US2915554A - Non-ionic surfactant derivatives of perfluoro alkane-sulfonamides - Google Patents
Non-ionic surfactant derivatives of perfluoro alkane-sulfonamides Download PDFInfo
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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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- 229940124530 sulfonamide Drugs 0.000 title description 6
- -1 perfluoro Chemical class 0.000 title description 4
- 239000002736 nonionic surfactant Substances 0.000 title description 3
- 150000001875 compounds Chemical class 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 description 10
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 7
- 238000006243 chemical reaction Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- 239000003995 emulsifying agent Substances 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003708 ampul Substances 0.000 description 3
- 239000008346 aqueous phase Substances 0.000 description 3
- 239000007859 condensation product Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000178 monomer Substances 0.000 description 3
- OVARTBFNCCXQKS-UHFFFAOYSA-N propan-2-one;hydrate Chemical compound O.CC(C)=O OVARTBFNCCXQKS-UHFFFAOYSA-N 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 159000000000 sodium salts Chemical class 0.000 description 3
- 150000003456 sulfonamides Chemical class 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 2
- GOOHAUXETOMSMM-UHFFFAOYSA-N Propylene oxide Chemical compound CC1CO1 GOOHAUXETOMSMM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000001804 emulsifying effect Effects 0.000 description 2
- 238000007720 emulsion polymerization reaction Methods 0.000 description 2
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229920000126 latex Polymers 0.000 description 2
- WCYWZMWISLQXQU-UHFFFAOYSA-N methyl Chemical compound [CH3] WCYWZMWISLQXQU-UHFFFAOYSA-N 0.000 description 2
- RRRXPPIDPYTNJG-UHFFFAOYSA-N perfluorooctanesulfonamide Chemical compound NS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F RRRXPPIDPYTNJG-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- GFZPUWKGPNHWHD-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,4-nonafluoro-n-methylbutane-1-sulfonamide Chemical compound CNS(=O)(=O)C(F)(F)C(F)(F)C(F)(F)C(F)(F)F GFZPUWKGPNHWHD-UHFFFAOYSA-N 0.000 description 1
- YUXIIBHHAPNFCQ-UHFFFAOYSA-N 1,1,2,2,3,3,4,4,5,5,6,6,7,7,8,8,9,9,10,10,10-henicosafluorodecane-1-sulfonamide Chemical compound FC(C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(S(=O)(=O)N)F YUXIIBHHAPNFCQ-UHFFFAOYSA-N 0.000 description 1
- BWJDOLYKJRIITN-UHFFFAOYSA-N C(C)NS(=O)(=O)C(C(C(C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F Chemical compound C(C)NS(=O)(=O)C(C(C(C(C(C(C(C(C(C(C(C(F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F)(F)F BWJDOLYKJRIITN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 239000004721 Polyphenylene oxide Substances 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 241001147416 Ursus maritimus Species 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- UWNADWZGEHDQAB-UHFFFAOYSA-N i-Pr2C2H4i-Pr2 Natural products CC(C)CCC(C)C UWNADWZGEHDQAB-UHFFFAOYSA-N 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000000123 paper Substances 0.000 description 1
- 125000005010 perfluoroalkyl group Chemical group 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 229920001515 polyalkylene glycol Polymers 0.000 description 1
- 229920000570 polyether Polymers 0.000 description 1
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036647 reaction Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000015227 regulation of liquid surface tension Effects 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000004753 textile Substances 0.000 description 1
Classifications
-
- 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.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Materials Engineering (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Polyethers (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
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
Claims (1)
1. A COMPOUND REPRESENTED BY THE FORMULA:
Priority Applications (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US673565A US2915554A (en) | 1957-07-23 | 1957-07-23 | Non-ionic surfactant derivatives of perfluoro alkane-sulfonamides |
GB22981/58A GB904111A (en) | 1957-07-23 | 1958-07-17 | Non-ionic surfactant derivatives of perfluoro alkane sulphonamides |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US673565A US2915554A (en) | 1957-07-23 | 1957-07-23 | Non-ionic surfactant derivatives of perfluoro alkane-sulfonamides |
Publications (1)
Publication Number | Publication Date |
---|---|
US2915554A true US2915554A (en) | 1959-12-01 |
Family
ID=24703163
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US673565A Expired - Lifetime US2915554A (en) | 1957-07-23 | 1957-07-23 | Non-ionic surfactant derivatives of perfluoro alkane-sulfonamides |
Country Status (2)
Country | Link |
---|---|
US (1) | US2915554A (en) |
GB (1) | GB904111A (en) |
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US3069432A (en) * | 1961-02-20 | 1962-12-18 | Olin Mathieson | 5-(aminoalkyl)-5, 11-dihydrodibenzo-oxazepines |
US3163547A (en) * | 1961-01-24 | 1964-12-29 | Minnesota Mining & Mfg | Aqueous polish composition |
US3217035A (en) * | 1961-09-07 | 1965-11-09 | Minnesota Mining & Mfg | Fluorinated polyols |
US3258423A (en) * | 1963-09-04 | 1966-06-28 | Richard L Tuve | Method of extinguishing liquid hydrocarbon fires |
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US3378399A (en) * | 1961-09-07 | 1968-04-16 | Minnesota Mining & Mfg | Organic materials, especially paper, treated with distally perfluoroalkyl amine |
US3705185A (en) * | 1969-04-14 | 1972-12-05 | Minnesota Mining & Mfg | N-aroyl sulfonamides |
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US4267087A (en) * | 1977-08-29 | 1981-05-12 | Ciba-Geigy Corporation | Perfluoroalkyl substituted anhydrides and polyacids, and derivatives thereof |
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US7893186B2 (en) | 2006-12-29 | 2011-02-22 | 3M Innovative Properties Company | Process for preparing long-chain polymethylene halide telomers |
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US8236425B2 (en) | 2006-12-29 | 2012-08-07 | 3M Innovative Properties Company | Long-chain polymethylene halide telomers |
US9777407B2 (en) | 2009-03-27 | 2017-10-03 | 3M Innovative Properties Company | Hydrophilic polyproylene melt additives |
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US8268186B2 (en) | 2009-10-15 | 2012-09-18 | E. I. Du Pont De Nemours And Company | Fluorinated amphoteric surfactants |
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JP2016504482A (en) * | 2013-01-29 | 2016-02-12 | スリーエム イノベイティブ プロパティズ カンパニー | Surfactant and production and use thereof |
EP2951217A4 (en) * | 2013-01-29 | 2016-07-13 | 3M Innovative Properties Co | Surfactants and methods of making and using same |
US9454082B2 (en) * | 2013-01-29 | 2016-09-27 | 3M Innovative Properties Company | Surfactants and methods of making and using same |
EP3263611A1 (en) * | 2013-01-29 | 2018-01-03 | 3M Innovative Properties Company | Surfactants and methods of making and using same |
WO2019207543A1 (en) | 2018-04-26 | 2019-10-31 | 3M Innovative Properties Company | Absorbent articles |
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