8.2 7.8 >5.0 25% Drain Time 2O)4 2O2 >150 Film Formation & Sealability pass pass pass Example L1 Extinguishment Time 40 40 SO 25% Burnback Time 410 369 >360 In Example L1, a 3% AFFF concentrate was formulated 50 as follows: The data in Table 4 show that an excellent AFFF 3% concentrate can be made by incorporating an O-branched perfluoroalkylcarbonyl amine oxide Surfactant in the con 3% AFFF Concentrate (% solids by weight): centrate at only 1.5% by weight. 1.5% - fluorinated amine oxide surfactant E1, 55 C.F.CF(CF.)CONHCHCHCHN(CH).O. M. Synthesis and Evaluation of C-Branched 2.0% - sodium n-octyl sulfate (Sipex TM OLS) Perfluorocarboxylic Acids and C.-Branched 3.0% - sodium cocoampho propionate (Miranol TM C2M-SF) 25.0% - dipropylene glycol n-propyl ether Perfluorocarboxylate Salts 68.5% - deionized water and surfactant co-solvents 60 Example M1 (pH of concentrate was adjusted to around 8.3 using glacial acetic acid) C.F.CF(CF)COOH was prepared by the hydrolysis of C.F.CF(CF)COF (from Example A1) using the following Three parts by Volume of the resulting concentrate was procedure. 860 g of CFCF(CF)COF was stirred with diluted each with 97 parts by volume of fresh water and 3000 mL of deionized water for 6 hours at room tempera synthetic sea water (ASTM D1141-52) to form 3% premixes 65 ture. Concentrated hydrochloric acid was added to obtain a which were evaluated for AFFF performance using the phase split. The bottom layer was separated and the resulting following test methods: Foam Expansion and Drain Time, crude acid was purified by distillation under reduced pres 6,015,838 39 40 sure (120-125 C/2 torr). 770 g of acid was received as a white Solid after cooling to room temperature. The Structure of the acid was confirmed using 'F NMR analysis. Ex. Perfluoroalkyl Carboxylic Acid/Salt M15. C.F.CF(CF)COO. H.N' Examples M2-M7 M16. CFCF(CF)COO. H.N' M17. CF, CF(CF)COO. H.N' M18. CFCF(CF)COO HN' The following C.-branched perfluorocarboxylic acids M19. CFCF(CFS)COO HN' (Examples M2-M9) were prepared from various M2O. CFCF(CF)COO. H.N"CHOH C.-branched perfluoroalkylcarbonyl fluorides using the same M21. C.F.CF(CF)COO K' procedure as described in Example M1. 1O M22. CFCF(CF)COO K' M23. C.F.CF(CF)COO K' M24. CF, CF(CF)COO K' M25. CFCF(CF)COO. Na' Ex. Perfluorocarboxylic Acid M26. C.F.CF(CF)COO. Na' M27. C.F.CF(CF)COO Li' M2. C.F.CF(CF.)COOH M28. CF, CF(CF)COO. Na' M3. CFCF(CF)COOH 15 M4. CFCF(C.F.)COOH M29. CFCF(CF)COO HN' MS. C.F.CF(C.F.)COOH M6. CF,CF(CF)COOH M7. CF, CF(CF)COOH M8. CFCF(C.F.)COOH Example M30 M9. CFCF(CF)COOH CFCF(CF)COO %HNC, HNHCH-NH) was prepared from the free acid using the following procedure. 4.0 g (7.78 mmol) of CFCF(CF)COOH (from Example Example M10 M1), 0.40 g (3.89 mmol) of diethylenetriamine, and 82.6 g. of deionized water were combined, warmed to 60° C. and CFCF(CF)COO HN" was prepared by neutralizing 25 cooled, resulting in a white pasty dispersion Solution con CFCF(CF)COOH (from Example M1) with ammonia taining 5.06% (wt) solids of the desired polyammonium using the following procedure. 300 g of CFCF(CF) perfluorocarboxylate Salt. COOH was dissolved in 500 mL of FluorinertTM FC-77 The carboxylate salts from Examples M14-M30 were Electronic Liquid (commercially available from 3M dissolved in deionized water at various Solids concentrations Company, St. Paul, Minn.) at room temperature. A Stoichio and the Surface tension of each resulting aqueous Surfactant metric amount of anhydrous ammonia gas was passed Solution was measured. Then the critical micelle concentra through the Solution, gradually forming a white precipitate. tion (CMC) was determined for each surfactant. The CMC Following neutralization, the Solvent was removed under for each Surfactant and the corresponding Surface tension at reduced pressure and the resulting white Solid was dried the CMC are presented in Table 5. Also presented in Table under ambient conditions. 35 5 for comparison is the Surface tension value measured for FluoradTM FC-143 Fluorochemical Surfactant, a perfluoro Examples M11-M13 carboxylate ammonium salt of structure C, FCOO HN", containing predominantly linear perfluoro groupS and essen Using the same procedure as described in Example M10, tially free from a-branching (commercially available from the following ammonium carboxylate Salts were prepared. 40 3M Company, St. Paul Minn.). M11. CFCF(CF)COO. H.N. M12. CFCF(CF)COO. H.N. TABLE 5 M13. CFCF(CF)COO. H.N" From Salt Surf. Tens. CMC 45 Ex. Structure (dynes/cm) (ppm) Example M14 M15 CFCF(CF)COO. H.N* 22.1 >1OOOO M21 C.F.CF(CF)COO K' 22.5 >1OOOO CFCF(CF)COO. H.N" was prepared from the free M16 CFCF(CF)COO. H.N' 17.9 8OOO acid using the following procedure. An aqueous dispersion M22 CFCF(CF)COO K' 17.5 1OOOO 50 M25 CFCF(CF)COO. Na' 19.8 1OOOO of CFCF(CF)COOH (from Example M1) was neutral M14 C.F.CF(CF)COO. H.N' 16.5 2500 ized with a Stoichiometric amount of concentrated aqueous M20 C.F.CF(CF)COO. H.N.C.H.OH 15.O 500 ammonium hydroxide (28-30%) at room temperature and M23 C.F.CF(CF)COO K' 15.O 2500 with mixing, resulting in the formation of an aqueous M26 C.F.CF(CF)COO. Na' 19.4 3OOO M27 C.F.CF(CF.)COO Li' 24.1 35OO solution of CFCF(CF)COO. H.N. The aqueous solu M17 CF, CF(CF.)COO. H.N* 14.7 23OO tion was dried under ambient conditions to give the desired 55 M24 CF, CF(CF)COO K' 16.4 3OOO ammonium Salt as a white Solid. M18 CF, CF(CF)COO. H.N* 14.8 6OO M30 C, F, CF(CF)COO 16.2 3OOO /3 HNC, HNHCH-NH. Examples M15-M27 FC-143 CFCOO HN 21.5 8OOO The following a-branched perfluorocarboxylate salts 60 (Examples M15-M27) were synthesized from their The data in Table 5 show that the a-branched perfluoro C.-branched perfluorocarboxylic acid analogues (Examples carboxylate Salts of this invention demonstrated excellent M1-M9) using the same neutralization procedure as Surface tension depression in water. Lower values of both described in Example M14 and keeping the molar ratio of surface tension and CMC were achieved with longer R, reactants the Same, except that the base was varied, using 65 chain Salts. Also, lower Surface tension values were obtained either ammonium hydroxide, ethanolamine, potassium with ammonium, polyammonium and potassium Salts as hydroxide, sodium hydroxide or lithium hydroxide. compared to Sodium and lithium Salts. Surface tensions 6,015,838 41 imparted by the C-branched perfluorocarboxylate ammo nium Salts were lower than the Surface tension demonstrated TABLE 6 by FC-143, the primarily straight chain perfluorocarboxylate Temperature ammonium Salt. Due to their excellent Surface properties, it ° C) for: is expected that the C-branched perfluorocarboxylate Salts of this invention would make excellent biodegradable replace 50% 90% ments for the Straight chain branched perfluorocarboxylate Ex. Acid Salt Structure (Reference) Onset loss loss Salts now used commercially as fluoropolymer emulsifiers. N2. CF, CF(CF)COONH' (Ex. M15) 166 178 188 N3. CFCF(CF)COO NH. (Ex. M16) 16S 179 193 N4. C.F.CF(CF)COONH' (Ex. M14) 151 163 174 N. Degradation Measurements of C-Branched N5. CF, CF(CF)COONH' (Ex. M17) 142 162 184 N6. CF, CF(CF)COONH' (Ex. M18) 164 181 188 Perfluoroalkylcarbonyl Derivatives N7. CFCF(CFS)COONH'(Ex. M19) 153 171 188 N8. CF, CF(CF)COONa" (Ex. M28) 236 2SO 263 Example N1 N9. CF, CF(CF)COOK" (Ex. M21) 167 178 188* 15 FC-143 C.F.COO NH" (FC-143) 173 188 2O2 The thermal degradation of an aqueous a-branched per U.S. Pat. 100 110 120 fluoroalkylcarbonyl fluoride and the characterization of the No. products produced from the degradation were carried out 2,567,011 COO K using the following procedure. 8 g of CFCF(CF)COF (made as in Example A4) was dispersed in deionized water and was refluxed for 2 hours. 5.7 g of volatile degradation *Stopped at 85% weight loss as remaining salt, KF, is not volatile products were then collected by azeotropic distillation using The data in Table 6 show that, when thermally degraded a Dean-Stark apparatus. The Structures of the products and as neat Salts, the temperatures at which the C-branched open their amounts, as determined by 'F NMR and GC spectra 25 chain Structures decomposed were only slightly lower than analysis, were 85% monohydride, C7F.CFHCF, and 15% the temperatures at which the primarily linear open chain olefin, CFCF–CFCF (a mixture of cis- and trans Structure decomposed. This is in marked contrast to isomers). No volatile products were formed when CFCF Example N1 where, in aqueous media, the C-branched open (CF)COF was replaced with n-CFCOF, a non-C.- chain Structures decomposed at far lower temperatures than branched perfluoroalkylcarbonyl fluoride, made by did the primarily linear open chain Structure. The neat closed chain perfluorocyclohexyl Structure decomposed at a Sig electrochemical fluorination of n-CHCOF. nificantly lower temperature than did either the C-branched The thermal degradation of CFCF(CF)COF (from or primarily linear open chain structures. Example A4) dispersed in water was also carried out by heating the aqueous mixture for Several hours at approxi 35 Example N10 mately 80 C. The same volatile products were formed as in The C-branched open chain ammonium Salt compounds Example N1 and were collected by phase Separation fol from Examples N3-N6 were dissolved in deionized water at lowed by distillation. a concentration of 5% by weight (0.5 gammonium salt in 10 mL water) and were Stored at room temperature. Many The thermal degradation of CFCF(CF)COOH (from 40 structures showed about 20-30% degradation after 1 year. Example L1) in aqueous Solution was carried out in a similar An aqueous solution of CFCOO. NH" (FC-143), way to give the same monohydride and olefin. which is primarily linear, would show no signs of degrada tion over the same 1 year time period. Examples N2–N9 45 Example N11 Thermal degradation measurements were made on a The environmental stability of CFCF(CF)COO Series of neat perfluorocarboxylate Salts, including Several NH, was investigated under ambient conditions using a ax-branched open chain structures (Examples N2–N9), a bacterial sludge contact test. In this test, bacterial Sludge was primarily linear open chain structure (Example N10 50 obtained from the municipal waste treatment plant at Pig's FluoradTM FC-143 Fluorochemical Surfactant, commer Eye, Minn., the sludge was centrifuged to collect the water cially available from 3M Company, St. Paul, Minn.), and a insoluble high density Solids, and was reconstituted in water closed chain (i.e., cyclic) structure (Example N11-made by to a standard level of about 2000 ppm of total suspended the electrochemical fluorination of benzoic acid and solids. A5 mL aliquot of the 2000 ppm sludge in water was hydrolysis in the presence of KOH, as described in U.S. Pat. 55 placed in each of Several 20 mL. Vials, and enough of the No. 2,567,011 (Diesslin et al.)). carboxylate Salt was added to each vial to achieve a con centration of about 496 ppm (1 millimolar). Each vial was The perfluorocarboxylate Salts were tested using a Perkin tightly capped with a Septum cap and was allowed to Stand Elmer TGA 7 thermogravimetric analysis apparatus and a at room temperature. At intervals, the concentrations of Salt sample size of approximately 5 mg, a heating rate of 10 60 perfluoroolefin and perfluoromonohydride gases in each C./min, and a nitrogen gas flow rate of 40–45 mL/min. headspace were measured by removing a gas Sample from Using the TGA 7 software, the following temperatures were the Space over the liquid, using a Hewlitt Packard Gas recorded: (1) the onset temperature of decomposition, (2) the Chromatograph with a headspace Sampling accessory. The temperature at which 50% of the sample weight was lost, peak areas determined from each gas Sample were compared and (3) the temperature at which 90% of the sample weight 65 to a Standard Series made by placing increasing concentra was lost. Results of these thermal degradation experiments tions of a defined mixture of perfluoroolefin and perfluo are presented in Table 6. romonohydride in water in the same types of Vials, and 6,015,838 43 44 Subjecting the headspaces in the Vials to the same analytical minutes, the peak became noticeably larger and a Second procedure. Results, given below, State the complete conver peak formed, corresponding to the olefin. After 217 minutes, Sion relative to theoretical percent of the amount of both peaks became Significantly larger. Post-exposure obser perfluoroolefin/perfluoromonohydride mixture formed rela Vation noted no evidence of toxicity (death) or evidence of tive to that expected from complete conversion of the Salt to wasting Syndrome; this reduced toxicity was probably attrib Volatile fluorocarbons. A control experiment using water utable to C.-branching and not decarboxylation and elimina with no sludge was also run at the 28 day test point. tion of the material. % Perfluoroolefin/Perfluoromonohydride Formed after: This experiment demonstrated that the a-branched per Day 1-4% fluorocarboxylate salt was being metabolized by the rat to volatile metabolites which were eliminated from the rat via Day 4-13% transpiration. This study documents a significant biological Day 7-23% elimination pathway for the C-branched material that is not Day 14-44% present for the Straight-chain analogs. This pathway, involv Day 28-70% ing gaseous exchange at the bload-air barrier in the lungs, Day 28 (no sludge)-32% 15 should be applicable for most other air-breathing animals, The data Supra show that, after 28 days at ambient including humans. conditions, the presence of the Sludge more than doubled the P. Use of Surfactants in Emulsion Polymerization amount of perfluoroolefin/perfluoromonohydride mixture produced. Example P1 The following procedure was used to evaluate CFCF O. Toxicity Measurements of C.-Branched (CF)COO. NH" (from Ex. M1) as an emulsifier to copo Perfluorocarboxylate Salts lymerize hexafluoropropylene (HFP) and vinylidene fluo ride. Example O1 25 A 1 gallon, Vertically agitated Stainless Steel reactor with Acute LDso measurements for a one-time feeding Study of preSSure and temperature controls was evacuated and twice rats were determined over a 21 day period for both the purged with nitrogen. Using an isolated vacuum, a Solution a-branched perfluorocarboxylate salt, C.F.CF(CF)COO comprised of 2 g of ammonium perSulfate (initiator) and 6 NH", and its straight chain isomer, CF (CF)COONH". g of dipotassium phosphate dissolved in 2800g of deionized The LDso value for CFCF(CF)COO. NH" was deter water was introduced into the reactor. The remaining mined to be in the range of 500-1000 mg/kg, which is only Vacuum on the reactor was vented with nitrogen, and the Slightly toxic. No wasting Syndrome was noted as deaths Solution was degassed twice under agitation using alternate from toxic doses occurred within 2-3 days. Rats began Vacuum and nitrogen purges. A Sufficient amount of a regaining weight after 3 dayS. solution of CFCF(CF)COO. NH" in approximately 20 35 g of 60-70° C. deionized water was introduced to the reactor The LDso value for CFCOO. NH was determined to under isolated vacuum to give a calculated final concentra be in the range of 50-100 mg/kg (ca. 10 times as toxic as the tion of 350 ppm emulsifier in the aqueous solution. The C.-branched isomer), which is moderately toxic. Wasting reactor was vented with nitrogen, the Solution was agitated Syndrome was observed in affected animals. very briefly, and the reactor was evacuated of nitrogen and isolated. Then the reactor was vented with hexafluoropro Example O2 40 pylene monomer to a preSSure of approximately 10 psig Additional biological testing of C7F.CF(CF)COO (1280 torr total pressure), and the temperature of the batch NH in rats was conducted using the following test appa was raised to 72 C. with high agitation. Maintaining the ratus. An uptake desiccator jar chamber was designed with temperature at 72 C., a monomer mixture of 60% (wt) of top and bottom portions, the top portion equipped with an 45 vinylidene fluoride and 40% (wt) hexafluoropropylene was inlet port, an outlet port, OXygen monitor and pressure gage. fed from a tared gas cylinder into the head Space of the An oxygen gas tank Supplied oxygen into the inlet port, and reactor to maintain a reactor pressure of 130 psig (7480 total the oxygen level in the chamber was maintained at a normal pressure). After feeding in about 1 kg of monomer blend ambient level as measured by the oxygen monitor and (approximately 3.75 hours duration), the introduction of preSSure gage. The outlet port was connected in Series with 50 monomer was ceased, the reaction was allowed to cool to a carbon dioxide Scrubber and particulate filter, which in turn room temperature, and any residual unreacted monomer was was connected to a loop containing a stainleSS Steel bellows vented. pump operating at about 2L/min. Most of the gas in the loop The resulting latex polymer was drained from the reactor, was recycled into the inlet port, but about 100 mL/min was and percent solids of the latex was determined to be 25% by directed through a Secondary loop to a gas chromatograph 55 weight as measured by drying 10 g of lateX in a forced air equipped with a 0.5 mL gas Sampling loop. oven for 16 hours at 105 C. Arat dosed at 500 mg/kg was placed in the bottom portion The reactor body was separated from the reactor head, and of the chamber, the top portion was attached, and the a visual inspection of the reactor was made to determine the assembled chamber was placed in an ice-filled pan to allow amount of coagulated polymer in the reactor (the amount for the condensation of water. The oxygen flow was Started, 60 should be minimal in a good polymerization reaction). A and the exhaust gases were monitored for the presence of qualitative rating was assessed, ranging from “none' to CFCF=CF(CF) and CFCFHCF, aqueous degrada “little' to “some. tion products of CFCF(CF)COOH, using known stan The latex stability was determined by half filling a 16 oz. dards of this olefin and hydride in the gas chromatograph. (450 mL) jar with latex and shaking several hours in the Initially, no olefin or hydride were detected in the exhaust 65 horizontal position, quantitatively rating the latex after Shak gases. After 24 minutes, one slight chromatographic peak ing using a 3-point Scale ranging from 0=very Stable to was noted, corresponding to the monohydride. After 92 3=unstable. 6,015,838 45 46 Particle size in the latex was determined using 900 Scattering on a Coulter Sub-micron particle Size analyzer. Degree of foaming was rated using the following quali . tative Scale: 0=not foamy, 1 =slightly foamy, 2=moderately CF (CF). CFCNHCHN (R").O foamy, and 3=very foamy.

Example P2 wherein n is between 4 and about 18 inclusive; In Example P2, the same experiment was run as in m is between 0 and about 9 inclusive; Example P1, except that the concentration of CFCF(CF) k is between 2 and 6 inclusive; and COO. NH" emulsifier was raised to 3500 ppm, the reaction R" is a lower alkyl group having from 1 to 4 carbon atoms time decreased from 3.75 to 3.5 hours, and the reaction or may combine with the depicted nitrogen atom to temperature increased from 72 C. to 78 C. from a pyridinyl, piperidino or morpholino heterocyclic 15 ring. Comparative Examples P3-P7 2. The composition of claim 1 comprising one or more In Comparative Examples P3-P6, the same experiment Surfactants of the formula: was run as in Example P1, except that CFSON(CHs) CF, CF(CF)CONH(CH.)N(CH).O. CHCOO K" (Fluorad TM FC-128 Fluorochemical CFCF(CF)CONH(CH.)N(CH).O. Surfactant, available from 3M Company, St. Paul, Minn.), CFCF(CF)CONH(CH.)N(CH)2O C, FCOOHN" (Fluorad TM FC-143 Fluorochemical CFCF(CF)CONH(CH.)N(CH)O Surfactant), and Surflon TM S111S Fluorochemical Surfactant CFCF(CF)CON(CHOH)(CH)N(CH)O (believed to be nominally telomer-based n-CFCOO CFCF(CF)CONH(CH)N(CH)O HN", commercially available from Asahi Glass Corp., 25 CFCF(CF)CONH(CH.)N(CH)O Japan) were substituted for CFCF(CF)COOHN CFCF(CF)CONH(CH)N(CH)O emulsifier. CFCF(CF)CONCCH)N(CH)Ol In Comparative Example P7, the same experiment was run as in Example P1, except that no emulsifier was used. Reaction conditions and results for all fluoropolymer / experiments are presented in Table 7. CFCFCOCHNHC N-O CF TABLE 7 O | Conc. Temp Time 35 CF15CFCNHCHN O Ex. Emulsifier ppm ( C.) (hrs) I O P1. C.F.CF(CF.)COONH' 350 72 3.75 P2. C.F.CF(CF.)COONH' 3500 78 3.5 21 P3. Florad TM FC-128 1OO 72 4.5 P4. Florad TM FC-128 350 72 4 40 CFCFCOCH4 N PS. Florad TM FC-143 350 74 4 N+ P6. Surfon TM S111S 350 72 3.75 P7. Ole 76 3.25 CF O Size Foam- Coagu- Latex Ex. Emulsifier (nm) ing lation Stability 45 a r P1. C.F.CF(CF.)COONH' 210 2 SOC 2 P2. C.F.CF(CF.)COONH' 69 1. Ole O cercocai, N and P3. Florad TM FC-128 237 2 SOC 2 P4. Florad TM FC-128 88 2 Ole O O P5. Florad TM FC-143 209 3 SOC 2 O O P6. Surfon TM S111S 2O3 2-3 SOC 2 50 P7. Ole 233 O SOC 3 effortistic|| || ( yN'-O. CF The data in Table 7 show that at the lower concentration (350 ppm), CFCF(CF)COO. NH" performs compara 55 3. The composition of claim 1 further comprising one or bly to Fluorad TM FC-143 and Surflon TM S111S, both com more fluorine-free Surfactants Selected from the group of mercially available fluorochemical Surfactants frequently nonionic Surfactants having a hydrophilic-lipophilic balance used as fluoropolymer emulsifiers, in creating Small particle of greater than or equal to about 10, anionic Surfactants Size with no coagulation but with less foaming. At the higher having a carbon chain length of 6 to 16 inclusive; and concentration (3500 ppm) of CFCF(CF)COO. NH", 60 amphoteric Surfactants. particle size was reduced from 210 nm to 69 nm, foaming 4. The composition of claim 3 wherein said fluorine-free was lowered (from “2” to “1” on a 3-point scale) and Surfactant comprises from 1 to about 30 percent by weight coagulation was eliminated, with Overall performance being of Said composition. comparable to FluoradTM FC-128. 5. The composition of claim 1 wherein said surfactant We claim: 65 comprises 1 to 10 percent by weight of the composition. 1. An acqueous film-forming foamable composition com prising one or more Surfactants of the formula k k k k k