Composition comprising a fluorine-containing surfactant

Abstract

The invention relates to a composition comprising a fluorine-containing surfactant having a cationic group, a divalent sulfur-containing group and a fluorinated group, further comprising an anion that corresponds to the cationic group of the fluorine-containing surfactant, the cationic group being an N-alkylated heterocyclic group.

Claims

1. A composition comprising: 1) a surfactant having: a cationic group, a bivalent or polyvalent sulfurous group, and a fluorinated group; 2) an anion corresponding to the cationic group of the surfactant; wherein the cationic group is an N-substituted heterocyclic group selected from the group consisting of an N,N-disubstituted imidazolium group, an N,N-disubstituted imidazolinium group, and an N,N-disubstituted benzimidazolium group.

2. The composition in accordance with claim 1, wherein the cationic group is an N,N-disubstituted imidazolium group.

3. The composition in accordance with claim 1, wherein the fluorinated group is a fully fluorinated hydrocarbon group of the type C.sub.nF.sub.2n+1, where n is 5, 6, or 7.

4. The composition in accordance with claim 1, wherein the sulfurous group is a thioether.

5. The composition in accordance with claim 1, wherein the anion is selected form the group consisting of a fluoride, a chloride, a bromide, an iodide, an aryl sulfonate, an alkyl sulfonate, an alkyl sulfate, a sulfate, an aryl phosphonate, an alkyl phosphonate, a monoalkyl phosphate, a dialkyl phosphate, a (di)hydrogen phosphate, a phosphate, a hexafluorophosphate, a hydrogen carbonate, a carbonate, a carbamate, an alkyl carbonate, a trifluoromethanesulfonate, a bis(trifluoromethane sulfonyl)imide, a nonaflate, and a carboxylate.

6. The composition in accordance with claim 1, wherein the anion is covalently bonded to the surfactant.

7. The composition in accordance with claim 6, wherein the anion is covalently bonded to a nitrogen atom of the cationic group via an interposed spacer.

8. The composition in accordance with claim 7, wherein the spacer is a linear or branched C1-C10 alkylene group.

9. The composition in accordance with claim 7, wherein characterized in that the spacer is a linear or branched C1-C5 alkylene group.

10. The composition in accordance with claim 7, wherein the spacer is an ethylene group.

11. The composition in accordance with claim 6, wherein the anion is covalently bonded to the sulfurous group of the surfactant, either directly or via an interposed spacer.

12. The composition in accordance with claim 1, wherein the fluorinated group is bonded to a nitrogen atom of the cationic group, either directly or via an interposed spacer.

13. The composition in accordance with claim 1, wherein the surfactant has one of the following structures: ##STR00014## where one of the residues R.sub.1, R.sub.2 or R.sub.3 represents a (CH.sub.2).sub.1-5(CF.sub.2).sub.3-10CF.sub.3 group and the two further ones of the residues represent, independently of one another, hydrogen or a linear or branched C1-C10 alkyl group that has a crosslinkable group or is covalently bonded to the anion.

14. The composition in accordance with claim 1, wherein the fluorinated group is covalently bonded to the sulfurous group, either directly or via an interposed spacer.

15. The composition in accordance with claim 1, wherein the fluorinated group is a fully fluorinated and linear group of the type C.sub.nF.sub.2n+1, wherein n is from 3 to 10.

16. The composition in accordance with claim 1, wherein the fluorinated group is a fully fluorinated and linear group of the type C.sub.nF.sub.2n+1, wherein n is 5, 6, or 7.

17. A method for altering a property of a solution comprising adding the composition of claim 1 to the solution, wherein said property is surface tension, foaming, an optical property, oxygen solubility or oxygen permeability.

18. A method of preparing a composition in accordance with claim 1, wherein said method comprises the step of a conversion of an uncharged compound having an N-alkylated heterocyclic group, a divalent sulfurous group, and a fluorinated group with an acid.

19. A method of preparing a composition in accordance with claim 1, wherein the method comprises a metathesis for exchanging the anion corresponding to the cationic group of the surfactant containing fluorine.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) Further details and advantages of the invention result from the embodiments inter alia described in the following with reference to the Figures. There are shown in the Figures:

(2) FIG. 1: a reaction equation for the synthesis of a polymerizable surfactant containing fluorine;

(3) FIG. 2: a reaction equation for the synthesis of a surfactant containing fluorine from thiamazole;

(4) FIG. 3: a reaction equation for the synthesis of a surfactant containing fluorine from a fluorine base with an acid;

(5) FIG. 4: a schematic reaction equation for the synthesis of a surfactant containing fluorine by metathesis;

(6) FIG. 5: a reaction equation for the synthesis of a surfactant containing fluorine by thionisation and alkylation;

(7) FIG. 6: a photographic image that shows the foam-inhibiting effect of 1-methyl-2-((perfluorohexylethyl)thio)imidazolium-O,S-dimethyl phosphorothioate;

(8) FIG. 7: a photographic image that shows the foam-generating effect of 3-(1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)imidazolium-3-yl) propane-1-sulfonate;

(9) FIG. 8: a representation of the crystal structure of 3-(1-methyl-2-((perfluorohexylethyl)thio)imidazolium-3-yl)propane-1-sulfonate; and

(10) FIG. 9: a representation of the crystal structure of 1-methyl-2-((perfluorohexylethyl)thio)imidazoliumiodide-Co-1-iodoperfluorooctylane.

(11) A compound containing fluorine that is preferred within the framework of the present invention, that acts as a surfactant, and that additionally comprises a crosslinkable functionality is shown in FIG. 1 with 2-acrylamido-2-methylpropanesulfonate as the counter-ion. The anion can be polymerized by the acrylamide functionality.

(12) FIG. 2 shows a reaction equation for the synthesis of a surfactant containing fluorine in accordance with the invention from thiamazole. This alkylation is successful with particularly good yields and is associated with low costs.

(13) The reaction equation in accordance with FIG. 3 is representative for a generally synthetic access to surfactants containing fluorine in accordance with the invention. Starting from a surfactant containing fluorine in accordance with the invention, an uncharged base containing fluorine can be produced here by a simple deprotonation by means of a base, preferably by means of carbonate, said base containing fluorine subsequently in turn resulting in alternative surfactants containing fluorine with an acid in high yields. The yields over all the synthesis steps are here typically above 90%.

(14) FIG. 4 shows a metathesis reaction of a surfactant containing fluorine in accordance with the invention. The designation Cat* stands for a cation here. A preferred metathesis is, for example, represented by the precipitation of sodium chloride in acetone with a simultaneous formation of a new fluorosurfactant.

(15) FIG. 5 describes a general synthetic access to surfactants in accordance with the invention from disubstituted imidazole as the pre-stage.

(16) It must generally be noted that protonated surfactants in accordance with the invention can be deprotonated again in dependence on the pH. This can be used in a targeted manner in some applications. In contrast, disubstituted fluorosurfactants in accordance with the invention are also relatively stable with a basic pH. Under extreme pH conditions, a beta-H elimination can take place in the dialkylated systems and thereupon an elimination of e.g. 1,H,1H,2H,2H-perfluorooct-1-ene. This can promote or facilitate a degradation in certain cases. The cationic charge can be used in a targeted manner here to filter waste waters, for example via ion exchangers, preferably in an acidic or neutral milieu. The above-named degradation reaction can subsequently be used to achieve a removal of the fluorine side chain. This enables a particularly environmentally compatible process.

(17) The image in accordance with FIG. 6 is based on the use of the 1-methyl-2-((perfluorohexylethyl)thio)imidazoliumO,S-dimethylphosphorothioate described in synthesis example 5 described below as a defoaming agent. Water and a commercial soap were mixed in equal amounts in both test tubes for the taking of this photograph. The fluorosurfactant in accordance with the invention was subsequently added to the left test tube. Both test tubes were then shaken for 1 minute. The photograph was taken after the test tubes had rested for 10 seconds. The inhibition of the foaming by the surfactant in accordance with the invention can be easily recognized.

(18) FIG. 7 shows a photograph in which a test tube can be seen on the left that is filled with 10 ml water in which 20 mg 3-(1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)imidazolium-3-yl) propane-1-sulfonate has been dissolved. A test tube having distilled water can be seen on the right. Both test tubes were shaken for 1 minute. A clear foaming due to the surfactant can be observed here.

(19) FIG. 8 shows the molecular structure determined from single crystal X-ray structure analysis of the fluorosurfactant in accordance with the invention used for taking the photograph of FIG. 7.

(20) FIG. 9 shows a halogen complex between a fluorosurfactant in accordance with the invention and 1-iodoperfluorooctane.

SYNTHESIS EXAMPLE 1

Synthesis of 1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)-1H-imidazolium-2-(methacryloyloxy)ethane-1-sulfonate

(21) ##STR00007##

(22) Formulation:

(23) 3.067 g (6.66 mmol) 1-methyl-2-((1H, 1H, 2H, 2H-perfluorooctyl)thio)-1H-imidazole 1.267 g (6.52 mmol) 2-methacryloylethane-1-sulfonic acid

(24) Performance:

(25) 3.067 g (6.66 mmol) 1-methyl-2-((1H, 1H, 2H, 2H-perfluorooctyl)thio)-1H-imidazole and 1.267 g (6.52 mmol) 2-methacrylamidoethane-1-sulfonic acid were admixed without solvent; an immediate reaction and precipitation of the product occurred in this process. The mixture was dissolved in 20 ml methanol in an ultrasound bath for a complete conversion. The solvent was removed at the rotary evaporator. The liquid product was washed with ether, with a white powder being precipitated that was filtered and washed three times with ether.

(26) Yield:

(27) 3.867 g 1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)-1H-imidazolium-2-(methacryloyloxy)ethane-1-sulfonate (5.91 mmol, 90.5%)

(28) .sup.1H-NMR (300 MHz; 25 C.; CD.sub.3OD):

(29) 7.73 (I=1; d (J3=3 Hz); CH-imidazolium); 7.69 (I=1; d (J3=3 Hz); CH-imidazolium); 6.12 (I=1; m; CH.sub.2=Trans); 5.61 (I=1; m; CH.sub.2=cis); 4.49 (I=2; t; CH.sub.2S); 3.96 (3H; s; CH.sub.3N); 3.43 (I=2; t; CH.sub.2NH); 3.17 (I=2; t; CH.sub.2SO.sub.3); 2.68 (I=2; m; CH.sub.2CF.sub.2); 1.92 (I=3; m; CH.sub.3C);

(30) .sup.13C-NMR (75 MHz; 25 C.; CD.sub.3OD):

(31) 168.71 (CO); 140.94 C.=); 137.71 (CS); 127.35 (CHN); 126.57 (CH.sub.2); 122.70 (CHN); 61.73 (CH.sub.2SO.sub.3.sup.); 51.33 (CH.sub.2N); 36.18 (CH.sub.3N); 32.65 (t; CH.sub.2CF.sub.2); 27.76 (t; CH.sub.2S); 18.51 (CH.sub.3);

(32) Melting point: 88.6-89.9 C.

(33) Determining the Solubility:

(34) 3.84 g 1-methyl-2-((1H, 1H,2H,2H-perfluorooctyl)thio)-1H-imidazolium-2-(methacryloyloxy)ethane-1-sulfonate was added to 5 ml water. The suspension was added to the ultrasound bath for 5 minutes and was centrifuged for 20 minutes. The supernatant was then weighed and was rinsed with argon for 5 minutes to remove any possibly dissolved oxygen. The aqueous, slightly yellow solution weighed 7.126 g. The experiment was performed at approximately 23 C.

(35) A solubility of approximately 430 g/L water results from these data.

SYNTHESIS EXAMPLE 2

Synthesis of 1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)-1H-imidazolium-2-acrylamido-2-methylpropanesulfonate

(36) ##STR00008##

(37) Theoretical Yield:

(38) 2.67 g of 1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)-1H-imidazolium-2-acrylamido-2-methylpropanesulfonate.

(39) Performance:

(40) 0.829 g (4 mmol) 2-acrylamido-2-methylpropanesulfonic acid were dissolved in 30 ml methanol and 1.841 g (4 mmol) 1-methyl-2-((1H, 1H, 2H, 2H-perfluorooctyl)thio)-1H-imidazol were slowly dripped into 10 ml methanol after 10 minutes of stirring. The mixture was stirred at room temperature for one day and the methanol was subsequently partially removed at the rotary evaporator. Washing with hexane then took place twice; the hexane phase was decanted and the residual solvent was subsequently removed at the rotary evaporator. A white, slightly yellowish product was obtained.

(41) Yield:

(42) 2.24 g (83.9% of the theoretical yield)

(43) Evaluation and Characterization

(44) .sup.1H NMR (300 MHz, CD.sub.3OD) 7.75 (I=1; d, CH-imidazolium), 7.70 (I=1; d, CH-imidazolium), 6.25 to 6.07 (I=2; m; Trans-CH.sub.2 and CHCO), 5.58 and 5.55 (I=1; dd; Cis-CH.sub.2), 3.96 (I=3; s; CH.sub.3N), 3.44 (I=2, t, CH.sub.2S), 3.24 (I=2, s, CCH.sub.2SO.sub.3), 2.78 to 2.60 (I=2, m, CH.sub.2CF.sub.2), 1.57 (I=6, s, 2CH.sub.3).

(45) .sup.13C NMR (75 MHz, CD.sub.3OD) 167.56 (CO), 140.93 (C2), 133.69 (CH-vinyl), 127.35 (CH.sub.2-vinyl), 125.73 (CH-imidazolium), 122.68 (CH-imidazolium), 60.28 (CH.sub.2SO.sub.3), 53.60 (CH.sub.2-amide), 36.21 (CH.sub.3N), 32.63 (txt, CH.sub.2CF.sub.2), 27.78 (t, 27.72 CH.sub.2S), 27.19 (2CH.sub.3).

(46) This surfactant is polymerizable and soluble in water.

(47) Use of Teflon as an Emulsifying Agent:

(48) A solution of 10 ml water, 0.100 g 1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)-1H-imidazolium-2-acrylamido-2-methylpropanesulfonate was dissolved in 10 ml water and 0.200 g Teflon 1 m (Sigmal-Aldrich) were subsequently added to this solution. A suspension was formed in this process that remained stable for at least 4 hours. After 2 days a white powder had been deposited on the bottom.

SYNTHESIS EXAMPLE 3

Synthesis of 1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)imidazoliumiodide

(49) ##STR00009##

(50) 100 g (0.876 mol) 1-methyl-1,3-dihydro-2H-imidazol-2-thion (thiamazole) and 500 g (1.05 mol) 1H,1H,2H,2H-perfluorooctyliodide were dissolved in 500 ml ethanol while heating slightly; the resulting reaction mixture was subsequently refluxed for 36 hours. The solution was then concentrated by means of a rotary evaporator for so long until excessive foaming makes a further concentration a lot more difficult. This saturated solution was then stored overnight at room temperature to allow the product to crystallize. To complete the precipitation of the product and to remove excessive 1H,1H,2H,2H-perfluorooctyliodide, 50 ml diethyl ether were added to the precipitated product. The mixture was shaken for some minutes; the product was then filtered and washed with a further 300 ml diethyl ether; the drying of the product took place for 24 hours in a high vacuum. 500 g of 1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)imidazoliumiodide were then isolated (97% of the theoretical yield).

(51) .sup.13C NMR (75 MHz, CDCl.sub.3) 140.65 (s, C(1)), 124.58 (s, C(3)), 121.72 (s, C(2)), 126-100 (m, perfluorohexyl), 36.21 (s, C(4)), 31.39 (t, C(6)), 27.88 (t, C(5)).

(52) .sup.1H NMR (300 MHz, CDCl.sub.3) 10.81 (1H, s(br), NH imidazolium, Note: the chemical displacement of this signal appears to be greatly dependent on the concentration), 7.50 (1H, d, C(3)H imidazolium), 7.44 (1H, d, C(2)H imidazolium), 3.91 (3H, s, CH.sub.3), 3.76 (2H, t, CH.sub.2S), 2.61 (2H, tt, CH.sub.2CF.sub.2).

(53) Solubility in MeOH: 1300 g/l

(54) Solubility in DMSO: 740 g/l

(55) Solubility in 3M Novec 71 IPA: 9.6 g/l

(56) Solubility in 3M Novec 71 IPA as 1-iodoperfluorooctyl-Co-complex: 20.5 g/l

SYNTHESIS EXAMPLE 4

Synthesis of 1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)imidazolium-hexafluoroacetylacetonate

(57) ##STR00010##

(58) 1.04 g (5.0 mmol) hexafluoroacetylacetone were dropped into 2.30 g (5.0 mmol) 1-methyl-2-((perfluorohexylethyl)thio)imidazole; the resulting reaction mixture was then shaken lightly for 2 minutes. The product represents a somewhat viscous, colorless liquid; the yield is quantitative.

(59) .sup.13C NMR (75 MHz, acetone-d6) 174.32 (q, carbonyl-C hexafluoroacetylacetonate), 139.24 (s, C(1)), 124.34 (s, C(3)), 122.92 (s, C(2)), 118.18 (q, CF.sub.3 hexafluoroacetylacetonate), 126-100 (m, perfluorohexyl), 85.64 (s(br), carbanion hexafluoroacetylacetonate), 34.27 (s, C(4)), 31.22 (t, C(6)), 26.32 (t, C(5)).

(60) .sup.1H NMR (300 MHz, acetone-d6) 15.83 (1H, s(broad), NH imidazolium), 7.63 (1H, d, C(3)H imidazolium), 7.40 (1H, d, C(2)H imidazolium), 5.85 (1H, s(broad), CH hexafluoroacetylacetonate), 3.87 (3H, s, CH.sub.3), 3.55 (2H, t, CH.sub.2S), 2.59 (2H, tt, CH.sub.2CF.sub.2).

SYNTHESIS EXAMPLE 5

Synthesis of 1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)imidazolium-O,S-dimethylphosphorothioate

(61) ##STR00011##

(62) A solution of 0.821 g (5.0 mmol) sodium-O,S-dimethylphosphorothioate in 25 ml acetone was dripped into a dispersion of 2.48 g (5.0 mmol) 1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)imidazoliumchloride in 25 ml acetone while stirring. The resulting reaction mixture was stirred overnight at room temperature; the arising sodium chloride was subsequently filtered. The solvent of the filtrate was removed in the rotary evaporator; a colorless, viscous oil remained. It was dried overnight in a high vacuum; 2.86 g 1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)imidazolium-O,S-dimethyl phosphorothioate resulted (95% of the theoretical yield).

(63) .sup.13C NMR (75 MHz, acetone-d6) 139.73 (s, C(1)), 126.11 (s, C(3)), 124.20 (s, C(2)), 126-100 (m, perfluorohexyl), 52.71 (d, OCH.sub.3 O,S-dimethylphosphorothioate), 35.27 (s, C(4)), 32.05 (t, C(6)), 26.62 (t, C(5)), 12.55 (s, SCH.sub.3 O,S-dimethylphosphorothioate).

(64) .sup.1H NMR (300 MHz, acetone-d6) 12.31 (1H, s(broad), NH imidazolium), 7.79 (1H, d, C(3)H imidazolium), 7.49 (1H, d, C(2)H imidazolium), 3.93 (3H, s, CH.sub.3), 3.56 (5H, apparently s(br), CH.sub.2S and OCH.sub.3 O,S-dimethylphosphorothioate), 2.71 (2H, tt, CH.sub.2CF.sub.2), 2.16 (3H, s, SCH.sub.3 O,S-dimethylphosphorothioate).

(65) This compound was added to a solution of water and commercially available soap. A test tube with water and soap without surfactant was used as a reference. Both test tubes were shaken for 1 minute and were photographed after 10 seconds (FIG. 6). It can be observed here that much less foam was formed by the fluorosurfactant.

SYNTHESIS EXAMPLE 6

Synthesis of 3-(1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)imidazolium-3-yl) propane-1-sulfonate

(66) ##STR00012##

(67) 3 g (6.52 mmol) 3-(1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)imidazol and 0.92 g (7.5 mmol) 1,3-propane sultone were dissolved in 5 ml acetonitrile and were refluxed for 16 hours, with a certain amount of product already being precipitated during this time. After cooling the reaction mixture, the precipitation of the product was completed by addition of 50 ml diethyl ether and storing the mixture at 20 C. for some hours. The product was subsequently filtered and washed twice with 30 ml diethyl ether in each case; it was then dried overnight at high vacuum. 3.56 g of white, powdery product were able to be isolated (94% of the theoretical yield).

(68) .sup.13C NMR (75 MHz, CD.sub.3OD) 140.66 (s, C(1)), 127.14 (s, C(3)), 125.63 (s, C(2)), 126-100 (m, perfluorohexyl), 49.70 (s, C(6)), 48.66 (s, C(4)), 37.06 (s, C(15)), 32.04 (t, C(8)), 27.96 (t, C(7)), 27.13 (s, C(5)).

(69) .sup.1H NMR (300 MHz, CD.sub.3OD) 8.00 (1H, d, C(3)H imidazolium), 7.89 (1H, d, C(2)H imidazolium), 4.65 (2H, t, C(4)H.sub.2), 4.09 (3H, s, CH.sub.3), 3.41 (2H, t, CH.sub.2S), 2.93 (2H, t, C(6)H.sub.2), 2.79 (2H, tt, CH.sub.2CF.sub.2), 2.39 (2H, quin, C(5)H.sub.2).

(70) The water solubility amounts to approximately 160 g/l.

(71) Approximately 20 mg of this compound was added to 10 ml water. A test tube with water and without surfactant was used as a reference. Both test tubes were shaken for 1 minute and were photographed after 10 seconds (FIG. 7). It can be observed in this process that this fluorosurfactant is active as a foam forming agent.

SYNTHESIS EXAMPLE 7

Synthesis of 3-((3-octyl-1-(1H,1H,2H,2H-perfluorooctyl)imidazolium-2-yl)thio)propane-1-sulfonate

(72) ##STR00013##

(73) 55.8 g (100 mmol) 3-octyl-1-(1H,1H,2H,2H-perfluorooctyl)-1,3-dihydro-2H-imidazol-2-thion and 15.9 g (130 mmol) 1,3-propane sultone were admixed with 65 ml acetonitrile and were carefully refluxed for 16 hours (high foam formation). After cooling the reaction mixture, 300 ml diethyl ether were added for the product precipitation and this mixture was then stored overnight at 20 C. The product was subsequently filtered and washed twice with 150 ml diethyl ether in each case; it was then dried at high vacuum for 24 hours. 37.5 g of white, powdery product resulted (55% of the theoretical yield).

(74) .sup.13C NMR (75 MHz, CD.sub.3OD) 141.51 (s, C(1)), 125.96 (s, C(3)), 125.89 (s, C(2)), 126-100 (m, perfluorohexyl), 51.23 (s, C(4)), 50.36 (s, C(22)), 43.15 (t, C(12)), 36.56 (s, C(20)), 32.85 (s, C(5)), 31.61 (t, C(13)), 31.07 (s, C(6)), 30.21 (s, C(7)), 30.10 (s, C(8)), 27.24 (s, C(9)), 27.00 (s, C(21)), 23.64 (s, C(10)), 14.34 (s, C(11)).

(75) .sup.1H NMR (300 MHz, CD.sub.3OD) 8.06 (1H, d, C(3)H imidazolium), 7.98 (1H, C(2)H imidazolium), 4.82 (2H, t, C(124)H.sub.2N), 4.43 (2H, t, C(4)H.sub.2N), 3.29 (2H, t, C(20)H.sub.2S), 3.01 (2H, tt, CH.sub.2CF.sub.2), 2.91 (2H, t, C(22)H.sub.2SO.sub.3), 2.09 (2H, quin, C(5)H.sub.2), 1.93 (2H, quin, C(21)H.sub.2), 1.33 (10H, m, C(6-10)H.sub.2), 0.89 (3H, t, C(11)H.sub.3).

(76) Values for the solubility of the product in different solvents are shown in the following Table 1.

(77) TABLE-US-00001 TABLE 1 Solvent Solubility (g/l) Et.sub.2O 0.5 Acetone 3.0 MeCN 9.0 EtOH 163 H.sub.2O 2.0

EXAMPLE 8

(78) Measurement of Surface Tensions:

(79) The surface tension was determined at suspended drop using a Drop Shape Analyser DSA 25 of the Krss corporation. The drop volume at most measurements amounted to approximately 5 l. The measurements were performed at temperatures between 24.5 and 25.1 C. and at a relative humidity of approximately 19%. Each sample was measured a total of ten times. The standard deviations are marked by s in the table shown below. In the measurements at a concentration of 0.05 wt % surfactant, larger drop volumes were used in some cases to obtain a better reproducibility of the measurement results. The measurement values are shown in the following Table 2.

(80) TABLE-US-00002 TABLE 2 Concentration Concentration of surfactant of surfactant in water 0.5 in water 0.05 wt % wt % n = 10 n = 10 OFS OFS (mN/m) s (mN/m) s 1-methyl-2-((1H,1H,2H,2H- 16.22 0.05 23.24 0.21 perfluorooctyl)thio)-1H-imidazolium-2- (methacryloyloxy)ethane-1-sulfonate 3-(1-methyl-2-((perfluorohexyl- 24.94 0.09 29.74* 0.16 ethyl)thio)-imidazolium-3-yl)-propane- 1-sulfonate Perfluorooctanoic acid 16 0.34 55.68** 0.26 Ammonium-4,8-dioxa-3H- 46.42 0.29 64.87** 0.07 perfluorononanoate 1-methyl-2-((1H,1H,2H,2H- 16.21 0.06 24.39 0.14 perfluorooctyl)thio)-1H-imidazolium- methanesulfonate *Sample volume was 8 l; **Sample volume was 20 l.

(81) Even further measurements of the surface tension were carried out for 1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)-1H-imidazolium-2-(methacryloyloxy)ethane-1-sulfonate in different concentrations in accordance with the same method as described above. The result is collected in Table 3 below.

(82) TABLE-US-00003 TABLE 3 c (%) OFS (mN/m) s 0.5 16.22 0.05 0.1 20.8 0.09 0.05 23.24 0.21 0.01 32.11 0.29 0.005 70.28 0.2

(83) At a concentration of 0.5 wt % in water, the values of the surfactants in accordance with the invention are comparable with the prior art. At lower surfactant concentrations, this is, however, easily exceeded. In addition, 1-methyl-2-((1H,1H,2H,2H-perfluorooctyl)thio)-1H-imidazolium-2-(methacryloyloxy)ethane-1-sulfonate can still be polymerized, which can, for example in lacquers, result in an additionally increased environmental compatibility.

EXAMPLE 9

(84) Synthesis of Hydrogels

(85) Different hydrogels were synthesized. The starting products are listed in the following Table 4.

(86) TABLE-US-00004 TABLE 4 Refer- Hydro- Hydro- Hydro- Hydro- ence gel 1 gel 2 gel 3 gel 4 Sodium 2-acrylamido-2- 48.00 39.18 43.20 43.20 39.18 methanepropanesulfonate Water 48.00 39.18 43.20 43.20 39.18 Ethyleneglycoldimeth- 2.96 2.42 2.66 2.66 2.42 acrylate 2-hydroxy-2-methyl-1- 1.04 0.85 0.94 0.94 0.85 phenyl-1-propanone 3-((1-(1H,1H,2H,2H- 18.37 10.00 perfluorooctyl)-3- vinyl-1H-imidazolium- 2-yl)thio)propane- 1-sulfonate 1-methyl-2- 10.00 20.00 ((1H,1H,2H,2H- perfluorooctyl)thio)- 1H-imidazolium 2-acrylamido-2- methylpropane sulfonate Weighted sample [g] 2.72 2.64 2.29 2.26 3.65 Swollen for 13 hours 77.69 21.72 27.59 32.26 47.55 in 800 ml water Ratio 28.56 8.23 12.05 14.27 13.03 Trans- Trans- Trans- Opaque White parent parent parent

(87) The examples show that the fluorosurfactants used are suitable for installation in a hydrogel. The swell behavior was furthermore changed in this process, but remained surprisingly high despite a high fluorine content. Hydrogels 1 and 2, that still remained transparent despite the high water absorption, are above all worthy of note. This could in particular be of advantage in contact lenses. With a high fluorine content in hydrogels, the refractive index of the hydrogel, on the one hand, and the oxygen solubility or oxygen permeability, on the other hand, can be modified in a targeted manner.

(88) The fluorosurfactants in accordance with the invention are inter alia also intended for use in an aqueous medium. A good water solubility can be of great interest here. Some of the compositions in accordance with the invention showed a surprisingly high water solubility in this process. Table 5 shown below comprises some measured values. The values are not exact and only serve a better understanding.

(89) TABLE-US-00005 TABLE 5 Solubility in water Substance [g/l] 1-methyl-2-((1H,1H,2H,2H- 1750 perfluorooctyl)thio)imidazoliumchloride 1-methyl-2-((1H,1H,2H,2H- 1200 perfluorooctyl)thio)imidazoliumbromide 1-methyl-2-((1H,1H,2H,2H- <1 perfluorooctyl)thio)imidazoliumiodide 3-(1-methyl-2-((1H,1H,2H,2H- 160 perfluorooctyl)thio)imidazolium-3-yl) propane-1- sulfonate 3-((3-octyl-1-(1H,1H,2H,2H- 2 perfluorooctyl)imidazolium-2-yl)thio)propane-1- sulfonate 1-methyl-2-((1H,1H,2H,2H- >4000 perfluorooctyl)thio)imidazolium-()-camphor-10- sulfonate

(90) A high viscosity gel that, however, had no visible solid residue was formed in some compounds.

(91) Further experiments showed that the fluorosurfactants in accordance with the invention can also be worked into sticky compositions such as in sticky hydrogels and that an adhesion to different substrates such as steel or the human skin is still achieved.

EXAMPLE 10

(92) Determining the Surface Tension

(93) The determination of the static surface tension for 3-(1H,1H,2H,2H-perfluorooctyl)-2-((1H,1H,2H,2H-perfluorooctyl)thio)-1-methyl-1H-imidazolium chloride in water produced the values indicated in the following Table 6 for the surface tension (OFS) in nN/m at different concentrations c in wt %. The values for OFS represent the mean value from 10 measurements. The standard deviation S [mN/m] for these values is likewise indicated.

(94) TABLE-US-00006 TABLE 6 c (wt %) OFS (mN/m) S [mN/m] 0.5000 14.5 0.04 0.2500 15.5 0.04 0.1000 15 0.1 0.0750 15.02 0.05 0.0500 15.05 0.04 0.0250 14.43 0.03 0.0100 16.29 0.04 0.0075 18.89 0.05 0.0050 21.29 0.05 0.0025 40.74 0.4

(95) The measurement values show that the surface tension of water considerably drops on the addition of the surfactant, with the surfactant itself still showing a large effect at very small concentrations.

EXAMPLE 11

(96) Fluorosurfactant for Use as a Ski Wax

(97) 95 g of a paraffin wax were melted at 150 and 5 g 1-octyl-3-(1H,1H,2H,2H-perfluorooctyl)-2-((1H,1H,2H,2H-perfluorooctyl)thio)-1H-imidazoliumiodide were added. The mixture was intensely stirred until a homogeneous melt was able to be recognized. The melt was brought to solidification by cooling to room temperature.

(98) The wax mixture thus obtained was applied to the running surface of a cross-country ski using an iron. The sliding properties of this ski were compared with the sliding properties of a ski treated with the pure paraffin wax under spring-like snow conditions. The ski treated with a wax in accordance with the invention showed considerably better sliding properties.

EXAMPLE 12

(99) Fluorosurfactant for Use as a Foam Forming Agent

(100) The components listed in the following Table 7 were mixed and the mixture was shaken in the ultrasound bath until homogeneity.

(101) TABLE-US-00007 TABLE 7 Substance Quantity 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1H- 2 g imidazoliumchloride 2,2-azobis(2-methylpropionamidine)-dihydrochloride 0.1 g Water 95.5 g

(102) The homogeneous mixture obtained was heated to 65 C. to start a polymerization reaction. Cooling took place to room temperature after 6 h. A stable emulsion was obtained. Subsequently, 1.9 g 2-((1H,1H,2H,2H-perfluorooctyl)thio)-1-methyl-1H-imidazoliumchloride and 0.5 g 3-(1H,1H,2H,2H-perfluorooctyl)-2-((1H,1H,2H,2H-perfluorooctyl)thio)-1-methyl-1H-imidazoliumchloride were added and the two components were carefully dissolved in the ultrasound bath.

(103) The mixture thus obtained was characterized by a particularly fast and stable foam formation. This property is significant, for example, in a use in fire extinguishing foams.