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Publication numberUS2759019 A
Publication typeGrant
Publication dateAug 14, 1956
Filing dateAug 9, 1954
Priority dateAug 9, 1954
Publication numberUS 2759019 A, US 2759019A, US-A-2759019, US2759019 A, US2759019A
InventorsHarvey A Brown, Arthur H Ahlbrecht
Original AssigneeMinnesota Mining & Mfg
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Perfluoro amine compounds and quaternary derivatives
US 2759019 A
Abstract  available in
Images(3)
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Claims  available in
Description  (OCR text may contain errors)

and waxes.

United States Patent i PERFLUORO AMINE COMPOUNDS AND QUATERNARY DERIVATIVES Harvey A. Brown, St. Paul, and Arthur H. Ahlbrecht,

White Bear Township, Ramsey County, Minn., assignors to lvliunesota Mining & Manufacturing Company, St. Paul, Minn., a corporation of Delaware No Drawing. Application August 9, 1954, Serial No. 448,734

'2 Claims. (Cl. 260-556) This invention relates to our discovery of a new and useful class of reactive fluorocarbon compounds. These compounds have utility as surface active agents, as surface treating and coating agents, as starting compounds for making derivatives, and for other purposes.

These novel compounds are fluorocarbon dialkylamines and their corresponding quaternary ammonium derivatives, uniquely characterized as to structure by having in the molecule a terminal sulfonyl-bonded fluorocarbon tail" that is both hydrophobic and oleophobic.

More specifically, our fluorocarbon-type amines may be termed perfluoroalkaneesulfonamidopolymethylenedialkylamine compounds and are represented by the generic formula:

where R1: is a perfluoroalkyl chain (CnF2n+1-) containing 5 to 12 carbon atoms, in (the number of carbon atoms in the intermediate polymethylene linkage) has an integer value of 2 to 6, and R and R" are alkyl groups each containing '1 to 6 carbon atoms. In a fluorocarbon chain structure two carbon atoms may be linked together by an oxygen atom, or three carbon atoms may be linked together by a nitrogen atom, since oxygen and nitrogen provide very stable linkages between fluorocarbon groups and do not interfere with the highly stable and inert character of the complete fluorocarbon structure (as is shown, for instance, in U. '8. Patents Nos. 2,500,388 and 2,616,927). A saturated fluorocarbon chain containing such oxygen or nitrogen linking atom is equivalent to a perfluoroalkyl chain.

As is evident from the above formula, the complete molecule has a fluorocarbon tail at one end and a tertiary amine group at the other end, the tertiary nitrogen atom being joined to :the fluorocarbon tail by an interposed sulfonamidopolymethylene linkage.

It has been discovered that these substituted sulfonamido compounds can be readily prepared by reacting perfluoroalkanesulfonyl fluoride compounds:

with dialkylaminop olymethyleneamine compounds H2N [0 Ha) m-N The stable and inert fluorocarbon tail is repellent not only to water but to oils and hydrocarbons and imparts to our compounds unique surface active and surface treatment properties not possessed by corresponding compounds having a hydrocarbon tail. The polymethylene chain provides a stable linkage between the terminal tertiary nitrogen atom and the nitrogen atom of the amido group, and also serves to impart solubility in oils The terminal dialkyl amino group renders the molecule oil-soluble at this end. Thus the molecule is sufliciently oil-soluble, and is oleophobic at one end ice and oleophilic at the other end. It is repellent to water, oils and waxes at the fluorocarbon end and yet is soluble in oils and waxes at the tertiary amine end. These amine compounds are relatively insoluble in water.

This makes possible water-insoluble molecules that can be dissolved in oils and waxes and yet will concentrate at the surface to form an oriented surface layer having the fluorocarbon tails pointing outwardly and the opposite ends of the molecules pointed inwardly and dissolved in the oil or wax mass. A surface film results that is both water and oil repellent, and which greatly reduces the surface tension.

The solubility of the present amine compounds in oils and waxes decreases with increase in length of the fluorocarbon tail and water-insolubility is enhanced. In contrast, the corresponding compounds of conventional organic chemistry having a sulfonyl-bonded hydrocarbon tail decrease as to water solubility but incerase as to oil solubility with increase in length of this chain, Increase in length of the alkyl groups that are bonded to the terminal tertiary nitrogen atom, and increase in the length of the intermediate polymethylene chain, serves to further decrease solubility in water but increase solubility in oils and waxes. Thus the properties can be varied to best serve a desired particular use.

These tertiary amine compounds can be readily quaternized to the corresponding quaternary ammonium compounds (as by using a hydrocarbon halide or a sulfate ester as the quaternizing agent), which provide powerful surface active agents not only for oils, waxes, etc., but also for aqueous systems. Quaterniza-tion renders the compounds much more soluble in water and surface active in aqueous systems, but does not destroy utility as surface active agents in oils and waxes.

The quaternization reaction and the quaternary ammonium product compounds can be represented as follows:

R [n somnqcnswn n A- where RA is the quaternizing agent (e. g., methyl iodide, benzyl chloride or dimethyl sulfate), R is the hydrocarbon group thereof (e. g., an alkyl or benzyl group) that is covalently bonded to the quaternary nitrogen atom of the product molecule, and A is the anion of the quaternizing agent that becomes eleotrostatically bonded to the quaternary nitrogen atom. The hydrocarbon R group contains 1 to 18 carbon atoms and is an alkyl, alkylcycloalkyl, or alkaryl group, and hence in any such case it is bonded to the nitrogen atom by an alkyl carbon atom.

For convenience the generic formula of the quaternary ammonium compounds can be written as follows:

In this type of compound, the ionic terminal structure can be represented as follows:

ltipmvides an organic cationogenic group united to the polymethylene linkage and contains a quaternary nitrogen atom covalently bonded to four acyclic hydrogenated carbon atoms and electrostatically bonded to an anion. I-t:-.is:-this: cationogenic group thatrcauses therorganimchain tobe=a cationgthaving a'positive charge at thetquaternary nitrogel1;=:p0sition. -When -the compound is.dissolved in water or other suitable ionizing solvent,'the ionizedrmolecules ,-provide surface-active free-.:cations which have a terminal Efluorocarbontail-that is both hydrophobic and oleophobic. :These compounds provide cations that can plate out from solutions to :form tightly adsorbed-polar surface on hydrophilic --or.- electronegative type surfaces, -such-as; glass, lithic materials, metals zpapen-xtextiles, ,etc.,:.with the fluorocarbon tails voriente drou-twards to provide a nonpolar fluorocarbon outer surface.

EFI'hese fluorocarbon-type tertiary amine compounds and quaternary ammoniumiderivatives providesurface active agents thatare highly effective as additives for oils and waxes. reduction canzbe achieved .at concentrations of 0.1% by weight andless in animal, vegetable and mineral oils and waxes, including petroleum solvents, gasoline,- kerosene, fuel -,oils,:lubricating-oils, and parafiin Waxes, thereby,- for instance, improving such properties as surface'protection, flow, spreading, penetration, and atomization or sprayability. The corresponding non-fluorina-ted compounds of conventional organic chemistry do not have any .significant surface .tension reduction efiec-tin'oils and'waxes. These compounds have utility'as emulsifying agents for fluorocarbons and oils (the agent, collecting at :theinterfaces .With thefluOIocarbon tails dissolved in-thefluorocarbon phase and the; opposite ends of themoleculesdissolved in the oil phase).

The quaternary ammonium compounds provide surface active agents that are also-highly eifectiveinwatenand in neutrah-acidic and basic aqueous solutions-servingrto greatly reduce the surface tension even when'present in minute concentrations. The fluorocarbontailvprovides a hydrophobic chain that can beeven more effective in,

aqueous solutions than is a much longer hydrocarbon chain such as is employed in corresponding compounds of conventional organic chemistry, The molecules concentrate at the surface to form an oriented surface layer having the fluorocarbon tails pointing outwardly, the quaternary nitrogen ends being dissolved in the water andpointing inwardly.

"Preparation of sulfonyl fluoride starting compounds As previously 1 mentioned, our substituted sulfonamido amines can be readilyprepared by employingiperfluoroalkanesulfonyl fluorides as reactants to:supplyrtthezfluoro- 'carbon-sulfonyl iportion-of the-product molecule. wThese perfluorin'ated istarting compounds have thezformula:

Where n" has an integer value'of 5 to 12. They canbe prepared in good yields bythe electrochemical fluorination of corresponding alkanesulfonyl fluoride" and chloride compounds, serving to replace the hydrogen atoms byfiuorine atoms and, when 's'ulfonyl chloride compounds are employed, serving also to replace the chlorine atoms so as to obtain .a sulfonyl fluoridezproduct.

According to this procedure, a mixture of liquidhydrogen fluoride and the alkanesulfonylfiuor'ide or chloride is electrolyzed in a nickel-anode cellaata cell voltage of approximately 4 .to 6 volts. '.'The=.saturated perfluorina ted sulfonyl.fluoridepnoductis ;insoluble in liquid HF and wil1.-.either :"evolve' in2admixture with the hydrogen and otherzc'ellgases ortwill settletobthe bottom of wthe.cell inadmixture with other products, depending on the volatility of the particular compound and the operating conditions. It can be recovered 'from the mixture by fractional distillation. This process and the perfluorinated sulfonyl fluoride'products are described in A substantial-degree of surface tension more detail and are claimed in the copending application of T. I. Brice and P. W. Trott, S. N. 334,083, filed January 29, 1953 and since issued as Patent No. 2,732,398 on January 24, 1956. The equipment and operating procedures used in the electrochemical process have been described in the US. patent to J. H. Sim-ons, No. 2,519,983 (August 22, '1950), and in a paper by E. A. "Kauck and A. R. Diesslin published' 'by the American Chemical Society in Industrial and "Engineering Chemistry, vol. =43,-pp. 23324384 (October 1951-).

The following table lists the approximate boilingzpioints (at 740 mm.) of illustrative perfluoroalkanesulfonyl fluorides which can be employed as reactants'for making our compounds:

Compounds: B. P. C.) OF3(CF2)4SO2F CF3(CF2)5SO2F 1'15 CF3(CF2)7SO2F 154 CE; (CF2)9SO2'F .19 0 OF3(C=F2)11SO2F 222 These perfluorinated sulfonyl fluorides .are waiterinsoluble, relatively unreactive, and are highly stablewto hydrolysis in neutral and acidic. aqueous solutions. They have a high degree of thermal stability. They. are soluble in oxy-genatedorganicsolvents.

Example The following experimental description serves. to= illustrate procedures 'for making our compoundspusing the preparation of uct w-as a 7 white crystalline material. having a im'eltiug point of 113.5-'116 C., andwas identifiedas relatively pure CFs'( C1 2) 7SO2'NHC2H4N(C2H5) 2 which may be termed N-.(beta-diethylaminoethyl) pei'fluoroootanesulfonamide. Analysis showed"28.1% C (28.1% calc.) and 4.70% N (4.68% calc.).

"This amine compound was relatively insoluble in water and was ineifective as an agent for materially reducing the surface tension of Water. "However, it had pronounced surface activity in hydrocarbon media, reducing the surface tension of a refined petroleumilubricating oil from a value 'of 30.6 dynes/cm. at"25"C. to"22'5 dynes/cm. at a concentration:of:0.l%.

This. compound was quaternized by reacting 3 ,;,.grams (0.005 mole) with 1.26 grams (0.01 mole) of dimthyl sulfate. The reaction is exothermic and was completed in a few minutes, producing the'desired quaternary ammonium salt:

and was then .dissolved in ml. water. "This solution wastested asa surface active additive and Was'iound' to .-ha-ve..a high degree of activity both in water and oil.

@It .was..found. that this quaternary ammonium comthe quaternary ammonium salt). The extreme activity was further shown by the fact that the surface tension was reduced to 17.5 dynes/cm. at a concentration of only 0.001%, and it was reduced to 48 dynes/cm. at the extremely minute concentration of 1 p. p. m. (0.000l% The surface tension of a refined petroleum lubricating oil was reduced from 30.6 dynes/cm. at 25 C. to 24.5 dynes/cm. at a concentration of 0.1%.

A further sample of the amine compound was quaternized with methyl iodide by dissolving 4 grams of the amine compound in 50 ml of ether, adding 1.5 ml. of methyl iodide, and refluxing for 48 hours. The reaction mixture was filtered and 1.3 grams of solid product was obtained, comprising in crude form the desired quaternary ammonium salt:

This salt product was dissolved in 100 ml. of water and tested for surface activity.

It was found that this particular compound was too insoluble in oil to be usefully effective. However, it was highly active in water, reducing the surface tension of pure water at 25 C. to a value of 17 dynes/cm. at a quaternary salt concentration of 0.01% and to 21.5 dynes/cm. at a concentration of 0.001%.

We claim:

1. The new and useful fluorocarbon compounds of the class consisting of the perfluoroalkane-sulfonamidopolymethylcne-dialkylamine compounds represented by the formula:

where R; is a perfluoroalkyl chain containing 5 to 12 carbon atoms, m has an integer value of 2 to 6, and R and R" are alkyl groups each containing 1 to 6 carbon atoms; and the corresponding quaternary ammonium compounds represented by the formula:

where R is a hydrocarbon group containing 1 to 18 carbon atoms which is bonded to the nitrogen atom by an alkyl carbon atom, and A is an anion.

2. The new and useful quaternary ammonium compounds which are represented by the formula:

References Cited in the file of this patent UNITED STATES PATENTS 2,403,207 Barrick July 2, 1946

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US2403207 *Mar 8, 1943Jul 2, 1946Du PontChemical process and products
Referenced by
Citing PatentFiling datePublication dateApplicantTitle
US2993829 *Sep 18, 1958Jul 25, 1961Upjohn CoHalobenzenesulfonyl hydrazide fungicides
US3034955 *Sep 8, 1958May 15, 1962Geigy Ag J RAryl sulphonamide insecticides
US3091619 *May 1, 1958May 28, 1963Du PontNitrogen derivatives of fluoroalkyl sulfonic acid sultones
US3128272 *Jun 11, 1957Apr 7, 1964Minnesota Mining & MfgPerfluoroalkyl-substituted triazines
US3147064 *Feb 2, 1959Sep 1, 1964Minnesota Mining & MfgFluorinated ethers and derivatives
US3207730 *Sep 28, 1962Sep 21, 1965Minnesota Mining & MfgPolymers comprising a fluorinated quaternary salt of an amine-substituted acrylic acid ester
US3245817 *Jul 14, 1961Apr 12, 1966Minnesota Mining & MfgResinous composition containing antimigration agent
US3258423 *Sep 4, 1963Jun 28, 1966Richard L TuveMethod of extinguishing liquid hydrocarbon fires
US3366663 *Nov 9, 1964Jan 30, 1968Monsanto CoProcess for preparing tetraalkyl-ammonium alkyl sulfates
US3378399 *Apr 13, 1964Apr 16, 1968Minnesota Mining & MfgOrganic materials, especially paper, treated with distally perfluoroalkyl amine
US3436262 *Sep 25, 1964Apr 1, 1969Dow Chemical CoCleaning by foam contact,and foam regeneration method
US3458571 *Apr 6, 1967Jul 29, 1969Minnesota Mining & MfgFluorocarbon polyamines
US3864396 *Dec 8, 1972Feb 4, 1975Bayer AgAcylated perfluoroalkanesulphonamides
US3970586 *May 7, 1975Jul 20, 1976Bayer AktiengesellschaftSurfactants
US3993744 *May 31, 1974Nov 23, 1976Alberto Culver CompanyLive human hair treatment compositions containing perfluorinated compounds
US3993745 *May 31, 1974Nov 23, 1976Alberto Culver CompanyHair sprays or conditioners
US4007150 *Feb 9, 1976Feb 8, 1977Bayer AktiengesellschaftUse of perfluoroalkanesulphonic acid amides and/or cyclimmonium salts of perfluoroalkansulphonic acids as mold release agents
US4013786 *May 31, 1974Mar 22, 1977Alberto Culver CompanyHair creme rinses and hair conditioners containing hydrophobic-lipophobic perfluorinated compounds
US4018689 *Jan 12, 1976Apr 19, 1977The Dow Chemical CompanyWith perfluorinated surfactants
US4028257 *Aug 23, 1976Jun 7, 1977The Dow Chemical CompanyComposition and method for reducing the surface tension of aqueous fluids
US4089804 *Dec 30, 1976May 16, 1978Ciba-Geigy CorporationMethod of improving fluorinated surfactants
US4108782 *Apr 27, 1977Aug 22, 1978The Dow Chemical CompanyFoaming and silt suspending agent
US4163754 *Jan 18, 1978Aug 7, 1979Ici Americas Inc.Fluorinated sulfonamides
US4166065 *Sep 15, 1978Aug 28, 1979Akzona IncorporatedReacting perfluoroalkane sulfonylfluoride with an amine in the presence of silica
US4170636 *Dec 29, 1977Oct 9, 1979Minnesota Mining And Manufacturing CompanyFluorine compounds
US4176176 *May 31, 1974Nov 27, 1979Alberto-Culver CompanyHydrophobic-liphobic perfluorinated compound
US4859349 *Oct 9, 1987Aug 22, 1989Ciba-Geigy CorporationFire-fighting
US4873020 *Oct 4, 1988Oct 10, 1989Minnesota Mining And Manufacturing CompanyFluorochemical surfactants and process for preparing same
US4921696 *Oct 11, 1988May 1, 1990The United States Of America As Represented By The Secretary Of AgricultureMethod for the control of insects
US4983769 *Jan 25, 1988Jan 8, 1991P C U K Produits Chimiques Ugine KuhlmannPerfluoroalkylamine oxides and use of these products in fire extinguishing compositions
US5043464 *Apr 24, 1990Aug 27, 1991Shin-Etsu Chemical Co., Ltd.Fluorine-containing surfactant and process for producing the same
US5144069 *Dec 13, 1990Sep 1, 1992Minnesota Mining And Manufacturing CompanyReaction of unsaturated acid and amino containing fluoroalkylsulfonamide
US5159105 *Feb 28, 1990Oct 27, 1992Minnesota Mining And Manufacturing CompanySurfactants; surface treatment of textiles
US5207996 *Oct 10, 1991May 4, 1993Minnesota Mining And Manufacturing CompanyAcid leaching of copper ore heap with fluoroaliphatic surfactant
US5286352 *Jul 15, 1992Feb 15, 1994Minnesota Mining And Manufacturing CompanyElectrolysis of solution of anhydrous hyudrogen fluoride in organic precursor
US5380778 *Sep 30, 1992Jan 10, 1995Minnesota Mining And Manufacturing CompanyFluorochemical aminoalcohols
US5451622 *Sep 30, 1992Sep 19, 1995Minnesota Mining And Manufacturing CompanyComposition comprising thermoplastic polymer and fluorochemical piperazine compound
US5468353 *May 5, 1994Nov 21, 1995Minnesota Mining And Manufacturing CompanyMist suppressant for solvent extraction metal electrowinning
US5478486 *Nov 18, 1993Dec 26, 1995Henkel CorporationComposition and method for treating substrates to reduce electrostatic charge and resultant article
US5525261 *Oct 18, 1994Jun 11, 1996Henkel CorporationAnti-static composition and method of making the same
US5534192 *Feb 22, 1995Jul 9, 1996Henkel CorporationCationic surfactants and nonionic surfactants for textiles as antistatic agents
US5576074 *Aug 23, 1995Nov 19, 1996Minnesota Mining And Manufacturing CompanyBinder converted to supercooled liquid upon exposure to coherent radiation, absorbing radiation with dye to heat exposure to lasers, forming patterns with toners and heating to fuse
US5852148 *Feb 4, 1997Dec 22, 1998Minnesota Mining & Manufacturing CompanyPerfluoroalkyl halides and derivatives
US5882466 *Aug 8, 1996Mar 16, 1999Minnesota Mining And Manufacturing CompanyAqueous bonding composition
US6048952 *Feb 4, 1997Apr 11, 20003M Innovative Properties CompanyPerfluoroalkyl halides and derivatives
US6201122Dec 8, 1992Mar 13, 20013M Innovative Properties CompanyFluoroaliphatic radical-containing anionic sulfonamido compounds
US6255363Sep 26, 1996Jul 3, 20013M Innovative Properties CompanyLiquid inks using a gel organosol
US6365769Feb 15, 2000Apr 2, 20023M Innovative Properties CompanyPerfluoroalkyl halides and derivatives
US6582759Apr 26, 2002Jun 24, 20033M Innovative Properties CompanyOptical elements comprising a fluorinated surface treatment comprising urethane, ester or phosphate linkages
US6632508Oct 27, 2000Oct 14, 20033M Innovative Properties CompanyOptical elements comprising a polyfluoropolyether surface treatment
US6734227Sep 24, 2001May 11, 20043M Innovative Properties CompanyOptical elements comprising a fluoropolymer surface treatment
US6815040Oct 24, 2001Nov 9, 20043M Innovative Properites CompanyFor retroreflective sheetings, pavement markings and beaded projection screens
US6884510Apr 29, 2003Apr 26, 20053M Innovative Properties CompanyOptical elements comprising a fluorinated surface treatment comprising urethane, ester or phosphate linkages
US6905754Apr 26, 2002Jun 14, 20053M Innovative Properties CompanyOptical elements comprising fluorochemical surface treatment
US7893186Dec 27, 2007Feb 22, 20113M Innovative Properties CompanyProcess for preparing long-chain polymethylene halide telomers
US8236425Dec 27, 2007Aug 7, 20123M Innovative Properties CompanyLong-chain polymethylene halide telomers
US8889230Aug 17, 2007Nov 18, 20143M Innovative Properties CompanySide chain fluorochemicals with crystallizable spacer groups
CN102489216BDec 6, 2011Jan 22, 2014华中师范大学Preparation method and application of amphoteric fluorinion-containing ionic surfactant
DE1140188B *Jul 22, 1958Nov 29, 1962Minnesota Mining & MfgVerfahren zur Herstellung von N-Polyoxyalkylenperfluoralkansulfon-saeureamiden
DE2008531A1 *Feb 18, 1970Nov 12, 1970 Title not available
DE2120868A1 *Apr 28, 1971Nov 18, 1971 Title not available
DE2523402A1 *May 27, 1975Dec 11, 1975Montedison SpaPolyoxapolyfluoralkansulfonate und verfahren zu deren herstellung
EP0256979A1 *Jul 27, 1987Feb 24, 1988Ciba-Geigy AgUse of organic fluorochemical compounds with oleophobic and hydrophobic groups in asphaltenic crude oils as viscosity reducing agents
EP0258179A1 *Jul 27, 1987Mar 2, 1988Ciba-Geigy AgUse of organic fluorochemical compounds with oleophobic and hydrophobic groups in crude oils as anti-depositin agents, and said compositions
EP0394963A1 *Apr 24, 1990Oct 31, 1990Shin-Etsu Chemical Co., Ltd.Fluorine-containing surfactant and process for producing the same
WO1979000455A1 *Dec 28, 1978Jul 26, 1979Minnesota Mining & MfgComposition and method for inhibiting plaque formation
WO1984002650A1 *Jan 4, 1984Jul 19, 1984Us AgricultureA method for the control of insects
WO1995014132A1 *Nov 15, 1994May 26, 1995Henkel CorpComposition and method for treating substrates to reduce electrostatic charge and resultant article
WO1996026629A1 *Feb 21, 1996Aug 29, 1996Henkel CorpTreating substrates to reduce electrostatic charge
Classifications
U.S. Classification564/96, 564/97, 558/27, 516/911, 516/201, 516/20, 516/DIG.500, 516/61
International ClassificationC07C311/05, C10L1/24, C07C311/09
Cooperative ClassificationC10M2219/044, Y10S516/05, C10M1/08, Y10S516/911, C10L1/2437
European ClassificationC10M1/08, C10L1/24C1