| PATENT NUMBER | This data is not available for free |
| PATENT GRANT DATE | 02.04.2002 |
| PATENT TITLE |
Perfluoroalkyl halides and derivatives |
| PATENT ABSTRACT |
Novel mixtures of perfluoroalkyl halides and derivatives thereof are described. These mixtures contain some compounds with a straight perfluoroalkyl group and some with a branched perfluoroalkyl group. Methods of preparation and use are also described. |
| PATENT INVENTORS | This data is not available for free |
| PATENT ASSIGNEE | This data is not available for free |
| PATENT FILE DATE | February 15, 2000 |
| PATENT REFERENCES CITED |
3M Company trade bulletin 90-0211-2213-4 (38.3) BPH, issued Mar. 1988. Banks, R.E., "Organofluorine Chemicals and their Industrial Applications," Ellis Horwood, Ltd., Chichester, England, 1979, pp. 213-234. Bernett, M.K., & Zisman, W.A., "Surface Properties of Perfluoro Acids as Affected by Terminal Branching and Chlorine Substitution," J. Phys. Chem., 71, 1967, pp. 2075-2082. The Journal of Organic Chemistry, vol. 23, "Applicability of the Arndt-Eistert Reaction to Fluorinated Acids and Their Derivatives", 1958, pp. 1166-1169. The Journal of Organic Chemistry, vol. 53, No. 24, "Electrochemical oxidation of Polyfluoroalkyl Iodides: Direct Anodic Transformation of C.sub.8 F.sub.17 CH.sub.2 CH.sub.2 I to Amides, Esters, and Ethers," 1988, pp. 5714-5720. Journal of Fluorine Chemistry, vol. 43, No. 2, "Synthesis of Fluorine-Containing Nitro Compounds," 1989, pp. 291-300. Park, J.D. et al., "Free-Radical Catalyzed Addition of Unsaturated Alcohols to Perhaloalkanes," 1961, pp. 2089-2095. |
| PATENT PARENT CASE TEXT | This data is not available for free |
| PATENT CLAIMS |
What is claimed is: 1. A composition comprising compounds of the formula R.sub.fsb --(Z), wherein R.sub.fsb represents a plurality of perfluoroalkyl groups, wherein about 60 to about 90% of the perfluoroalkyl groups in said compounds are straight chain and about 10 to about 40% of the perfluoroalkyl groups in said compounds are branched chain, and Z is an organic functional moiety selected from carbonyl-containing, sulfonyl-containing, alkylene-containing, nitrogen-containing, and oxygen-containing moieties. 2. The compounds of claim 1, wherein R.sub.fsb --(Z) is a tetrahydroalcohol. 3. The compounds of claim 2, wherein Z is C.sub.2 H.sub.4 OH. 4. The compounds of claim 1, wherein R.sub.fSb --(Z) is a carboxylic acid or a metal or ammonium salt thereof. 5. The compounds of claim 4, wherein Z has the formula --COOM.sub.1/v, wherein M is a metal atom having a valence v. 6. The compounds of claim 5, wherein M is K or Na. 7. The compounds of claim 1, wherein R.sub.fSb --(Z) is an ester. 8. The compounds of claim 7, wherein Z has the formula --COOR, and where R is selected from the group consisting of alkyl, or alkylaryl groups. 9. The compounds of claim 1, wherein R.sub.fsb --(Z) is an amide. 10. The compounds of claim 9, wherein Z has the formula --CONR.sup.1 R.sup.2, and wherein R.sup.1 and R.sup.2 are the same or different and are alkyl, aryl, or alkylaryl groups. 11. The compound of claim 1, wherein Z is a sulfonic acid, or a metal or ammonium salt thereof. 12. The compounds of claim 1, wherein Z is selected from the group consisting of --CH.sub.2 OCOCR.sup.4.dbd.CH.sub.2 and --CH.sub.2 OCOCF.sub.2 SF.sub.5, wherein R.sup.4 is H or CH.sub.3. 13. The compounds of claim 1, wherein z is a vinyl ether. 14. The compounds of claim 13, wherein Z is --CH.sub.2 --O--CH.sub.2 CH.dbd.CH.sub.2. -------------------------------------------------------------------------------- |
| PATENT DESCRIPTION |
FIELD OF THE INVENTION This invention relates to perfluoroalkyl halides and derivatives thereof, and to the preparation and use of such halides and derivatives. BACKGROUND OF THE INVENTION Fluorocarbon derivatives (sometimes called organofluorine compounds or fluorochemicals) are a class of substances containing portions which are fluorocarbon in nature, e.g. hydrophobic, oleophobic, and chemically inert, and portions which are organic or hydrocarbon in nature, e.g. chemically reactive in organic reactions. The class includes some substances which are familiar to the general public, such as those which give oil and water repellency and stain and soil resistance to textiles, e.g. Scotchgard.TM. carpet protector. Other substances of the class have various industrial uses, such as reducing the surface tension of liquids, reducing evaporation and flammability of volatile organic liquids, and improving the leveling of organic polymer coatings. Examples of industrial substances are the Fluorad.TM. fluorochemical surfactants described in 3M Company trade bulletin 98-0211-2213-4 (38.3) BPH, issued March, 1988. Conventional fluorochemicals can be prepared from precursors such as fluoroalkyl iodides, fluoroalkyl carboxylic acid fluorides, and fluoroalkyl sulfonyl fluorides. See for example, "Organofluorine Chemicals and Their Industrial Applications", R. E. Banks, Ed., Ellis Horwood, Ltd., Chichester, England, 1979, pp. 214-234. Some perfluoroalkyl iodides can be prepared by telomerization of C.sub.2 F.sub.5 I or (CF.sub.3).sub.2 CFI with C.sub.2 F.sub.4 yielding C.sub.2 F.sub.5 (C.sub.2 F.sub.4).sub.n I or (CF.sub.3).sub.2 CF(CF.sub.2 CF.sub.2).sub.n I, respectively, where n is typically from 1 to 4. See R. E. Banks, supra. All of the perfluoroalkyl iodides obtained from (CF.sub.3).sub.2 CFI contain perfluoroalkyl groups with a terminal branch, and such branched-chain perfluoroalkyl groups will hereinafter be represented by "R.sub.fb ". All of the perfluoroalkyl iodides obtained from C.sub.2 F.sub.5 I contain straight-chain perfluoroalkyl groups without branches, and such straight-chain (or "linear") perfluoroalkyl groups will hereinafter be represented by "R.sub.fs ". For brevity, "R.sub.f " will hereinafter be used to represent a perfluoroalkyl group with either a straight or a branched-chain. Perfluoroalkyl iodides can be converted into other functional (or reactive) materials, for example by the following illustrative schemes. R.sub.f --I+CH.sub.2.dbd.CH.sub.2.fwdarw.R.sub.f --CH.sub.2 CH.sub.2 --I R.sub.f --CH.sub.2 CH.sub.2 --I+H.sub.2 O.fwdarw.R.sub.f CH.sub.2 CH.sub.2 --OH R.sub.f --CH.sub.2 CH.sub.2 --I+H.sub.2 NC(S)NH.sub.2.fwdarw.R.sub.f --CH.sub.2 CH.sub.2 --SH R.sub.f --CH.sub.2 CH.sub.2 --I.fwdarw.R.sub.f --CH.dbd.CH.sub.2 The alcohol, thiol, and olefin derivatives of the above schemes can be further converted to a great variety of derivatives, e.g., acrylates and polymers thereof, sulfates and salts thereof, carboxylic acids and esters thereof, etc. These further derivatives retain the original structure of the R.sub.f group, that is, the R.sub.f group remains either straight or branched. Functional materials derived from telomer iodides will (as stated above) contain either 100% straight-chain (R.sub.fs) or 100% branched-chain (R.sub.fb) perfluoroalkyl groups. Contradictory data have been reported in the literature regarding the relative advantage of straight-chain versus branched-chain perfluoroalkyl groups. In U.S. Pat. No. 4,127,711 (Lore et al.) perfluoroalkyl straight-chains are said to be preferred for textile applications, whereas in U.S. Pat. No. 3,525,758 (Katsushima et al.) it is disclosed that surfactants containing 100% branched-chain perfluoroalkyl groups are more effective than surfactants containing straight-chain perfluoroalkyl groups in lowering the surface tension of aqueous solutions. However, it has generally been accepted that among fluorinated surfactants of the same carbon number, straight-chain products generally give lower surface tension in aqueous solutions. Banks, supra at 222-223, describes that, except at very low concentrations (less than 0.01% or 100 ppm), lower surface tension is attained with straight-chain fluorochemicals. Additionally, an article written by Bennett and Zismann (J. Phys. Chem., 71, 1967, p. 2075-2082) discloses that a condensed monolayer of a fully fluorinated straight-chain alkanoic acid has a lower critical surface energy than its terminally branched analogue with the same chain length. In addition to the telomerization procedure described above, another method of producing many fluorochemicals or their precursors is the fluorination process commercialized initially in the 1950s by 3M Company, which comprises passing an electric current through a mixture of the organic starting compound and liquid anhydrous hydrogen fluoride. This fluorination process is commonly referred to as "electrochemical fluorination" or "ECF". Some early patents describing such technology include U.S. Pat. No. 2,519,983 (Simons), U.S. Pat. No. 2,567,011 (Diesslin et al.), U.S. Pat. No. 2,666,797 (Husted et al.), U.S. Pat. No. 2,691,043 (Husted et al.), and U.S. Pat. No. 2,732,398 (Brice et al.); they describe the preparation of such fluorochemical compounds as perfluoroalkyl carbonyl fluorides, e.g. C.sub.4 F.sub.9 --COF, and perfluoroalkyl sulfonyl fluorides, e.g. C.sub.4 F.sub.9 --SO.sub.2 F, and derivatives thereof When perfluoroalkyl carbonyl fluorides and perfluoroalkyl sulfonyl fluorides are prepared by electrochemical fluorination (ECF) of appropriate hydrocarbon precursors, the resulting products are mixtures of compounds, where some of said compounds contain a straight-chain perfluoroalkyl group, e.g., R.sub.fs --SO.sub.2 F, and others of said compounds contain a branched-chain perfluoroalkyl group, e.g., R.sub.fb --SO.sub.2 F. Such mixtures of compounds result even when the starting materials contain only compounds with straight-chain alkyl groups. Such mixtures of compounds, e.g. a mixture of R.sub.fs --SO.sub.2 F and R.sub.fb --SO.sub.2 F, can be represented, for brevity, by the formula, R.sub.fsb --SO.sub.2 F, which formula represents a mixture of compounds. The "sb" subscripts indicate that the formula represents a mixture of compounds, that is, a mixture of R.sub.fs --SO.sub.2 F and R.sub.fb --SO.sub.2 F. ECF-derived acid fluorides can be converted into other functional materials, for example by the following illustrative schemes. R.sub.fsb --COF .fwdarw. R.sub.fsb --CH.sub.2 --OH dihydro derivatives R.sub.fsb --COF .fwdarw. R.sub.fsb --CON(R)CH.sub.2 CH.sub.2 --OH carboxamido derivatives R.sub.fsb --SO.sub.2 F .fwdarw. R.sub.fsb --SO.sub.2 N(R)CH.sub.2 CH.sub.2 --OH sulfonamido derivatives Each R.sub.fsb containing formula, e.g., R.sub.fsb --COF, represents ECF derived mixtures which contain some compounds with a straight-chain perfluoroalkyl group and other compounds with a branched-chain perfluoroalkyl group. U.S. Pat. No. 2,950,317 (Brown et al) describes a process for the preparation of fluorocarbon sulfonyl chlorides from the corresponding fluorocarbon sulfonyl fluorides. An article by Park et al. (23, J. Org. Chem, 1166-1169 (1958)) describes the preparation of certain fluorochemical compounds with three or less fully-fluorinated carbon atoms. Compounds described include n-C3F.sub.7 --CH.sub.2 CH.sub.2 --I and n-C3F.sub.7 --CH.sub.2.sup.- CO.sub.2 H. SUMMARY OF THE INVENTION Briefly, the present invention, in one aspect, provides novel fluorochemical compositions which comprise a mixture of perfluoroalkyl halide compounds. Some of the perfluoroalkyl halide compounds of the mixture contain a straight-chain group (the term "straight-chain" is used herein in its accepted sense to mean normal or unbranched perfluoroalkyl group, e.g., CF.sub.3 CF.sub.2 CF.sub.2 CF.sub.2 --), and some contain a branched-chain perfluoroalkyl group (e.g., (CF.sub.3).sub.2 CFCF.sub.2 --). The perfluoroalkyl halide compounds comprise a perfluoroalkyl group, a halogen atom selected from the group consisting of Cl, Br, and I, and a fluorine-free alkylene linking group bonded to the perfluoroalkyl group and to the halogen atom. The alkylene linking group contains at least two catenary carbon atoms, one of which is bonded to the perfluoroalkyl group, and the other of which is bonded to the halogen atom (e.g., as in R.sub.fsb --CH.sub.2 CH.sub.2 --I, but not as in R.sub.fsb --CH(CH.sub.3)--I). The carbon atom of the alkylene linking group which is directly bonded to the perfluoroalkyl group will be referred to as the alpha carbon atom, and the catenary carbon atom of the alkylene linking group which is bonded to said alpha carbon atom will be referred to as the "beta carbon atom". Such .alpha. and .beta. carbon atoms are illustrated, for example, in the formula ##STR1## In another aspect, this invention provides novel fluorochemical compositions which comprise a mixture of perfluoroalkyl derivative compounds of said perfluoroalkyl halide compounds. Some of said perfluoroalkyl derivative compounds of said mixture contain a straight-chain perfluoroalkyl group, e.g., CF.sub.3 CF.sub.2 CF.sub.2 CF.sub.2 --, and some contain a branched-chain perfluoroalkyl group, e.g., (CF.sub.3).sub.2 CFCF.sub.2 --. Said derivatives are obtained from said halides by one or more steps, and retain from the precursor halides the perfluoroalkyl group and the alpha and beta carbon atoms of the linking group. One or both of said alpha and beta carbon atoms may be converted, for example, to a carbonyl (C.dbd.O) or alkenylene carbon atom (C.dbd.C), but they are always retained in some form in the derivative. DETAILED DESCRIPTION OF THE INVENTION Preferably, the compositions of this invention comprise a mixture of compounds wherein 50 to 95% of said compounds contain a straight-chain perfluoroalkyl group (R.sub.fs), and wherein 5 to 50% of said compounds contain a branched-chain perfluoroalkyl group (R.sub.fb). Most preferably, the compositions of this invention comprise a mixture of compounds wherein 60 to 90% of said compounds contain a straight-chain perfluoroalkyl group (R.sub.fs) and wherein 10 to 40% of said compounds contain a branched-chain perfluoroalkyl group (R.sub.fb). The compositions of this invention also may contain mixtures of compounds such that the number of carbon atoms in the perfluoroalkyl groups are predominately, e.g., greater then 70%, of one length, for example where greater then 70% of all perfluoroalkyl groups in the mixture of compounds have 8 carbon atoms. Because of the wide variety of the fluorochemical compositions of this invention, they can be used in numerous applications, including those where conventional fluorochemicals are used. Such applications are described, for example, in Banks, supra, which descriptions are incorporated herein. The fluorochemical compositions of this invention are useful in improving or imparting properties to solutions and substrates such as wetting, penetration, spreading, leveling, foaming, foam stabilization, flow properties, emulsification, dispersability, and oil, water, and soil repellency. A class of the fluorochemical compositions of this invention comprises a mixture of perfluoroalkyl halide compounds which mixture can be represented by Formula I. R.sub.fsb --CH.sub.2 CH(R.sup.1)R.sup.2 --X I. In Formula I, the "fsb" subscript is meant to indicate that Formula I represents a mixture of compounds, that is, a mixture of R.sub.fs --CH.sub.2 CH(R.sup.1)R.sup.2 --X and R.sub.fb --CH.sub.2 CH(R.sup.1)R.sup.2 --X. Some of said compounds contain a straight-chain perfluoroalkyl group (R.sub.fs) and all others of said compounds contain a branched-chain perfluoroalkyl group (R.sub.fb). In Formula I, R.sub.fsb is a perfluoroalkyl group. Said perfluoroalkyl group is saturated, mono-valent, and has at least 4 fully-fluorinated carbon atoms. While the perfluoroalkyl group can contain a large number of carbon atoms, compounds where the perfluoroalkyl group is not more than 20 carbon atoms will be adequate and preferred since larger radicals usually represent a less efficient utilization of the fluorine (lower fluorine efficiency) than is obtained with shorter chains. Perfluoroalkyl groups containing from about 4 to about 10 carbon atoms are most preferred. In Formula I, R.sup.1 is a lower alkyl group, e.g., with 1 to 4 carbon atoms, or an aromatic group, e.g., phenyl, or combinations thereof, e.g., tolyl. R.sup.1 may also contain hetero atoms, e.g., S, O, N, Si, for example R.sup.1 may be --CH.sub.2 --OH. In Formula I, R.sup.2 is a covalent bond or an alkylene group such as (CH.sub.2)m, where m is from 1 to 20, or --CH(R) where R is as defined for R.sup.1, and R.sup.2 may also contain said hetero atoms. In Formula I, the carbon atom bonded to the perfluoroalkyl group may be referred to as the alpha carbon atom and is represented in Formula I as the "C" in CH.sub.2. The other depicted carbon atom, which is bonded to the alpha carbon atom, may be referred to as the beta carbon atom and is represented in Formula I as the "C" in CH(R.sup.1). In Formula I, X is I, Cl, or Br. A subclass of the fluorochemical compositions of this invention comprises a mixture of perfluoroalkyl halide compounds which mixture can be represented by Formula II. R.sub.fsb --(CH.sub.2 CH2).sub.n --X II In Formula II, R.sub.fsb and X are as described above for Formula I and n is an integer from 1 to 5. The perfluoroalkyl halide mixtures of this invention are reactive chemicals and can be converted into their reactive or functional derivatives by one or more steps. A class of such derivatives can be represented by the formula R.sub.fsb --Z where R.sub.fsb is as defined and described above and Z is an organic moiety or an oxygen-containing inorganic moiety that is a one-step or multi-step derivative of the halide compounds. Various functional embodiments of Z make the derivatives useful reagents for the introduction of the R.sub.fs b moiety into molecules. Z can be an organic functional moiety, i.e., one which contains one or more carbon atoms, such as carbonyl-containing, sulfonyl-containing, alkylene-containing, nitrogen-containing, and oxygen-containing moieties or Z can be an oxygen-containing inorganic moiety, such as sulfonyl-containing and sulfonyloxy-containing moieties. Representative functional Z moieties are, for example, polymerizable groups which will undergo electrophilic, nucleophilic, or free radical reaction, derivatives with such groups being useful to form polymers comprising polymeric chains having a plurality of pendant perfluroalkyl groups. Derivative compounds of this invention include carboxylic and sulfonic acids and their metal and ammonium salts, esters, including alkyl and alkenyl esters, amides, tetrahydroalcohols (--C.sub.2 H.sub.4 OH), esters of tetrahydro-alcohols, acrylates (and polyacrylates), mercaptans, alkenyl ethers, etc. Stated otherwise, Z in the above formulas can contain --COOH, --COOM.sub.1/v, --COONH.sub.4, --CH.sub.2 COOR, --CONH.sub.2, --COONR.sup.1 R.sup.2, --NR.sup.1 R.sup.2, --CONR.sup.1 R.sup.3 A, --CH.sub.2 OH, ##STR2## --SO.sub.3 M.sub.1/v, --SO.sub.3 NH.sub.4, --SO.sub.2 NR.sup.1 R.sup.2, --SO.sub.2 NR.sup.1 R.sup.3 A, --SO.sub.2 NH.sub.2, --SO.sub.3 R, --CH.sub.2 SH, --CH.sub.2 NR.sup.1 R.sup.2, --CH.sub.2 OCOCR.sup.4.dbd.CH.sub.2, CH.sub.2 OCOCF.sub.2 SF.sub.5, and the like, where M is a metal atom having a valence "v", such as a monovalent metal atom like K or Na; R is alkyl (e.g. with 1 to 14 carbon atoms), aryl (e.g. with 6 to 10 or 12 ring carbon atoms), or a combination thereof (e.g. alkaryl or aralkyl); R.sup.1 and R.sup.2 are each independently H or R; R.sup.3 is alkylene (e.g. with 1 to 13 carbon atoms; R.sup.4 is H or CH.sub.3 ; A is an aliphatic or aromatic moiety, which can contain a carboxy or sulfo group or an alkali metal or ammonium salt or ester thereof, a carboxamido, a sulfonamido, or contain 1 to 3 hydroxy groups, 1 or more ether-oxygen or oxirane-oxygen atoms, a cyano group, a phosphono group, or one or more primary, secondary, or tertiary amine groups, or quaternized amine group, or other functional group. The above illustrated derivatives can be converted to other derivative fluorochemical compositions of this invention. For example, hydroxy functional derivatives can be converted to corresponding sulfate derivatives useful as surfactants as described, for example, in U.S. Pat. No. 2,803,656 (Ahlbrecht et al.) or phosphate derivatives useful as textile and leather treating agents as described, for example, in U.S. Pat. No. 3,094,547 (Heine). Hydroxy functional derivatives can also be reacted with isocyanates to make carbamato-containing derivatives such as urethanes, carbodiimides, biurets, allophanates, and quanidines useful in treating fibrous substrates such as textiles as described, for example, in U.S. Pat. Nos. 3,398,182 (Guenthner et al.), U.S. Pat. No. 4,024,178 (Landucci), U.S. Pat. No 4,668,406 (Chang), U.S. Pat. No. 4,606,737 (Stern), and U.S. Pat. No. 4,540,497 (Chang et al.), respectively. Amine functional derivatives can be converted to corresponding amine salts useful as surfactants, as described, for example, in U.S. Pat. Nos. 2,764,602 (Ahlbrecht), U.S. Pat. No. 2,759,019 (Brown et al.) or amphoteric surfactants as described, for example, in U.S. Pat. No. 4,484,990 (Bultman et al.). Amine functional derivative can be successively reacted to form an amphoteric surfactant as described, for example, in U.S. Pat. No. 4,359,096 (Berger) (see Table I thereof). The polymerizable functional derivatives of this invention can be used to make polymers such as polyacrylates, polyesters, polyurethanes, polyamides, and polyvinyl ethers. Such polymers can be made by conventional step-growth, chain-growth, or graft polymerization techniques or processes. The step-growth polymers can be made, for example, from those derivatives having hydroxyl, carboxyl, isocyanato, or amino polymerizable groups. The acrylate, methacrylate, or vinyl derivatives of this invention can be used to make chain-growth polymers, such as polyacrylates. Fluorochemical ethylenically unsaturated monomers of this invention can be homopolymerized to make homopolymers, or copolymerized with copolymerizable monomers to make random, alternating, block, and graft polymers. Copolymerizable monomers which can be used include fluorine-containing and fluorine-free (or hydrocarbon) monomers, such as methyl methacrylate, ethyl acrylate, butyl acrylate, octadecylmethacrylate, acrylate and methacrylate esters of poly(oxyalkylene) polyol oligomers and polymers, e.g., poly(oxyethylene) glycol dimethacrylate, glycidyl methacrylate, ethylene, vinyl acetate, vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylonitrile, vinyl chloroacetate, isoprene, chloroprene, styrene, butadiene, vinylpyridine, vinyl alkyl ethers, vinyl alkyl ketones, acrylic and methacrylic acid, 2-hydroxyethyl acrylate, N-methylolacrylamide, 2-(N,N,N-trimethylammonium)ethyl methacrylate and the like. The polymers can be applied in the form of an aqueous or non-aqueous solution or emulsion as a coating or finish to modify the free surface energy of a substrate, e.g. a non-porous substrate such as glass, metal, plastic, and ceramic or a fibrous or porous substrate such as textile, e.g., nylon carpet fiber or polyester outerwear fabrics, leather, paper, paperboard, and wood to impart oil and water repellency thereto, as described, for example, in the Banks reference supra. The relative amounts of various comonomers which can be used with the monomers of this invention generally will be selected empirically and will depend on the substrate to be treated, the properties desired from the fluorochemical treatment, e.g., the degree of oil and/or water repellency desired, and the mode of application to the substrate. Generally, in the case of copolymers, of the interpolymerized or repeating units in the polymer chain, 5 to 95 mole percent of such units will contain pendant perfluoroalkyl groups. The fluoroaliphatic polymers of this invention can be blended with other or known polymers, such as perfluoromethyl-terminated fluoroaliphatic vinyl polymers, and the blend used to modify surface properties, e.g. of textiles such as fabrics to provide them with improved properties such as oil and water repellancy. Fluorochemicals of this invention which are useful as surfactants generally are those having a polar group such as --CO.sub.2 Na, --SO.sub.2 NHC3H.sub.6 N.sup.+ (CH.sub.3).sub.3 Cl.sup.-, --SO.sub.2 N(C.sub.2 H.sub.5)C.sub.2 H.sub.4 O(C.sub.2 H.sub.4 O).sub.7 H, and --CONHC3H.sub.6 N.sup.+ (CH.sub.3).sub.2 CH.sub.2 CO.sub.2.sup.-, these moieties being representative of the polar groups in anionic, cationic, non-ionic, and amphoteric surfactants, respectively. The surfactants are useful in improving or imparting properties to aqueous and non-aqueous (organic) liquid systems such as wetting, penetration, spreading, leveling, foaming, foam stabilization, flow properties, emulsification, dispersability, and oil, water, and soil repellency. Said liquid system generally will comprise a liquid phase (in which the surfactant will be dissolved or dispersed) and one or more other phases selected from the group consisting of another liquid phase, a gas phase, and a phase of dispersed solids (e.g. polymer solids), and the system can be in the form of an emulsion, suspension, or foam (such as an air foam). Examples of such liquid systems, or application areas for said surfactants, include rinsing, cleaning, etching, and plating baths, floor polish emulsions, photographic processes, water base coatings, powder coatings, solvent based coatings, alkaline cleaners, fluoropolymer emulsions, soldering systems, and specialty inks, such as described, for example, in 3M Bulletin 98-0211-2213-4 (38.3) BPH. The fluorochemicals useful as surfactants also can be incorporated into or mixed with other substances. For example, if sufficiently thermally stable, they can be incorporated into polymeric materials, such as polyamides, e.g. nylon, or polyolefins, e.g., polypropylene, which are cast, blown, extruded, or otherwise formed into shaped articles, such as films and fibers, the so-incorporated fluorochemicals modifying the properties of the shaped articles, such as the oil and water repellency of their surfaces. The fluorochemical surfactants of this invention can also be mixed with other surfactants, such as hydrocarbon surfactants and/or the conventional fluorochemical surfactants, e.g. those disclosed in said U.S. Pat. Nos. 2,567,011 and 2,732,398, and such mixed surfactants used to form, for example, aqueous, film-forming foams as described in U.S. Pat. No. 3,562,156 (Francen). In the following examples, it is shown that the fluorochemical compositions of this invention impart improved properties. As shown in the working examples below, some of the compositions of this invention impart improved oil repellency to textile substrates compared to fluorochemical compositions derived from ECF and containing a sulfonamido linking group. As also shown, some of the compositions of this invention provide lower surface tension to, and have better solubility in, organic or aqueous systems compared to fluorochemical compositions obtained from telomerization (compositions where all compounds have straight-chain, or where all compounds have branched-chain perfluoroalkyl groups). A convenient route to the perfluoroalkyl halide mixtures of this invention utilizes perfluoroalkyl sulfonyl fluorides (obtained from ECF) according to the following illustrative schemes. R.sub.fsb.sup.- SO.sub.2 F+Na.sub.2 SO.sub.3 +I.sub.2.fwdarw.R.sub.fsb --I R.sub.fsb --I+C.sub.2 H.sub.4.fwdarw.R.sub.fsb --C.sub.2 H.sub.4 --I A R.sub.fsb --SO.sub.2 F.fwdarw.R.sub.fsb --SO.sub.2 Cl R.sub.fsb --SO.sub.2 Cl+C.sub.2 H.sub.4.fwdarw.R.sub.fsb --C.sub.2 H.sub.4 --Cl B R.sub.fsb --SO.sub.2 F.fwdarw.R.sub.fsb --SO.sub.2 Br R.sub.fsb --SO.sub.2 Br+C.sub.2 H.sub.4.fwdarw.R.sub.fsb --C.sub.2 H.sub.4 --Br C The perfluoroalkyl halide mixtures from Schemes A, B and C are readily converted to various derivatives containing for example hydroxyl, thiol, amino, acids, acid salts, esters, etc., and adducts and derivatives thereof, e.g., urethanes, acrylates and polymers thereof, etc., using conventional synthetic procedures, many of which are described in the examples. Each perfluoroalkyl halide mixture can be converted to either of the other two perfluoroalkyl halide mixtures. In the following examples, all of the perfluoroalkyl sulfonyl fluorides utilized in Examples of this invention were prepared from the hydrocarbon precursors by electrochemical fluorination (ECF). EXAMPLES The following procedures were used where referred to in the examples. Padding Application Procedure Polymer emulsions were applied to a 100% cotton fabric (bleached mercerized cotton poplin, style #407, obtained from Test Fabrics, Inc., Middlesex, N.J.) by immersing the fabric in the treatment bath using a padding technique well known to those skilled in the art. The saturated fabric was run through a roller to remove excess emulsion to give a wet pick-up of approximately 60%. After treatment, the wet cotton fabric was dried and cured by placing in a forced air oven set at 150.degree. C. for 10 minutes to give a percent solids on fabric of approximately 0.3% SOF. Oil Repellency Test The oil repellency of the treated fabric was measured using AATCC Test Method 118-1975, "Oil Repellency: Hydrocarbon Resistance Test" as described in AATCC Technical Manual, 1977, 53, 223. This test measures the resistance of a fibrous substrate to wetting by a series of hydrocarbon liquids, with a range of surface tensions. Treated fabrics are given an "Oil Repellency" (OR) value ranging from "0" (least repellent) to "8" (most repellent). Spray Rating Test The resistance of the treated fabric to wetting with water, was measured using AATCC Test Method 22-1977, "Water Repellency: Spray Test" as described in American Association of Textile Chemists and Colorists Technical Manual, 1977, 53, 245. Treated fabrics are given a "Spray Rating" (SR) value on a scale of "0" to "100", with "0" indicating complete wetting of the upper and lower surfaces of the substrate and with "100" indicating no wetting. Laundering Procedure The procedure set forth below was used to prepare treated samples designated in the examples below as "5.times.Laundered". A 230 g sample of generally square, 400 cm.sup.2 to about 900 cm.sup.2 sheets of treated substrate is placed in a conventional washing machine along with a ballast sample (1.9 kg of 8 oz fabric in the form of generally square, hemmed, 8100 cm.sup.2 sheets). Conventional detergent (TlDE.TM., 46 g, available from Procter & Gamble Co., Cincinnati, Ohio) is added and the washer is filled to high water level with hot water (40.degree. C..+-.3.degree. C.). The substrate and ballast load is washed five times using a 12-minute normal wash cycle and the substrate and ballast are dried together in a conventional clothes dryer set on the "heat" setting for about 45 minutes. The dry substrate is pressed using a hand iron set at the temperature recommended for the particular substrate fabric. Dry Cleaning Procedure Substrate samples designated in the examples below as "Dry Cleaned" were treated as set forth in AATCC Test Method 7-1975, note 8.1. One dry cleaning cycle was used in all cases. |
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