US2915554A - Non-ionic surfactant derivatives of perfluoro alkane-sulfonamides - Google Patents

Non-ionic surfactant derivatives of perfluoro alkane-sulfonamides Download PDF

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US2915554A
US2915554A US673565A US67356557A US2915554A US 2915554 A US2915554 A US 2915554A US 673565 A US673565 A US 673565A US 67356557 A US67356557 A US 67356557A US 2915554 A US2915554 A US 2915554A
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sulfonamides
ionic surfactant
perfluoro alkane
surfactant derivatives
ethylene oxide
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US673565A
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Arthur H Ahlbrecht
Duane E Morin
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3M Co
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Minnesota Mining and Manufacturing Co
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    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/004—Surface-active compounds containing F
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C311/00—Amides of sulfonic acids, i.e. compounds having singly-bound oxygen atoms of sulfo groups replaced by nitrogen atoms, not being part of nitro or nitroso groups
    • C07C311/01—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms
    • C07C311/02—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton
    • C07C311/09—Sulfonamides having sulfur atoms of sulfonamide groups bound to acyclic carbon atoms of an acyclic saturated carbon skeleton the carbon skeleton being further substituted by at least two halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K23/00—Use of substances as emulsifying, wetting, dispersing, or foam-producing agents
    • C09K23/26—Sulfonamides
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S516/00—Colloid systems and wetting agents; subcombinations thereof; processes of
    • Y10S516/01—Wetting, emulsifying, dispersing, or stabilizing agents
    • Y10S516/03—Organic sulfoxy compound containing
    • Y10S516/05—Organic amine, amide, or n-base containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
    • Y10S8/907—Nonionic emulsifiers for dyeing

Definitions

  • This invention relates to non-ionic surfactants and more particularly to certain N-(polyoxa-alkyl)-perfiuoroalkanesulfonamides.
  • n is controllable by variations in the amount -of ethylene orpropylene oxide used as well as the temcules to accumulate at interfaces, either of water'to air .orwater to container walls. Because of their dual nature, i su'rfactants ofthis'type. are useful emulsifiers and dispersants.
  • N-(polyoxa-alkyD-perfluoroalkane sulfonamides which can be representedv by the general formula
  • RrSOr-N-R carbon atoms is a member of the group consisting of hydrogen, lower alkyl'radicals and R; and R is a polyoxa-alkyl group having the formula:
  • RI! f onnmqoomdn ..+o-R" inIwhich'rii'is'an integer from two to three, n is a number from two to about twenty, and each R" is hydrogen or a methyl radical, are surface active agents of excepit onalactivit-y.
  • R is hydrogen or a methyl radical
  • the compounds of the invention are surprisingly elfective in lowering the surface tension of water, and are extremely useful where that effect is desired; as well as for emulsifying agents .or as surfactants in compositions such as floor wax, to
  • N-polyoxa-alkyl-perfiuoroalkanesulfonamides of the invention can be prepared by the condensation in.- alkaline medium of ethylene or propylene oxideand an appropriately substituted perfluoroalkylsulifonylamidoalkanol (produced by the method of Ahl- 'brecht and.-Brown, described in application Ser. No. 560,-
  • the sodium salt of a perfluoroalkanesulfonamide can be condensed with a polyethylene glycol halidehaving the desired number of molesof ethylene oxide.
  • polyalkylene glycol halides which are reacted with'these compounds are conveniently identified as to chain length by their molecular'weight.
  • a polyethylene glycol chloride of average molecular weight 410 contains about 8 to 9 condensed ethylene oxide units; one of average molecular weight 610 contains about 13 cont 3 densed ethylene oxide units; one of average molecular weight 975 contains about 22 condensed ethylene oxide units, and so on.
  • Example 1 A flask fitted with a mechanical stirrer, a gas inlet tube and a reflux condenser cooled with a mixture of acetone and solid carbon dioxide was charged with 20 grams (0.035 mole) of N-ethyl-N-Z-hydroxyethyl perfiuorooctane sulfonamide 2 a CaFnS OrNCHzCHzOH and 0.8 gram of 50% sodium hydroxide (0.01 mole). Ethylene oxide gas was passed into the flask, the temperature of the reactants being held at about 90 to 110 C., for 4 hours. A total of 15.5 grams (0.35 mole) of ethylene oxide was absorbed, indicating the formation of a polyether of the approximate formula:
  • the product was a substantially colorless viscous oil at room temperature which was more fluid at elevated temperatures.
  • the surface tension of pure water is about 74 dynes/cm. at 18 C.
  • Example3 A mixture or 7.3 g. 0.02 mole) of the sodium salt of N-methyl-perfluorobutanesulfonamide and 12.2 g. (0.02 m.) of polyethylene glycol chloride 610 (corre- 'sponding approximately to C1(CH CH O) H) was heated on the steam bath for about 1.5 hours; The sulfonamide salt soon dissolved and a finely divided precipitate formed. The reaction product was a viscous, ambercolored liquid. Surface tension measurements of aqueous solutions ofthis product, determined with a Du Nouy tensiometer, gave the following values:
  • Example 5 This example illustrates'the preparation of addition products of perfluoroalkane sulfonamides and alkylene oxides, in which two positions on the nitrogen atom are occupied by polyxoaalkylene groups.
  • each R" is a member of the group consisting of hydrogen and the methyl radical
  • m is an integer of the group consisting of 2 and 3
  • n is a number from 2 to 20.

Description

NON-Ionic SURFACTANT DERIVATIVES on Y IPERFLUORO ALKANE-SULFONAMIDES 5 "rain it. Ahlbrecht, White Bear Lake, and Duane E. I
I Morin, St. Paul, Minn., assignors to Minnesota Mining fand ManufacturingCompany, St..Paul,'Minn., a corporation 'of'Delawai-e I I 1N0 Drawing. Application July 23, 1951' 5 Serial No. 673,565
5 Claims. (Cl. 260-556) This invention relates to non-ionic surfactants and more particularly to certain N-(polyoxa-alkyl)-perfiuoroalkanesulfonamides.
Substances which in small amounts, radically depress the surface tension of their solutions below that of the solvent are. termed surface active and as a broad class Lare'knoivnfas surfactants. These are frequently'characterized by the presence of a large lipophilic end-portion and a'sm'alllipophobic but hydrophilic ionized portion.
:The li'pophilicQ portion then tends to dissolve only in hydrocarbon or non aqueous phases while the lipophobic portion'is soluble'in'aqueous phases. In theabsence of a non-aqueous phase there is a tendency for these mole- H I h The value of n is controllable by variations in the amount -of ethylene orpropylene oxide used as well as the temcules to accumulate at interfaces, either of water'to air .orwater to container walls. Because of their dual nature, i su'rfactants ofthis'type. are useful emulsifiers and dispersants.
1 (In the, new field of fiuorochemical monomers it has ,be'en'found, that fluorocarbons commonly do not have 'lipo'philic charactersnor are they hydrophilic, They are both oleophobic'and hydrophobic; For the emulsion polymerization of fluorocarbon monomers, ordinary surfactants are generally inadequate. unore teflficient emulsifying; agentis .one which possesses a hydrophilic end together with a portion'which has .aflinity :for fluorinated materials ,which may be conveniently-be termed fiuophilic'. For example, fluorocarbon In such systems, a
.endshave greateraflinityfor highlyfluorinated materials J I .thanid o the more conventional lipophilic portions of the lus'ualsurface-active. agents such as sodium lauryl sulfate.
isan object of this invention-to provide novel surfactant'compounds." It is another. object of the invention to' provide s'urfaceactive agentspossessing both a hydrophilic portion and a fiuophilic portion. Other objects of the invention will become evident from the disclosure set forth hereinafter.
' According to the above andother objects of the invention, it has been found that N-(polyoxa-alkyD-perfluoroalkane sulfonamides which can be representedv by the general formula;
RrSOr-N-R carbon atoms, is a member of the group consisting of hydrogen, lower alkyl'radicals and R; and R is a polyoxa-alkyl group having the formula:
RI! f onnmqoomdn ..+o-R" inIwhich'rii'is'an integer from two to three, n is a number from two to about twenty, and each R" is hydrogen or a methyl radical, are surface active agents of excepit onalactivit-y. Inaddition to possessing the general de- .,s irable' characteristicsof high surface activity, they are particularly useful in emulsifying fiuorochemical monoe'rs, as, fol-example, in producing elastomers of high o l ;res stance by emulsionpolymerization processes.
f atented Dec. 1, 1959 They possess the further advantage of-being non-ionic so that their surfactant activity is substantially independent of pH over wide ranges.
As solutes in minute amounts the compounds of the invention are surprisingly elfective in lowering the surface tension of water, and are extremely useful where that effect is desired; as well as for emulsifying agents .or as surfactants in compositions such as floor wax, to
produce leveling effects. They also find utility as additives to aqueous solutions used in the treatment of textiles, paper, leather and other materials, as well as additives for petroleum products.
Broadly speaking, the N-polyoxa-alkyl-perfiuoroalkanesulfonamides of the invention can be prepared by the condensation in.- alkaline medium of ethylene or propylene oxideand an appropriately substituted perfluoroalkylsulifonylamidoalkanol (produced by the method of Ahl- 'brecht and.-Brown, described in application Ser. No. 560,-
899, filed January 23., 1956, now U.S. Patent 2,803,656). The following equation illustrates the course of the reac tion:
perature and duration of the reaction from 2 or 3 to an average of 20 or'more. Alternatively, the sodium salt of a perfluoroalkanesulfonamide, of the type described in U.S.- Patent No. 2,732,398, can be condensed with a polyethylene glycol halidehaving the desired number of molesof ethylene oxide. The following equation, showing the preparation of the condensation product of N- -methyhperfluoro-dodecancsulfonamide with a polyethylene glycol chloride of molecular weight about 365, illus- Another method for preparation of the compounds of the invention which have terminal methoxy groups on the polyoxyalkylene moiety, comprises the condensation of a perfluoroalkanesulfonyl fluoride such as those described in U.S. Patent 2,732,398, with a polyglycolamine 'having the desired 'chain length.
perfiuorooctanesulfonamide, N isopropyl perfiuorooctanesulfonamide, N ethyl perfluorododecanesulfonamide and perfluorodecanesulfonamide. 'The polyalkylene glycol halides which are reacted with'these compounds are conveniently identified as to chain length by their molecular'weight. For example, a polyethylene glycol chloride of average molecular weight 410 contains about 8 to 9 condensed ethylene oxide units; one of average molecular weight 610 contains about 13 cont 3 densed ethylene oxide units; one of average molecular weight 975 contains about 22 condensed ethylene oxide units, and so on.
The following examples, which are illustrative only rather than limiting or delineative of the scope of the invention, serve to describe the novel compounds, their method of preparation and their properties.
Example 1 A flask fitted with a mechanical stirrer, a gas inlet tube and a reflux condenser cooled with a mixture of acetone and solid carbon dioxide was charged with 20 grams (0.035 mole) of N-ethyl-N-Z-hydroxyethyl perfiuorooctane sulfonamide 2 a CaFnS OrNCHzCHzOH and 0.8 gram of 50% sodium hydroxide (0.01 mole). Ethylene oxide gas was passed into the flask, the temperature of the reactants being held at about 90 to 110 C., for 4 hours. A total of 15.5 grams (0.35 mole) of ethylene oxide was absorbed, indicating the formation of a polyether of the approximate formula:
The product was a substantially colorless viscous oil at room temperature which was more fluid at elevated temperatures.
By repeating this procedure, using about 21 grams of propylene oxide, there is obtained a similar colorless, viscous oil consisting of the condensation product of propylene oxide and N-ethyl-N-Z-hydroxyethyl perfluoro- Surface tension Concentration surfactant (percent) (dynes/cm.)
The surface tension of pure water is about 74 dynes/cm. at 18 C. V
For comparison, there are tabulated surface tension values heretofore determined for several known surfactant compounds, as set forth in U.S. Patent No. 2,723,999:
Concen- Surface tration Compound (percent) Condensation product of hetpafluorobutanol and 4.3 moles of ethylene oxide CF;(CF;):CH:O- 2 40) 1 Is apropyl-nuphthalene Sodium sulionate Diisobutyl sodium snll'osuccinate..- Diamyl sodium sullosuccinate Latices were prepared from 1,1-dihydroperflorohexyl methacrylate in water-acetone mixtures using C F SO N C H -CI -I CH (OCH CH OH as the emulsifying agent. One hundred parts by weight of monomer mixed with 180 parts of acetone-water mixture, 0.5 partof the above-named emulsifier andi0.5 part of potassium persulfate were heated in a sealed glass container for about 20 hours at 50 C. In three different runs, in which 10, 20 and30,% by weight of acetone were used respectively in the acetone-water fimixture, latices consisting of poly-1,l-dihydroperfluorohexyl methacrylate were obtained in substantially quantitative yield with small amounts of1precoagulum.
Example Each of the six surfactants of the general formula:
I? cmasomwmem-(oemennron inwhich R was methyl, ethyl and butyl and n hadvaluejs of S9 and about 13 wasprepared byreacting stoichiometric amounts of the N-alkyl perfiuorooctanesulfonamide sodium salt with polyethylene glycol chlorides of average molecularwe jights 410 (n=8-9) and 610 (rt-:ca. 13). In this way, 26 grams .'(0.05 mole) of CgF -{SO N(CH )Na were reacted with 20.5 grams (0.05 more of Cl( CH CH O) I-I (molecular weight about 410) by heating together with swirling. in a flask at until an exothermic [reaction commenced which raised the temperature to about C. After this reaction had subsided, heating was continued at 100 C. for about '2 hours. The product was a heavy viscous liquid. The other five surfactants were prepared in the same manner and were likewise heavy, viscous liquids.
Example3 A mixture or 7.3 g. 0.02 mole) of the sodium salt of N-methyl-perfluorobutanesulfonamide and 12.2 g. (0.02 m.) of polyethylene glycol chloride 610 (corre- 'sponding approximately to C1(CH CH O) H) was heated on the steam bath for about 1.5 hours; The sulfonamide salt soon dissolved and a finely divided precipitate formed. The reaction product was a viscous, ambercolored liquid. Surface tension measurements of aqueous solutions ofthis product, determined with a Du Nouy tensiometer, gave the following values:
Concentration, gi moles/l. Dynesgm 25 The molecular weight of this material is about 900 and it is evident that it an eflective surface active agent.
Exanzple 4' This example illustrates a further method of synthesis which is particularly suitable for the preparation of certain compositions of this invention which are otherwise difficult to prepare.
In a flask fitted with stirrer, condenser and dropping Co. as polyglycolamine H-221-M. The exothermic reaction represented by the reaction wherein R, is a perfluoroalkyl group having from 4 to 12 carbon atoms, R is a member of the group consisting of efiected a steady refluxing of the ethereal solution. The reaction mixture was allowed to stand for 16 hours after all of the amine had been added and was then washed with water and with dilute hydrochloric acid (about 0.5 N). The organic layer was concentrated to give a viscous brownish residue of N-(4,7,10,13-tetraoxatetradecyl) perfluorooctanesulfonamide.
Example 5 This example illustrates'the preparation of addition products of perfluoroalkane sulfonamides and alkylene oxides, in which two positions on the nitrogen atom are occupied by polyxoaalkylene groups.
A mixture of about 3.04 g. of perfluorooctanesulfonamide and about 5.3 g. of ethylene oxide was placed in a heavy-walled glass ampoule. The ampoule was evacu ated and sealed, and then was heated for about 14 hours at about 125 to 128 C. The ampoule was then cooled, the contents were frozen with liquid air, and the tube was opened. Any unreacted ethylene oxide was removed by RgSOrllI-R' hydrogen, lower alkyl radicals and R', and R' is a poly oxa-alkyl group represented by the formula:
f v (CH2)m-(OCHzCH),,0R"
wherein each R" is a member of the group consisting of hydrogen and the methyl radical, m is an integer of the group consisting of 2 and 3, and n is a number from 2 to 20.
2. A compound represented by the formula:
3. A compound represented by the formula:
(llHs C4FnSOzNCzH4(OCH2CHz) 3-03 4. A compound represtend by the formula:
C F SO NH( CH (OCH CH -OCH 5. A compound represented by the formula:
CzHr (EH2. CsFuSOzN-C:H;(OCH2CH)10OH References Cited in the file of this patent UNITED STATES PATENTS 2,677,700 Jackson et a1. May 4, 1954 2,803,656 Ahlbrecht et al Aug. 20, 1957 FOREIGN PATENTS 513,646 Canada June 14, 1955

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