Crosslinkable Composition And Method For Producing A Coated Article

Abstract

The invention relates to a crosslinkable composition comprising functionalized monomers comprising a crosslinkable group, a cationic group and a fluorinated group, wherein the composition comprises anions corresponding to the cationic groups of the functionalized monomers, wherein the cationic group is an N-substituted cyclic and in particular heteroaromatic group comprising a 5-membered ring and/or at least two heteroatoms and wherein a spacer which is an uncharged and unfluorinated organyl group and preferably an alkylene group is arranged between the cationic group and the fluorinated group.

Claims

1. A crosslinkable composition comprising functionalized monomers that have a crosslinkable group, a cationic group, and a fluorinated group, wherein the composition comprises anions corresponding to the cationic groups of the functionalized monomers, characterized in that the cationic group is an N-substituted cyclic group that comprises a 5-membered ring and/or at least two heteroatoms; and in that a spacer is arranged between the cationic group and the fluorinated group, said spacer being an uncharged and unfluorinated organyl group.

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

3. The composition in accordance with claim 1, characterized in that the cross-linkable group comprises a crosslinkable ethylenic functionality.

4. The composition in accordance with claim 1, characterized in that the spacer is a linear alkylene group having 1 to 10 carbon atoms.

5. The composition in accordance with claim 1, characterized in that the fluorinated group is a completely fluorinated hydrocarbon group.

6. The composition in accordance with claim 1, characterized in that the functionalized monomer further comprises a thioether.

7. The composition in accordance with claim 6, characterized in that the sulfur-bonded organyl residue of the thioether carries the or a further crosslinkable group, with the further crosslinkable group being able to be a crosslinkable ethylenic functionality or a non-ethylenic crosslinkable group, for example an isocyanate group or an epoxide group.

8. The composition in accordance with claim 6, characterized in that the functionalized monomer has a further group that is substituted at the organyl residue of the organyl sulfide group or that represents the sulfur-bonded organyl residue of the thioether.

9. The composition in accordance with claim 6, characterized in that the sulfur-bonded organyl residue of the thioether carries the anion corresponding to the cationic group, with the anion being able to be a sulfate group, a sulfonate group, a phosphonate group, a phosphate group, a carbonate group, a carbamate group, a triflate group, or a carboxylate group substituted at the organyl residue.

10. The composition in accordance with claim 1, characterized in that at least some of the anions are not covalently bonded to the copolymer, with provision being made that the free anion is chloride, iodide, bromide, aryl sulfonate, alkyl sulfonate, alkyl sulfate, sulfate, aryl phosphonate, alkyl phosphonate, monoalkyl phosphate, dialkyl phosphate, hydrogen phosphate, phosphate, hexafluorophosphate, hydrogen carbonate, carbonate, carbamate, alkyl carbonate, trifluoromethanesulfonate, bis(trifluoromethane)sulfonamide, nonaflate, or carboxylate.

11. The composition in accordance with claim 1, characterized in that at least some of the anions are covalently bonded to the functionalized monomer, with it being an organyl-bonded sulfate group, sulfonate group, phosphonate group, phosphate group, carbonate group, carbamate group, triflate group, or carboxylate group.

12. The composition in accordance with claim 1, characterized in that at least some of the anions are a halogenide.

13. The composition in accordance with claim 12, characterized in that the composition further comprises a halogenoalkane.

14. The composition in accordance with claim 1, characterized in that the composition comprises additional monomers that have at least one crosslinkable group, but do not further have either a cationic group or a fluorinated group.

15. The composition in accordance with claim 1, characterized in that the composition further comprises an initiator; and/or in that the composition further has an ionic additive.

16. A method of manufacturing a coated article, characterized in that the surface of the article is wetted with a crosslinkable composition in accordance with claim 1; and in that the composition is subsequently crosslinked to form a coating.

17. A coated article, characterized in that it was manufactured by a method in accordance with claim 16.

18. The crosslinkable composition of claim 1, wherein said spacer is an alkylene group.

19. The crosslinkable composition of claim 1, wherein said crosslinkable group comprises a substituted or unsubstituted vinyl group.

20. The crosslinkable composition of claim 1, wherein the fluorinated group has the formula C.sub.nF.sub.2n+1, where n is 3 to 10.

Description

[0103] Further details and advantages of the invention result from the embodiments described in the Figures and in the following. There are shown in the Figures:

[0104] FIG. 1: an example of a preferred functionalized monomer without additional thioether functionalization;

[0105] FIG. 2: an example of a preferred functionalized monomer with additional thioether functionalization and with an anionic group at the thioether;

[0106] FIGS. 3A-3C: examples of preferred functionalized monomers with additional thioether functionalization and with crosslinkable functionalities at the thioether;

[0107] FIG. 4: a representation of a reaction for forming functionalized monomers with additional thioether functionalization from a precursor with thione functionalization;

[0108] FIG. 5: crystal structures of the thione monomer used in the reaction in accordance with FIG. 4;

[0109] FIG. 6: an example of a functionalized monomer with a sigma complex anion;

[0110] FIG. 7: crystal structures of the complex in accordance with FIG. 6;

[0111] FIG. 8: the measurement result for the particle size distribution of coated nanoparticles in accordance with Example 2;

[0112] FIG. 9: molecular structure of a difluorinated functionalized monomer;

[0113] FIG. 10: an image of a coating in accordance with the invention that is manufactured in accordance with Example 17 and that is oil-repellant and water-repellent;

[0114] FIG. 11: an image of a coated cotton in accordance with Example 10; and

[0115] FIGS. 12A-12B: microscopic images of a coating obtained in accordance with Example 23.

[0116] A functionalized monomer that is particularly preferred within the framework of the present invention is shown in FIG. 1 with idoide as the counterion. This monomer is soluble in polar organic solvents, can be easily polymerized, and forms, after a film polymerization, a polymer coating that has excellent hydrophobic and oleophobic properties and that adheres well to the substrate, in particular when the surface of the substrate is negatively charged or polarized.

[0117] A further particularly preferred functionalized monomer is shown in FIG. 2. The anionic group bonded to the monomer can be advantageous over free anions in some embodiments. For it has a good solubility in polar solvents and additionally has a very pronounced surfactant effect through its two charged groups and through the fluoroalkyl group. It can also be crosslinked in the polymer, which results in increased biocompatibility since no surfactants can be released from the polymer. General preferred properties of zwitterionic coatings are described by Schlenoff in Langmuir 2014, 30, 9625-9636.

[0118] Examples of preferred anions having an additional thioether functionalization and crosslinkable functionalities at the thioether group are shown in FIGS. 3A-3C. The monomers carry at least two crosslinkable groups and can therefore serve as transverse crosslinkers. Where, as shown in FIG. 3A, the thioether group comprises a further ethylenic crosslinkable group, a transverse crosslinking of polymer chains of the same kind can take place. If a non-ethylenic crosslinkable group is selected, as shown in FIGS. 3B and 3C, the monomers thus functionalized can connect different polymers to one another as crosslinkers. For example, the isocyonate group of FIG. 3B can be integrated into a polyurethane chain by a catalytic polymerization reaction with alcoholic groups. The epoxy group of FIG. 3C can, as also the ethylenically crosslinkable group, be radically crosslinked or crosslinked by addition of a nucleophile.

[0119] The thioether group can be obtained by substitution reaction from a thione group and, for example, from a halogenated hydrocarbon. FIG. 4 schematically illustrates such a reaction. This reaction is simple and typically has a satisfactory to good yield. FIG. 5 shows a crystal structure of the thione monomer used in the reaction in accordance with FIG. 4. FIG. 9 shows a molecule structure of an exemplary difluorinated functionalized monomer.

[0120] FIG. 6 shows an example of a functionalized monomer having a halogen complex anion or a sigma complex anion. The anion is formed by the delocalization of charge over an iodide anion and the iodine atom of a fluorinated iodoalkane. Electron density is pulled off from the cationic group of the functionalized monomers by the delocalization of the negative charge in the anion and the hydrophobic and oleophobic effect of the system is significantly increased by the functionalization of the iodoalkane with the perfluoroalkyl group.

[0121] The molecular structure of a single crystal radiograph structural analysis of this complex is shown in FIG. 7.

EXAMPLE 1

3-(1H,1H,2H,2H Perfluorooctyl)-1-vinyl-1H-imidazoliumiodide

[0122] ##STR00009##

[0123] 18.9 g (200 mmol) vinylimidazole and 31.7 g (66.8 mmol) 1H,1H,2H,2H-perfluorooctyliodide were boiled in a backflow process in 70 ml acetonitrile for 48 hours, 300 ml diethyl ether was then added after the cooling of the reaction solution; the mixture was then stored at 20 C. for 18 hours. The solid obtained was filtered, washed with a total of 300 ml diethyl ether, and was dried in high vacuum.

[0124] Yield: 32.84 g (86% of the theoretical yield)

[0125] .sup.13C NMR (75 MHz, CD.sub.3OD) 137.25 (s, C(2)), 129.76 (s, C(6)), 124.67 (s, C(5)), 121.11 (s, C(4)), 110.55 (s, C(7)), 126-100 (m, perfluorohexyl), 43.48 (t, C(8)), 31.94 (t, C(9)).

[0126] .sup.1H NMR (300 MHz, CD.sub.3OD) 9.53 (1H, t, C(2)H imidazole), 8.09 (1H, t, C(5)H imidazole), 7.94 (1H, t, C(4)H imidazole), 7.31 (1H, dd, C(6)H vinyl), 5.98 (1H, dd, C(7)H.sub.2 vinyl), 5.53, (1H, dd, C(7)H.sub.2 vinyl), 4.74 (2H, t, C(8)H.sub.2N), 3.10 (2H, ft, C(9)H.sub.2CF.sub.2).

[0127] A crosslinkable composition was prepared as follows using the monomer in accordance with Example 1:

[0128] 500 m diethylacrylamide (65.79 wt %, 150 g of the monomer in accordance with Example 1 (19.74 wt %), 100 l trimethylolpropane triacrylate (13.16 wt %) and 10 l 2-hydroxy-2-methylpropiophenone (1.32 wt %) were mixed into a small test tube and were held in the ultrasound bath for 10 minutes. A homogeneous yellow solution was produced.

[0129] Some of the solution was applied between two PET films having siliconized inner sides and a spacer of 75 m.

[0130] Both films were subsequently polymerized using a 365 UV LED lamp at 24 W/cm.sup.2 for 30 seconds.

[0131] Characterization took place using an IR spectrum.

[0132] The polymer film was frozen in liquid nitrogen and simultaneously pestled for the recording of the IR spectrum. An IR spectrum of the obtained powder was recorded. The characteristic CF bands at 1237 cm.sup.1, 1213 cm.sup.1 were identified in this process. The CO vibrations of the two acrylates were likewise recognized.

EXAMPLE 2

Cocrystal Having 1-iodoperfluorooctane

[0133] ##STR00010##

[0134] 17.04 g (30.0 mmol) 3-(1H,1H,2H,2H perfluorooctyl)-1-vinyl-1H-imidazoliumiodide were dissolved in 50 ml MeOH. Subsequently, 16.38 g (30.0 mmol) iodoperfluorooctane was dropped in and the produced reaction mixture was stirred at room temperature for 5 minutes. Once the time had elapsed, the solvent was removed at the rotary evaporator. The success of the synthesis was proved, on the one hand, with reference to the solubility and, on the other hand, with reference to the crystal structure.

[0135] To determine the solubility, saturated solutions of the indicated compounds were prepared in the respective solvents and the solid was subsequently separated by means of a centrifuge. The solvent was then separated at the rotary evaporator and the solid residue was weighed. The results are collected in Table 1:

TABLE-US-00001 TABLE 1 Solubility Solvent (g/L] 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl- 3M Novec 8 1H-imidazoliumiodide 71 IPA 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl- 3M Novec 500 1H-imidazoliumiodide cocrystal having 71 IPA 1-iodoperfluorooctane 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl- 3M Novec 6 1H-imidazoliumiodide 7500 + 4 wt % propane-2-ole 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl- 3M Novec 53 1H-imidazoliumiodide cocrystal having 7500 + 4 wt % 1-iodoperfluorooctane propane-2-ole

[0136] An increase of the solubility due to the halogen complex formation can be clearly recognized.

[0137] The crystal structure of the 3-(1H, 1H,2H,2H-perfluorooctyl)-1-vinyl-1H-imidazoliumiodide with iodide as the anion is shown in FIG. 7, with a halogen complex being recognizable having 1-iodoperflurooctane.

[0138] A composition comprising this cocrystal was used for coating SiO.sub.2 nanoparticles.

[0139] For this purpose, 5.36 g of the monomer in accordance with Example 2 in 3M Novec 71 IPA (25 g/55 ml) and 0.306 g methylenebisacrylamide were dissolved in 50 dichlormethane, 2.515 g SiO.sub.2 nanoparticles (porous, 5-15 nm) were subsequently added. The suspension was held in the ultrasound bath for 2 hours, the dichloromethane was subsequently removed at the rotary evaporator, and 2.064 g of the slightly yellowish particles were removed. 50 ml 3M Novec 7500 (hydrofluoroether) were then added and the suspension was again held in the ultrasound bath for 10 minutes; 0.1 g Darocur 1173 were subsequently added. A 15-minute irradiation of the suspension then followed with stirring. A 365 nm LED UV lamp (Phoseion FJ100) was used here at approximately 1 W/cm.sup.2.

[0140] The particles obtained had a clear maximum of the particle size at 11.9 m and an averaged particle size of 24.9 m. They formed a stable suspension that remained stable without being deposited for 1 day in a solvent containing fluorine.

[0141] The measurement result of the particle size distribution is shown in FIG. 8.

[0142] The described nanoparticle suspension in 3M Novec 7500 was applied using a spray bottle to a ski that was coated with a polymer film likewise in accordance with the invention. A white film was produced on the ski after some minutes. It was removed using a brush until no more white residue was recognizable. The sliding properties of the ski were able to be clearly modified by this method.

EXAMPLE 3

Synthesis of 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1H-imidazolium 3H-perfluoro-3-((3-methoxy-propoxy)propanoate

[0143] ##STR00011##

[0144] 2.27 g (4 mmol) 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1H-imidazoliumiodide were presented and mixed with 4 ml water and 25 ml dichloromethane; 5.3 g H-perfluoro-3-((3-methoxy-propoxy)propanoic acid) ammonium salt 30% was then dripped into water (4 mmol) and the resulting reaction mixture was stirred overnight at 25 C. Subsequently, 20 ml 3M Novec 7200 were added and the mixture was briefly shaken to bring the produced precipitation into solution. The organic/fluoroorganic phase was separated from the watery phase and was dried over Na.sub.2SO.sub.4, the solvent mixture was finally removed in the rotary evaporator, and the product obtained (a colorless oil that becomes solid over time) was dried in high vacuum overnight. 29.2 g (89% of the theoretical yield) were able to be obtained in this manner.

[0145] .sup.13C NMR (75 MHz, CD.sub.3CN) 164.68 (t, carboxyl-C DONA), 138.26 (s, C(2)), 130.23 (s, C(6)), 125.07 (s, C(5)), 121.23 (s, C(4)), 110.29 (s, C(7)), 126-100 (m, perfluorohexyl), 43.60 (s, C(8)), 32.34 (s, C(9)).

[0146] .sup.1H NMR (300 MHz, CD.sub.3CN) 10.10 (1H, s, C(2)H imidazole), 8.05 (1H, s (br), C(5)H imidazole), 7.93 (1H, s (br), C(4)H imidazole), 7.35 (1H, dd, C(6)H vinyl), 6.55 (1H, ddd, CHF DONA), 5.98 (1H, dd, C(7)H.sub.2 vinyl), 5.35 (1H, dd, C(7)H.sub.2 vinyl), 4.74 (2H, t, C(8)H.sub.2N), 2.97 (2H, tt, C(9)H.sub.2CF.sub.2).

EXAMPLE 4

Synthesis of 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1,3-dihydro-2H-imidazole-2-thione

[0147] ##STR00012##

[0148] 4 g (24.6 mmol) 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1H-imidazoliumiodide, 0.79 g (24.6 mmol) sulfur and 3.40 g (24.6 mmol) potassium carbonate were presented in a 250 ml round bottom flask and was mixed with 50 ml methanol. The reaction mixture was refluxed for 3 hours. Extraction subsequently took place three times with a respective 150 ml diethyl ether. The combined ether phases were liberated from the solvent at the rotary evaporator; 11.5 g of product was obtained (99% of the theoretical yield). The melting point of the product was 93 C.

[0149] .sup.13C NMR (75 MHz, CDCl.sub.3) 163.42 (s, C(2)), 130.26 (s, C(6)), 118.55 (s, C(4)), 112.82 (s, C(5)), 126-100 (m, perfluorohexyl), 101.36 (s, C(7)), 40.46 (t, C(8)), 29.63 (t, C(9)).

[0150] .sup.1H NMR (300 MHz, CDCl.sub.3) 7.53 (1H, dd, C(6)H vinyl), 6.99 (1H, d, C(5)H imidazole), 6.75 (1H, d, C(4)H imidazole), 5.16 (1H, dd, C(7)H.sub.2 vinyl), 4.96 (1H, dd, C(7)H.sub.2 vinyl), 4.36 (2H, t, C(8)H.sub.2N), 2.70 (2H, tt, C(9)H.sub.2CF.sub.2).

EXAMPLE 5

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

[0151] ##STR00013##

[0152] 15 g (31.76 mmol) 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1,3-dihydro-2H-imidazole-2-thione and 4.27 g (35 mmol) propanesultone were dissolved in 50 ml acetonitrile and were refluxed for approximately 20 hours. The solution already turned milky during cooling; the subsequent addition of 300 ml diethyl ether precipitated the product as an extremely sticky yellow solid; the preparation was stored for 6 hours at 32 C. to complete the precipitation. The diethyl ether was decanted after the cooling phase; the residue was dissolved in as little ethanol as possible; the product was subsequently again precipitated from the ethanolic solution using 300 ml diethyl ether. Oil separation again tool place and it slowly became solid in the freezer. Once the product had become solid, the liquid phase was decanted again and the product was subsequently dried in high vacuum overnight. 12.50 g of almost white product (66% of the theoretical yield) resulted.

[0153] .sup.13C NMR (75 MHz, CD.sub.3OD) 141.82 (s, C(2)), 129.65 (s, C(6)), 126.29 (s, C(5)), 122.65 (s, C(4)), 112.67 (s, C(7)), 126-100 (m, perfluorohexyl), 50.23 (s, C(19)), 43.13 (t, C(8)), 36.50 (s, C(17)), 31.65 (t, C(9)), 26.98 (s, C(18)).

[0154] .sup.1H NMR (300 MHz, CD.sub.3OD) 8.36 (1H, d, C(5)H imidazole), 8.17 (1H, d, C(4)H imidazole), 7.62 (1H, dd, C(6)H vinyl), 6.11 (1H, dd, C(7)H.sub.2 vinyl), 5.69 (1H, dd, C(7)H.sub.2 Vinyl), 4.88 (2H, t, C(8)H.sub.2N), 3.36 (2H, t, C(17)H.sub.2S), 3.06 (2H, tt, C(9)H.sub.2CF.sub.2), 2.96 (2H, t, C(19)H.sub.2SO.sub.3.sup.), 2.14 (2H, quin, C(18)H.sub.2).

EXAMPLE 6

Synthesis of 3,3-(hexane-1,6-diyl)bis(2-((1H,1H,2H,2H-perfluorooctyl)thio)-1-vinyl-1H-imidazolium) diiodide

[0155] ##STR00014##

[0156] 1.25 g (3.74 mmol) 3,3-(hexane-1,6-diyl)bis(3-vinylimidazole-2-thione) and 7.11 g (15.0 mmol) 1H,1H,2H,2H-perfluorooctyliodide were dissolved in 30 ml acetonitrile and were refluxed for 72 h. 300 ml diethyl ether were subsequently added to initiate precipitation; the reaction mixture was then placed in the freezer at 32 C. for 6 hours. The solid was filtered, washed four times with 30 ml diethyl ether, and was then dried in high vacuum overnight. 3.50 g of yellowish powder (73% of the theoretical yield) were isolated. According to .sup.1H-NMR, there is still approximately 5-10% dithione reactant in the product; further purification was, however, dispensed with.

[0157] .sup.13C NMR (75 MHz, DMSO-d6) 138.14 (s, C(2), 128.57 (s, C(6)), 125.07 (s, C(5)), 120.88 (s, C(4)), 110.52 (s, C(7)), 126-100 (m, perfluorohexyl), 49.02 (s, C(8)), 30.39 (t, C(13)), 28.92 (t, C(12)), 27.18 (s, C(9)), 25.04 (s, C(10)).

[0158] .sup.1H NMR (300 MHz, DMSO-d6), 8.53 (2H, d, C(5)H imidazole), 8.25 (2H, d, C(4)H imidazole), 7.51 (2H, dd, C(6)H vinyl), 6.07 (2H, dd, C(7)H.sub.2 vinyl), 5.54 (2H, dd, C(7)H.sub.2 vinyl), 4.30 (4H, t, C(8)H.sub.2N), 3.27 (4H, t, C(12)H.sub.2S), 2.72 (4H, tt, C(13)H.sub.2CF.sub.2), 1.82 (4H, quin, C(9)H.sub.2 alkyl), 1.39 (4H, t, C(10)H.sub.2 alkyl).

[0159] It is noteworthy in the reaction that the vinyl group can be completely removed in other solvents. This was noted with different alkylations at the thione. This secondary reaction can be used directly for an alternative functionalization.

EXAMPLE 7

Synthesis of 3-(1H,1H,2H,2H-perfluorooctyl)-2-((1H,1H,2H,2H-perfluorooctyl)thio)-1-vinyl-1H-imidazoliumiodide

[0160] ##STR00015##

[0161] 1 g (2.12 mmol) 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1,3-dihydro-2H-imidazole-2-thione and 1 g (2.12 mmol) 1H,1H,2H,2H-perfluorooctyliodide were dissolved in 5 ml acetonitrile and were refluxed for approximately 20 h. The cooled reaction mixture was subsequently mixed with 50 ml diethyl ether to completely precipitate the product. It was filtered and washed 3 times with 30 ml diethyl ether in each case; it was then dried in high vacuum. 1.02 g (50% of the theoretical yield) of white powder thus resulted.

[0162] The recording of the .sup.1H-NMR spectrum took place as a perfluorooctyliodide adduct since the pure product is very difficult to dissolve in conventional solvents.

[0163] .sup.1H NMR (300 MHz, acetone-d6), 8.49 (1H, d, C(5)H imidazole), 8.37 (1H, d, C(4) imidazole), 7.75 (1H, dd, C(6)H vinyl), 6.20 (1H, dd, C(7)H.sub.2 vinyl), 5.71 (1H, dd, C(7)H.sub.2 vinyl), 5.07 (2H, t, C(8)H.sub.2N), 3.61 (2H, t, C(17)H.sub.2S), 3.20 (2H, tt, C(9)H.sub.2CF.sub.2), 2.89 (2H, tt, C(18)H.sub.2CF.sub.2).

EXAMPLE 8

Synthesis of 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1H-imidazolium 3-(2-thioxo-3-(1H,1H,2H,2H-perfluorooctyl)-2,3-dihydro-1H-imidazole-1-yl)propane-1-sulfonate

[0164] ##STR00016##

[0165] 0.157 g (0.33 mmol) 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1H-imidazoliumchloride and 0.200 g (0.33 mmol) potassium 3-(2-thioxo-3-(1H,1H,2H,2H-perfluorooctyl)-2,3-dihydro-1H-imidazole-1-yl)propane-1-sulfonate were stirred into 10 ml acetone at room temperature overnight, the produced KCl was subsequently filtered, and the acetone was removed using a rotary evaporator. The conversion is quantitative; 263 mg (79% of the theoretical yield) was isolated.

[0166] .sup.1H NMR (300 MHz, acetone-d6), 9.86 (1H, t, C(2)H imidazole), 8.28 (1H, t, C(5)H imidazole), 8.12 (1H, t, C(4)H imidazole), 7.43 (1H, dd, C(6)H vinyl), 7.22 (1H, t, C(20)H imidazole), 7.21 (1H, t, C(19)H imidazole), 6.05 (1H, dt, C(7)H.sub.2 vinyl), 5.55 (1H, dt, C(7)H.sub.2 vinyl), 4.75 (2H, t, C(8)H.sub.2N), 4.35 (2H, t, C(21)H.sub.2N), 4.13 (2H, t, C(28)H.sub.2N), 3.25 (2H, s (br), C(30)H.sub.2SO.sub.3), 3.13 (2H, tt, C(9)H.sub.2CF.sub.2), 2.81 (2H, tt, C(22)H.sub.2CF.sub.2), 2.48 (2H, quin, C(29)H.sub.2).

EXAMPLE 9: Synthesis of 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1H-imidazolium Acid Blue 215

[0167] ##STR00017##

[0168] 0.600 g (1.18 mmol) Acid Blue 215, sodium salt and 0.562 g (1.18 mmol) 1-(1H,1H,2H,2H-perfluorooctyl)-3-vinyl-1H-imidazoliumchloride were stirred into 20 ml acetone at room temperature overnight, the produced NaCl was subsequently filtered, and the acetone was removed using a rotary evaporator. The conversion is quantitative; 973 mg (1.05 mmol, 89% of the theoretical yield) were isolated.

[0169] .sup.1H NMR (300 MHz, acetone-d6), 12.00 (1H, s, NH sec. amine), 9.75 (1H, s, C(2)H imidazole), 8.28, 7.78 & 7.63 (9H, m, CH aromatic), 8.15 (1H, s, C(5)H imidazole), 8.06 (1H, s, C(4)H imidazole), 7.41 (1H, dd, C(6)H vinyl), 7.03 (1H, dd, CH vinylsulfone), 6.43 (1H, dd, CH.sub.2 vinylsulfone), 6.19 (1H, dd, CH.sub.2 vinylsulfone), 6.00 (1H, dd, C(7)H.sub.2 vinyl), 5.43 (1H, dd, C(7)H.sub.2 vinyl), 4.89 (2H, t, C(8)H.sub.2N), 3.25 (2H, s(br), NH.sub.2), 3.17 (2H, tt, C(9)H.sub.2CF.sub.2).

EXAMPLE 10

Preparation of Hydrophobic and Oleophobic Cotton:

[0170] A cotton fabric having a size of 1845 cm and a weight of 10.53 g was washed with 1.3 liters water and 2.45 kg wetting agent (Kiralon Jet B of BASF). The room temperature was 77.5 C. Half an hour after the end of washing, the temperature was still 55.7 C.

[0171] The textile was subsequently rinsed 3 times with warm mains water.

[0172] It was then dried at 95 C. for three minutes. A piece having the dimensions 1110 cm and a weight of 1.41 g was subsequently cut out. It then had the recipe shown in Table 2 that had previously been treated in the ultrasound bath for 10 minutes dripped on it by a pipette until the total fabric was completely saturated with the liquid.

TABLE-US-00002 TABLE 2 3-(1H,1H,2H,2H perfluorooctyl)-1-vinyl- 3.01 1H-imidazoliumiodide Azobis(iosobutyronitrile) 1.00 Ethanol, denat. 96% 95.95 3,3-(hexane-1,6-diyl)bis(2-((1H,1H,2H,2H- 0.04 perfluorooctyl)thio)-1-vinyl-1H-imidazolium) diiodide 100.00

[0173] The tissue was now liberated from the excess liquid between two rollers at a pressure of 2 bar and was left in the open at room temperature for 5 minutes. The textile was subsequently placed in the drying oven at 95 C. for 5 minutes. It was then washed 5 times with water at 55 C. The cotton fabric was subsequently placed in the drying oven at 150 C. for 5 minutes.

[0174] The textile treated in this manner was now water-repellent and oil-repellant and drops applied to this material were not absorbed even after 1 minute. The contact angle of water was 124 on average. The contact angle for diiodomethane was 123 on average. FIG. 11 shows an image of water droplets on the fabric.

[0175] Different fabrics were also able to be made hydrophobic with slightly modified parameters.

EXAMPLE 11

Manufacturing a Coating for Winter Sports Equipment

[0176] 3 g 3-(1H,1H,2H,2H perfluorooctyl)-1-vinyl-1H-imidazoliumiodide were partially pre-dissolved with 1.0 g diethylacrylamide and subsequently mixed with 1.5 g laurylacrylate. 40 ml isopropanol and 0.1 g 2-hydroxy-2-methyl-1-phenyl-1-propanone were subsequently added. This mixture was then stirred for 10 minutes in a 100 ml glass beaker while stirring using a UV lamp at approximately 365 nm and at a power of 4 W/cm.sup.2 and at a distance of 10 cm. The solution thereupon changed color to a reddish brown hue.

[0177] The alcohol was subsequently removed and the gel-like polymer was thus obtained. 1.3 g of the polymer mixture obtained in this manner were mixed with 0.03 g SiO.sub.2 nanoparticles 10-20 nm of Sigma Aldrich.

[0178] The coating for winter sports equipment obtained in this manner was then ironed onto a cross-country ski at 130-150 C.

[0179] The obtained product was tested against a commercial product (Fluoropow Middle of HWK) on hard, coarse-grain artificial snow, at an air temperature of 4 C., at a snow temperature of 0.3 C., and at a snow moisture of 25-30%. The test was performed on a slight downhill slope. To exclude external influences, the average time was determined over 6 runs. The time was taken by means of 2 light barriers.

[0180] The Fluoropow Middle product had a time of 11.49 seconds.

[0181] The newly manufactured product had an average time of 11.45 seconds and was thus 0.04 seconds faster over this short distance.

[0182] In addition, this product had no harmful C.sub.8F.sub.17 chains or longer fluoroalkanes. It has a much higher environmental compatibility in comparison with the conventional products.

Examples 12 to 19 and Comparison Examples A to C

[0183] All the examples and comparison examples shown in Table 3 were mixed in the indicated percentage ratios and were subsequently placed briefly into the ultrasound bath. The films were subsequently applied to a glass plate. Spacers of a thickness of 75 m were inserted on both sides and a PET film was then added with the siliconized side facing downward. A slight pressure was subsequently applied to the PET film so that a homogeneously distributed film is produced. The samples thus prepared were then irradiated with UV light at 365 nm for approximately 10-30 seconds.

[0184] Example 12 uses a functionalized monomer in accordance with FIG. 1 having a transverse crosslinker. The composition furthermore contains SiO.sub.2 nanoparticles and solvents. Better contact angles are achieved than for Comparison Examples B and C and values equivalent to Comparison Example A were achieved (problematic from a technical environmental aspect).

[0185] Example 13 uses a functionalized monomer having a halogen complex and a transverse crosslinker, SiO.sub.2 nanoparticles, and solvent. Better contact angles are achieved than for Comparison Examples B and C and even better values were achieved than Comparison Example A (problematic from a technical environmental aspect).

[0186] 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1H-imidazoliumbis(trifluormethanesulfonyl)amide is present as the functionalized monomer in Example 14. Better contact angles were achieved than for Comparison Examples B and C.

[0187] Example 15 shows a composition without particles that contribute to the surface roughness. Due to the lack of a lotus effect, the values for the contact angles are lower than in the remaining examples in accordance with the invention.

[0188] Example 16 comprises a crosslinker monomer in accordance with FIG. 3A and, as an additive, an ionic liquid having fluoro chains that is not polymerizable. The results are so-to-speak superior to the Comparison Examples.

[0189] Examples 17 and 18 comprise functionalized monomers having longer perfluoroalkyl chains, with good results being achieved, but with the long perfluoroalkyl chains being of concern from a technical environmental aspect. The coating in Example 17 is here on the non-siliconized side of a PET film and not, as in the other examples, on a glass carrier. FIG. 10 shows an image of the coating manufactured in accordance with Example 17. A drop of olive oil is at the top left and a water droplet at the bottom right.

[0190] Example 19 comprises a functionalized monomer having a short fluoro chain, with competitive results likewise being achieved.

[0191] Comparison Example A comprises an acrylate monomer known from the prior art that has good contact angles, but is pollutive.

[0192] Comparison Example B comprises an acrylate monomer known from the prior art and having a short perfluoroalkyl chain that is environmentally compatible, but achieves worse values than the compositions in accordance with the invention.

[0193] Comparison Example C comprises a vinylimidazolium known from the prior art without fluoro side chains that is environmentally compatible, but that likewise achieves worse results than the compositions in accordance with the invention.

TABLE-US-00003 TABLE 3 12 13 14 15 16 17 18 19 A B C 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1H- 15.7 imidazoliumiodide 2-hydroxy-2-methyl-1-phenylpropane-1-one 5.4 1.7 2.6 5.6 2.7 3.6 3.6 3.1 2.6 2.4 3.4 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl- 15.3 1H-imidazoliumiodide-1-iodoperfluorooctane 3M.sup. Novec 71 IPA 43.3 33.9 44.9 27.1 27.2 27.2 28.8 19.5 Isopropanol 27.6 33.9 27.1 45.3 45.3 28.8 32.5 8.6 3M Novec 7500 27.3 Hexanediol diacrylate 50% SiO.sub.2 50% 11.1 15.3 12.8 9.1 9.1 19.2 13.0 50.0 35.0 (Nanocryl C140) 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1H- 39.7 47.4 imidazolium bis(trifluormethanesulfonyl)amide 3,3-hexamethylenbis(1-vinylimidazolium)- 47.0 di(bis(trifluormethanesulfonyl)amide) SiO.sub.2 nanoparticles saturated with 1-methyl- 0.7 2-((1H,1H,2H,2H-perfluorooctyl)thio)-1H- imidazole 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl- 13.5 2-((4-vinylbenzyl)thio)-1H-imidazoliumchloride 1-methyl-2-((1,H,1H,2H,2H-perfluorooctyl)thio)- 28.9 1H-imidazolium 1,1,1,5,5,5-hexafluoro-2,4- dioxopentane-3-ide 3-(1,H,1H,2H,2H-perfluoropentyl)-1-vinyl- 19.2 1H-imidazoliumiodide 3-(1,H,1H,2H,2H-perfluoro decyl)-1-vinyl- 14.8 14.8 1H-imidazoliumiodide 1H,1H,2H,2H-perfluoroalkyl-1-methacrylates 32.5 (CAS: 65530-66-7) Pentafluoropropylacrylate 47.6 3-octyl-1-vinyl-1H-imidazoliumiodide 53.0 Water contact angle [] 134 146 130 105 145 151 139 137 141 109 94 Diiodomethane contact angle [] 126 136 114 90 147 144 126 130 124 76 55

EXAMPLE 20

Measurement of the Surface Tension of 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1H-imidazoliumchloride

[0194] The surface tension was determined at a suspended drop using a Drop Shape Analyser DSA 25 of the Krss corporation. The measurements were performed at temperatures between 23.5 and 25.0 C. and at a relative humidity of approximately 15-30%. The sample was measured a total of ten times. The standard deviation is marked by s in Table 4 shown below.

TABLE-US-00004 TABLE 4 c OFS (w/w %) (mN/m) s 1 20.58 0.15 0.5 21.94 0.63

[0195] The monomer in accordance with the invention produced a considerable reduction of the surface tension of water in the indicated concentration ranges.

EXAMPLE 21

Copolymer for Textile Coatings

[0196] The components listed in Table 5 below were mixed, were heated to 80 C., and were treated with ultrasound for 10 minutes. An emulsion was produced here.

TABLE-US-00005 TABLE 5 Substance Quantity Butylacrylate 4.24 g 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1H- 5 g imidazoliumchloride (purity >95%) 3-(1H,1H,2H,2H-perfluorooctyl)-2-((1H,1H,2H,2H- 3.26 g perfluorooctypthio)-1-vinyl-1H-imidazoliumchloride (purity >95%) Water 72 g

[0197] The emulsion produced was rinsed with argon. A solution of 0.20 g 2,2-azobis(2-methylpropionamidine)-dihydrochloride in 2 g water was subsequently added at 80 C. The reaction mixture was held at 80 C. overnight.

[0198] Approximately 2 g of a macroscopic copolymer that was then removed using a paper filter was formed at the bottom of the test tube.

[0199] The (latex) emulsion thus obtained was diluted with 20 g water, was applied to a textile of cotton, and was dried at 50 C. for 5 minutes. The fabric was subsequently heated at 150 C. for 1 minute.

[0200] The textile thus treated was examined as to its hydrophobic and oleophobic properties. Pronounced water-repellant and oil-repellant properties were displayed. A value of 5.5 was obtained in the AATCC Test 118 with n-dodecane. The test is described in detail in paragraph [0038] of EP 2 057 201 B1.

[0201] In addition to the textile fabric, a paper was wetted with the emulsion and was dried in air overnight. A film was formed that was repellant with respect to dodecane.

EXAMPLE 22

Copolymer for Textile Coating

[0202] The components listed in Table 6 below were mixed, were heated to 40 C., and were treated with ultrasound for 15 minutes to produce a stable emulsion. A temperature increase to almost 60 C. was observed during the ultrasound treatment.

TABLE-US-00006 TABLE 6 Substance Quantity Octadecylacrylate 1.5 g Butylacrylate 0.5 g 3-(1H,1H,2H,2H perfluorooctyl)-1-vinyl-1H- 0.2 g imidazoliumchloride (purity >95%) 3-(1H,1H,2H,2H-perfluorooctyl)-24(1H,1H,2H,2H- 2 g perfluorooctyl)thio)-1-vinyl-1H-imidazoliumchloride (purity >95%) Hydroxyethylmethacrylate 0.1 g N-(Isobutoxymethyl)acrylamide 0.11 g Glycidylmethacrylate 0.15 g GenopolX080 (=polyethylenglycolmonoalkylether of the 0.1 g Clariant corporation) Diethyleneglycolmonobutylether 7.25 g Water 40 g Dodecanethiol 0.2 g

[0203] The emulsion was subsequently heated to 80 C. and held under a protective gas atmosphere. After an hour, a solution of 0.2 g 2,2-azobis(2-methylpropioneamidina)-dihydrochloride in 3 ml water was added and the resulting mixture was held at 80 C. for 6 hours up to the complete reaction. The solution obtained was diluted with 30 g water to obtain a product solution.

[0204] A cotton fabric was wetted with this product solution, was dried at 50 C., and was fixed at 150 C. for 2 minutes. It demonstrated water-repellant and oil-repellant properties.

EXAMPLE 23

Copolymer for Lacquer Applications

[0205] The components listed in the following Table 7 were mixed at room temperature.

TABLE-US-00007 TABLE 7 Substance Quantity 2,2-dimethoxy-2-phenylacetophenone 10 mg 3-(1H,1H,2H,2H perfluorooctyl)-1-vinyl- 85 mg 1H-imidazoliumiodide (purity >99%) Ethylenedimethacrylate 100 L 1-Propanol 125 L Acetonitrile 125 L Water 75 L

[0206] Two glass plates were pretreated with triethoxyvinylsilane in 96% ethanol. The glass plates were then placed face on face and were set using a spacer to a spacing of 75 m. The mixture in accordance with Table 7 was introduced between the plates using a pipette. Curing was subsequently performed with a UV lamp at 365 nm. The two plates were subsequently carefully separated from one another. A macroscopic coating that was water-repellant and oil-repellant formed on both glass plates.

[0207] The measured contact angles of the coated surfaces were above 160 both for water and for diiodomethane and hexadecane.

[0208] Microscopic photographs of the coated surfaces are shown in FIGS. 12A and 12B. A very rough surface was to be expected due to the high contact angles of the coating in accordance with the invention, which was able to be confirmed by these photographs. The surface roughness is an important feature of superomniphobic coatings. The lotus leaf is often used as a model from nature; it has a rough surface that has omniphobic and therefore self-cleaning properties.

[0209] An influence of the solvents used on the contact angles was able to be determined. The mixture used of 1-propanol, acetonitrile, and water here resulted in high contact angles and in a high surface roughness. Other mixtures demonstrated similarly good contact angles and surface roughnesses.

EXAMPLE 24

Copolymer for Textile Coating

[0210] The components indicated in the following Table 8 were intensely stirred in an autoclave under an inert gas atmosphere at 60 C. to produce an emulsion.

TABLE-US-00008 TABLE 8 Substance Quantity Stearyl acrylate 22.5 g Vinylidene chloride 15.5 g N-methoxymethylacrylamide 1 g Hydroxyethylmethacrylate 1 g Dipropyleneglycol 30 g Dodecanethiol 0.5 g Genapol 100 (oligoethyleneglycolmonoalkylether/ 4 g Sigma Aldrich) Hexadecyltrimethyl ammonium chloride (25% 3.5 g solution in water) Water 200 g 1H,1H,2H,2H-perfluorooctylmethacrylate 40 g 3-(1H,1H,2H,2H-perfluorooctyl)-2-((1H,1H,2H,2H- 15 g perfluorooctyl)thio)-1-vinyl-1H-imidazoliumchloride (purity >95%) 3-(1H,1H,2H,2H-perfluorooctyl)-1-vinyl-1H- 5 g imidazoliumiodide (purity >95%)

[0211] 0.6 g 2,2-azobis(2-methylpropioneamidine)-dihydrochloride were added to the emulsion thus obtained. The resulting reaction solution was held at 60 C. for 6 h to perform the polymerization reaction. Non-reacted vinylidene chloride was subsequently distilled. The solid portion of the residue was approximately 30%. 5 g/l of a polyisocyanate (Cassurit FF, Archroma) was added to the residue for better adhesion to the textile fabric.

[0212] A textile of cotton was wetted with the product solution thus obtained, was dried at 50 C., and was fixed at 150 C. for 1 minute. The textile obtained was water-repellent and oil-repellant. These properties were also still observed after five washing procedures.

EXAMPLE 25

Copolymer for Lacquer Applications

[0213] 0.15 g 3-(1H,1H,2H,2H-perfluorooctyl)-2-((1H,1H,2H,2H-perfluorooctyl)thio)-1-vinyl-1H-imidazoliumchloride and 0.05 g 3-(trimethoxysilyl)propylmethacrylate were stirred in 5 ml ethanol with 0.005 g azobisisobutyronitrile at 65 C. under an argon atmosphere for 6 h. A glass body was subsequently pretreated with 3-(trimethoxysilyl)propylmethacrylate and then wetted with the prepolymer solution obtained as described above and with 0.005 g 2-hydroxy-2-methylpropiophenone. The prepolymer was then covalently bonded to the glass using a UV lamp at a wavelength of 365 nm.

[0214] The glass coated in this manner also demonstrated even more hydrophobic and oleophobic properties than untreated glass after an intense washing.

EXAMPLE 26

Hydrogel

[0215] The components listed in Table 9 below were stirred to form a homogeneous solution.

TABLE-US-00009 TABLE 9 Substance Quantity Hydroxyethylmethacrylate 30 ml Ethyleneglycoldimethacrylate 0.52 g Water 18 ml 3-(1H,1H,2H,2H perfluorooctyl)-1-vinyl-1H- 5 g imidazoliumchloride 2,2-dimethoxy-2-phenylacetophenone 0.52 g

[0216] The solution thus obtained was applied to a substrate and was cured using UV light at 365 nm. A transparent hydrogel was produced. These and comparable compositions could be used in contact lenses.