DE1768939A1 - Fluoroalkylamino or ammonium compounds which have a long-chain perfluoroalkyl radical in the ss-position to the nitrogen - Google Patents

Description

Fluoroalkylamino or ammonium compounds which are in the ß-position to the Nitrogen carry a long-chain perfluoroalkyl radical.

The present invention relates to a new class of compounds the surface tensions in organic or aqueous solutions of less than Can generate 20 dynes / cm and, when absorbed, produce an oleophobic effect. This effect is achieved by chemical cross-linking and anchoring in accordance with the invention these layers on the suostrat are washable and solvent-proof.

The compounds according to the invention are due to the high surface activity Excellent as wetting agents and foam stabilizers for the production of plastic foams suitable. By simultaneous reaction during foaming of polyurethane reaction mixes After foaming, the wetting agents no longer make themselves troublesome due to creep and put noticeable. The simultaneous oleophilic effect gives the solid foams Excellent dirt and oil repellency, as is desirable for textile applications is.

These properties are mainly achieved in that just a 2 carbon atom chain between nitrogen and a long fluorocarbon chain which means that at this point, without affecting the nature of the nitrogen, a minimally oleophilic kest is connected. This applies to light for Ver @ indun en according to dom US Pat. 3 257 407, British Pateiit 689 425, 717, 232 US Pat 2,537,976 U.S. Pqt 2,624,746 and described by Henne A.L. and Stewart J.J., Journal of the American Chemical Society Volume 77, Page 1901, Volume 1951 a Another part of the invention is the use of these Verbinaungen, as far as they are with formaldehyde or methylol resins are conaensable as oleophobic and hydrophobic Impregnating agents for textiles, paper and leather.

An additional part of this invention relates to the manufacture of the Compounds according to the invention from 1-iodo-1,1,2,2-tetrahydroperfluoroalkanes through Reacting with primary or secondary amines, which despite the high sensitivity of the Starting material against elimination of hydrogen iodide proceeds with quantitative yield.

This is particularly surprising because when these iodine compounds are implemented with other nucleophilic agents such as sodium alcoholates, KCN, sodium acetylacetone only very low yields can be obtained as a result of the elimination of hydrogen iodide. This is also true for nucleophilic reagents that are primary amines or quaternary Ammonium compounds should lead.

This high sensitivity for, 3-elimination-cleavage is exclusive the 1-iodo-1,1,2,2-tetrahydroperfluoroalkanes inherent.

In this easily accessible group of substances, ds according to the invention Process to avoid splitting off of hydrogen iodide.

This new class of surface-active substances is secondary, tertiary and quaternary ammonium fluorine compounds, which are characterized by the fact that the compounds in position to the nitrogen contain at least one terfluoroalkyl radical of 6 to 20, advantageously 7 to 16, in particular carry 8 to 14 carbon atoms and contain at least one further non-fluorinated organic substituent bonded to nitrogen, which advantageously carries strongly polar functional groups. That class of compounds which is characterized by the general formula of the amines is advantageous here wherein or ammonium compounds of E'ormelr [RfCH2.CH2ÜR32 where Rf is a perfluoroalkyl radical of 6 to 25 0 atoms, advantageously 7 to 18 carbon atoms, in particular CF3 (CF2 # 7, CF3 (CF2 # 9, CF3 (CF2 # 11, R1 is an aliphatic radical, advantageously a small alkyl radical, of 1 to 3 carbon atoms, especially methyl or, advantageously, an aliphatic radical that contains strongly polar functional groups, R2 is hydrogen or an organic radical, advantageously a small alkyl radical of 1 to 3 0 atoms, in particular methyl, or advantageously an organic radical that contains strongly polar functional groups, R3 is hydrogen or a small alkyl radical of 1 to 3 carbon atoms, an acid residue, advantageously the residue of a strong kineral acid, in particular chloride ion, bromine ion, or a sulfate ion equivalent.

But especially those amines according to the above formula in which R1 has the formula with n = 1 to 6, advantageously 1, Z1, Z2, Z2, Z3 and R2 - hydrogen or a small alkyl radical with 1 to 3 carbon atoms, advantageously a functional aliphatic radical of the formula: - (C2H4O) mH with m = 1 to 20, advantageously 1, -C2H4COOH, in which the carboxyl group can also be present as a salt, -C2H4CONX1X2, in which X, X2 is hydrogen or CH2OH, or tertiary amines or ammonium compounds with a fluorine-free cyclic. Double ligands, characterized in that R1 and R2 form a contiguous ring of the formula form, where Z is defined according to claim 3. A particularly valuable group of compounds which stands out from the general inventive concept due to special properties which are very valuable for textile impregnation are amines of the general formula defined above characterized in that Rf is a perfluoroalkyl radical having 6 to 25, advantageously 7 to 18, but especially 7 to 12 carbon atoms, R1 is a small alkyl radical having 1 to 3 carbon atoms, and that all groups R, Z defined in this description , Z the formula: givenialis in the form of the hydrochloride, in which X1, X2, X3, X4 is hydrogen or -CH2OH, X1 and X3 in particular hydrogen and X2 and X4 = CH2OH, the group -CH2OH optionally also being acetal-like to ethylene or polyethylene glycol or glycerol, accordingly of the formula -CH2O- (C2H4O) nH can be bonded. Of that group of compounds, those parts are particularly effective which the formula 1 (c, rl Iv CE '? NC CN N N t N 3 '\ 4 where n = 7 or 9, xl, X2, X3, X4 s hydrogen or CH2-O (C2H4O) pH with p = 0 to 20, preferably 0, where advantageously X and X3 are hydrogen and X2 and X4 -CH2OH.

These compounds are prepared according to the invention by a.) 1-iodo-1,1,2,2-tetrahydroperfluoroalkanes having 8 to 27 carbon atoms with primary or secondary amines of the general formula R1 a small alkyl radical, or a radical of the formula or-C2H4.NH.C2H4NH2, with R4, R5 = hydrogen, or a small alkyl radical of 1 to 3 carbon atoms, R2 = hydrogen or a small alkyl radical of 1 to 3 carbon atoms, but advantageously with HN (CH3) 2, H2NCH3, or H2N.C2H4NH2, is, in which one works in homogeneous solution, preferably at temperatures of 20 to 100 ° C, and in ethers, in particular a gamiscil of 50 GeN.% Tetrahydrofuran and diisopropyl ether, with a molar excess of amine and Verwilzeiten provides from 1 minute to 1 hour, b.) optionally reacting the free amines formed with ethylene oxide, acrylic acid, or their derivatives or alkylating agents, cL) and / or optionally the free amines formed which still contain at least 1 hydrogen atom bonded directly to nitrogen, advantageous the secondary amines are reacted with 2,4,6-chloro- or amino-s-triazines or dicyanamide, optionally at higher temperatures, with the use of 2,4,6-triamino-striazines also the mineral acid salts of F luoroalkylamines can be used, c2.) and, if appropriate, converts the amines with formula aldehyde obtained thereby, preferably in alkaline aqueous media. in the case of the preparation of particularly valuable 2-fluoroalkyl-4,6-diamino-s-triazines, the best yields are obtained in a smooth reaction, characterized in that secondary-'fluoroalkylamines prepared according to the invention are obtained with 2-chloro-4,6-diamino- striazine or dicyanamide at leuperatures of 80 to 1600C, if necessary in a solvent, and the 2-fluoroalkyl-4,6-diamino-s-triazines formed with formaldehyde or a formaldehyde donor, such as paraformaldehyde, hexamethylene triamine or hemiacetals (the formaldehyde with ethylene glycol or polyethylene preferably by means of alkaline catalysis between = 7.1 to 10.5 with 1 to 8 molar amounts of formaldehyde, at temperatures of 30 to 80 ° C.

With the compounds prepared in this way, if they are used as a methylol compound present or condense with formaldehyde or methylol compounds are good Produce oil-repellent impregnations on substrates of a fibrous-porous type. It deals are all compounds defined in this invention which the grouping en -CONH2, -CONHCH2OH, -CON (CH2OH) 2.

Particularly permanent effects on substrates of a fibrous-porous type, such as According to the invention, textiles, paper or leather are obtained by eating them Substrates in aqueous solutions or dispersions of the fluoroalkylamino according to the invention or methylolamino-s-triazine together with an acid-releasing catalyst or Magnesium chloride is moistened or soaked, and substrates are dried and then dried to 120 ° C heated to 1600C and rewashed if necessary.

An increase in the deophobic effect is achieved with simultaneous use known hydrophobic impregnations, advantageous together with reactive anti-crease impregnations, In particular, formaldehyde-urea or nelamine condensates are obtained.

The compounds according to the invention are distinguished by their extraordinary properties Reduction of the surface tension in aqueous organic solvents the end. Interfacial tensions of 15 dyn / cm are achieved. The critical one Micellar concentration is exceptionally low, s @ da # the products in their grounding are extremely economical. Kit iiien can be polishing waxes with high Create use value? I. The FluoralKylmelaminmethylolverbindungen are surface-active Substances that can be inactivated by heating and thereby permanent oleophobic Can produce surfaces on solids. Used to make connections the corresponding 1-iodo-1,1,2,2-tetrahydroperfluoroalkanes with primary or secondary Amines made in homogeneous solutions, with some LiNO3 as a catalyst advantageous is added and an approximately 10-fold stoichiometric excess of amine is used will. At whom optimal reaction temperatures between 40 to 100 ° C are required when applying of primary or secondary monoamines not necessarily a solvent, when using die or polyamines, is a solubilizer however absolutely necessary, whereby tetramethylene sulphate, but especially a Proven from tetrahydrofuran with diisopropyl ether. One works best doing this under slightly increased pressure by about 80 ° C and almost always gets within Complete and quantitative conversion within 10 minutes. From the reaction mixture the heavier phase, if any, is separated off and the lighter phase is carried out fractional distillation freed from solvent and lower amine. The heavy one Phase and the distillation residue is then concentrated in a vacuum using caustic soda or a concentrate Potassium hydroxide solution is distilled off, bound to caustic soda with the water that has passed over and that Amine starting material is removed from the distillate by hectic. This imine so far if they still contain a hydrogen atom bound to nitrogen, they can become tertiary Amines can be converted by addition to ethylene oxide or acrylic acid derivatives.

If you work with ethylene oxide, then unpressurized introduction of ethylene oxide is sufficient in solutions of these amines. After evaporation, completely ethoxylated ones are obtained Products with excellent surfactant properties.

If you work with a large excess of Äthylenoxya at 100 ° C under Pressure in the presence of alkali as a catalyst gives connections, @ie carry a long residue of polyethylene glycol, the length of which is equal to the excess ethylene oxide used depends.

The products are excellent surfactants for foaming polyurethane. In contrast, the addition of acrylic acid salts, acrylonitrile but especially acrylic acid amide pressureless at approx.

50 0C to 100 ° C. A solvent can be used well here.

Fluoroalkylated melamines and their methylol compounds can be simply by stoichiometric conversion of all primary, secondary amine groups of the Fluoroalkylamines with dicyanamide at 1200C to 200 ° C. Very uniform However, products are made by reacting the amines with 2-chloro-4,6, diamino-s-triazine obtained in polar or non-polar solvents, but also in water.

The reaction times are 5 minutes to 3 hours. For provision the tetramethylolmelamine must work with molar amounts of formaldehyde of 1 s 6 earth. The products are carefully neutralized. As an aqueous solution or dispersion at PH = 7 they have good stability. You can always be with water dilute @, to which magnesium chloride is added as a catalyst. If you wet it with such Solutions that can contain 0.1 to 1% perfluoroalkyl groups @, a fibrous-porous substrate, such as textiles, leather or paper, or it adds to the If papermaking uses the pulp, oil repellency values are obtained after drying and hardening from 100 to 130 points.

These oil repellency values are determined by the paraffin-n-heptane solution woraen, uie not yet wetted; they are calculated from the n-heptane content the highest possible concentration in paraffin oil + 50. Selects as hardening temperature temperatures from 100 ° C to 1600C and times up to 15 minutes. For improvement the oil and water repellency values can simultaneously be known hydrophobic impregnations with the exception of the silicones. The washability of impregnations achieved in this way is good.

EXAMPLE 1 10 g of C8F17.CH2.CH2J and 30 mg of LiNO3 were dissolved in a mixture of 4 g of tetrahydrofuran, 4 g of diisopropyl ether and 8 g of isopropanol with gentle heating, and 10% of CH3NH2 was then added at -300C. The inclusion tube was then heated to 80 ° C. with shaking. After 3 hours the Bemben tube was cooled and opened. Excess amine was evaporated off together with the solvent via a spinning band column and 10.4 g of C8F17.CH2.CH2.NH.CH3.HJ were obtained as Bückstana, which according to gas chromatographic analysis of the free base was 6.4% (C8F17.CH2.CH2 ) Contained 2NCH3.HJ. The amine was released from this by means of concentrated ratron hydroxide solution and distilled off at 10 mm Hg. 7.65 g of C8F17.CH2.CH2.NH.CH3 get what 92 9 corresponds to the theory. The hydrochloride of this imine has a high surfactant power in neutral and acidic areas. It allows a better homogenization of emulsions of immiscible organic phases than non-fluorinated surfactants.

Example 2 As in Example 1, 10 g of C10F21C2H4J with 8 g of CH3NH2 implemented and processed. 7.7 g of C10F21C2H4 .NH.CH3 in 90 ffi Yield obtained.

Example 3 As in Example 1, 10 g of C10F21C2H4J were added with 1 g of (CH3) 2NH implemented. After working up, 8.6 g of C10F21.C2H4.N (CH3) 2 with 9 @% yield obtained. The hydrochlorides and sulfates, according to Example 2 and 3 prepared amines, allow as an additive to polishing wax in amounts of 0.01% a suppression of water staining. As an additive to polyurethane-polyether reaction mixtures very fine-cell foams are obtained.

Example 4 As in Example 1, 10 g of C8F17.C2H4J were mixed with 10 g of anhydrous Ethylenediamine implemented. It was only 1 hour at atmospheric pressure with stirring boiled on reflux. Two liquid phases formed and were separated. The lighter phase was neutralized with aqueous hydrochloric acid in a rotary evaporator evaporated in an additional stream of air. The dry pasty mass was taken up in 20 cc of water. This solution mainly contained that Chlorine of the amine C8F17C2H4.NH.C2H4.NH2 next to the bisalkylated amine. The surfactant power aqueous solutions was very large #. With a concentration of 0.01%, 16.5 dynes / cm could be achieved (measured according to the @@ r capillary method).

The product was well suited for the foam stabilization of organic systems and bilaete very fine-cell foams. The free amine could by adding excess 20% sodium hydroxide solution can be precipitated in aer heat as the heavier liquid phase solidified at room temperature and soluble in water in the complete absence of lye ar. This precipitation gave 8.5 e of crude amine, as according to gas chromatography Analysis approx.

7, b 'g C8F17.C2H4.NH.C @ 2H4NH2. The yield based on Fluoroiodalkane was 87%.

Example 5 5 g of C12F25.C2H4J were, as in Example 4, with 1 g of diisopropylamine implemented. 4.6 g of C12F25.C2H4N [CH (CH3) 2] 2 were obtained, which in a vacuum of less than 2 mm Eg column could be deutillated. The yield was 95%.

This amine was a very good surfactant in salt form, which in concentrations of less than 0.01% the surface tension of aqueous solutions to about 16 dynes / cm lowered. As a foam stabilizer for the production of polymer foams, such as polyurethane, but also polyethylene, very fine-cell, stable structures could be achieved.

Example 6 5 g of (CF3) 2CF (CF2) 6C2H4J were reacted with 5 g of piperazine as in Example 4. 4 g obtained in 87% yield, based on fluoroalkyl iodide.

Excess piperazine was recovered. When used in small concentrations, the amine salt produced very stable foams in aqueous and organic media. It was suitable as a good foam stabilizer in the production of plastic foams. Example 7 As in Example 4, 2 g of C18F37C2H4J were reacted with 0.35 g of piperidine. After all the flat compounds had evaporated, the hydroiodide remained in an amount of 2.1 g. The free solid base could be precipitated as a solid paste by finely dispersing it in 3% sodium hydroxide solution.

Example 8 As in Example 4, 5 g of C10F21C2H4J were mixed with 2 g of morpholine implemented.

There were 5.5 g of amine hydroiodide in almost 100% yield.

The salt was able to be neutralized by precipitation of the free base and subsequent neutralization can be converted into the chloride with hydrochloric acid.

The salts had @ute surfactant properties and were used as foam stabilizers suitable for plastics.

Example 9 10 g of C7 15C2R4J were mixed with 12 g of H2N.C2H4.NH.C2H4NH2, such as in Example 4, implemented. After the solvent had been distilled off, with 20 ccm 20 pointer sodium hydroxide solution and the amine mixture of C7F15.C2H4.NH.C2H4NH.C2H4NH2 and C7F15.C2H4.N (C2H4NH2) 2 as well as some difluoroalkylamine as the heavy liquid phase precipitated and severed.

After neutralization with dilute o-phosphoric acid to the neutral salt a strong surfactant without corrosive effects on iron could be obtained.

Example 10 As in Example 4, 5 g of CloF21C2H4J were mixed with 10 g of 1,6-diaminohexane implemented and after neutralization of the reaction mixture with aqueous hydrochloric acid Evaporated to dryness in the porcelain chamber in the drying cabinet. From the thus obtained Salt were released with 20% sodium hydroxide bases and extracted with ether.

Then everything was excess on the spinning band column with a 20 mm Hg column Solvent and excess 1,6-diaminohexane distilled off. In the residue were 5.7 g of fluoroalkylamine containing 5.0 g of C10F21.C2H4.NH (CH2) 6NH2 are obtained, The salts of the amine are highly surface-active when dissolved in water.

Example 11 5 g of C8F17C2H4J became 5 g of anhydrous ethylenediamine dissolved in 10 cc of tetrahydrofuran and 10 cc of diisopropyl ether and the mixture boiled with vigorous stirring under reflux for 2 hours. This was followed by cooling and cliuttelt with 25 com water and 5 ccm 20 pointer sodium hydroxide solution. Make an addition of 20 cc CFCl2.CF2Cl was shaken well and the organic phase as the heavier Liquid extract deposited. The remaining aqueous solution was again with a mixture of 5 g tetrahydrofuran, 5 g diisopropyl ether and 10 g CFCl2.CF2Cl shaken out and also this organic phase together with after the deposition the first extract is rectified via a spinning band column. After separating the Solvent remained 4.3 g of amines as residue, the 3.8 g of C8F17.CH2.CH2.NH.C2H4NH2 contained. The yield of this alkylated amine was 86 P based on fluoroiodoalkane. If used much less Ethylenediamine levels could be higher Weiden shares of doubly alkylated diamines. If, on the other hand, you set 15 cc Isopropallol is added at the beginning of the experiment, yields of more than 90 are obtained % of theory.

Example 12 10 g of C8F17C2H4.NH.CH3, prepared according to Example 1, were added to a slurry of 3.35 g of 2-chloro-4,6-diamino-s-triazine in 10 cc of dioxane and 10 cc of water and with stirring slowly heated to reflux. Some phenolphthalein was added to the mixture. By adding sodium hydroxide solution dropwise, the mixture was always obtained in a weakly alkaline manner in the conversion range of phenolphthalein. After about 4 hours, about 0.02 mol of sodium hydroxide solution had been consumed and the mixture was cooled and the precipitate was filtered off, washed free of chloride with water and dried at 80.degree. It was supposed to be 8g 1 3 C ÆN O8F17. OH2.0H2-NN n Cg-NHS K N <Cz 2 obtained in 96% yield. The elemental analysis showed 15.1% N and 54 ffi F (theory 14.4% N, 55.5% F) Example 13 10 g of C10F21.C2H4NH.CH3, prepared according to Example 2, was used together with 3 g of 2-chloro 4,6-diamino-s-triazine in 15 ccm dioxane heated to reflux with stirring. By adding dropwise 40% aqueous sodium hydroxide solution, as in Example 12, it was ensured that the mixture was always weakly alkaline. After 4 hours, most of the dioxane was distilled off and replaced by an equal amount of water. It was then cooled, filtered and washed. This resulted in 10.6 g obtained in 90% yield. Elemental analysis showed 12.8% nitrogen and 57% fluorine (theory 12.3% N, 58.5% F).

Example As in Example 12, 5 g of (CF3) 2.CF (CF2) 6.C2H4NH.CH3 and 1.8 g of 2-chloro-4,6-diamino-s-triazine resulted in 5.7 g can be obtained. Example 15 CR3 NN 10 g C8F17wCH2iCE2, P CH3CH "- CCI NR2, prepared according to Example 12 II - NN > flflUÖ) ((Ä4 hycirot; ra ge NO. 2 together with 3.5 g of 37% formaldehyde solution, which was adjusted to pH = 8.0 by means of soda solution, were heated to 670 ° C. for about 20 minutes with stirring and then cooled. An aliquot of the sample was evaporated in vacuo and obtain.

The major part of the reaction mixture, however, was with water further diluted to a content of 0.7 ffi. After adding 1 g / l MgC12. 6 H20 was a cotton poplin; a polyester-cotton blend fabric and a woolen fabric therein submerged and pinched-off to about 80%. It was then dried at about 80 ° C and then heated at 14500 for 5 minutes. After washing and drying everything was done Textiles can be tested for an oil repellency value of 120 points. This effect fell to 110 points after 3 delicate washes.

As the oil repellency value, that number was taken according to the formula t Oil repellency value u 50 + s n-eeptane in paraffin oil DAB 6 for the solution with the highest n-heptane content was obtained, which just did not wet the test fabric. If you put the Dad solution 1.2% of a commercially available impregnating agent, for example assign pyridinium compounds, so were also with further dilution on the Half, oil repellency values of 120 points in addition to very good water repellency of the samples achieved.

Example 16 As in Example 15, a mixture of and 20 g of tetrahydrofuran with 5 g of 37 of the above cE 70 g C10F21o2E4§ C-NH Formaldehyde NE2 in water which had been adjusted to pH 8 7.8 with sodium hydroxide solution, heated to reflux with stirring. After 40 minutes the solution was cooled. Evaporation of an aliquot and iodometric determination revealed that there was thus 11 g of a product of the composition was won.

In a 0.6% solution of this product in water together with 2 % MgCl2 were test fabrics made of cotton, and a mohair plush and dipped at 1000C pre-dried. This was followed by heating to 1350 ° C. for 5 minutes and then washing out and dried.

The test samples had oil repellency values of 120 points, which dropped only 10 points after 3 delicate washes. After adding a commercially available, reactive stearyl pyridinium impregnation, about 2%, to the bath, oil repellency values of more than 130 points were obtained in an otherwise identical manner. This increase in the effect was wash-permanent in the same way. Example 17 CH I. 10 g of 0919.02H4-NH were heated to 1500C together with 2 g of dicyanaside and the temperature increased to 21000 within half an hour. The cooled product was finely ground and, as in Example 15, reacted with 8 g of 37% formaldehyde at pH 7.5 for 45 minutes at 750C. A product was obtained that mainly consists of and which, as in Example 16, applied to cotton gabardine in a mixture with 50 g / l trimethylolmelamine and condensed, produced oil repellency values of 120 to 130 points.

By using varying or small amounts of formaldehyde during the condensation, 15 to 17 varying degrees of methylolation could be observed in Examples from 1 to 4 can be achieved through longer periods condensation could obtain usable precondensates of higher molecular weight in the same way will. By heating these products with various alcohols such as methanol bia butanol, but especially with glycol, polyglycol, or glycerine, they could Solution and curing properties can be varied within wide limits. Especially high oil repellency values resulted in mouifications with lauryl alcohol and polyglycol.

Example 18 According to Example 16, by increasing the proportion of formaldehyde the corresponding tetramethylol compound to 1.7 times the specified amount obtain. 3 g of this compound were used for etherification with hydrophilic polyglycols and mixed with 7 g of polyglycol 400 to which 1% concentrated hydrochloric acid was added heated to 10 ° C. for 20 minutes with stirring. After cooling the mass was with dilute sodium hydroxide solution neutralized to pH = 7. The product lowered the surface tension aqueous solutions to about 17 dynes / cm, also in great dilution. It was suitable Excellent for stabilizing the foams in the production of polyurethane-polyether foams.

Example 19 8 g of C10F21-C2H4N (CH3) 2, prepared according to Example 3, were in a small autoclave with 3 g of methyl iodide at 1100C for 5 hours heated. After cooling, excess methyl iodide was evaporated off to 12 g [C10F21C2H4N (CH3) 3] + [l obtained in saline form. The product was in the barrel well soluble una possessed very high surface-active properties. In water, at a concentration of 0.07%, the Achieved surface tension of 16 dynes / cm.

Example 20 10 g of C8F17C2H4-NH-C2H4NH2, prepared according to Example 4, were heated with shaking to 1400 ° C. in 15 cc of dioxane in the presence of 40 mg of sodium hydroxide powder in a small shaking autoclave, whereupon 35 g of ethylene oxide were injected using a small metering pump. After cooling for 2 hours, the solution was removed and the dioxane was distilled off. A viscous liquid remained as residue which had an equivalent weight of 960 in relation to nitrogen, which is a molecular weight of 1920 for a compound of the formula corresponded. This compound was a preliminary emulsifier and produced very small, uniform cells when plastics were foamed.

The surface tension of aqueous and organic systems could up to 15.5 dynes / cm can thus be lowered. The surfactant was acidic and weak effective in the alkaline range.

EXAMPLE 21 10 @ of the surfactant obtained according to Example 20 was refluxed for 4 hours with 2.1 g of sodium acrylate in the presence of a little sodium hydroxide in 10 cc of dioxane. After distilling off the dioxane, 12.0 g of a paste-like compound were obtained can be obtained in almost 100% yield. The substance was an excellent amphoteric surfactant with a high foaming effect, which could effectively lower the surface tension to 16 dynes / cm in water in all pH ranges.

Example 22 Analogously to Example 20 and 21, 5 g of C10F21C2H4N (CH3) H with 15 g ethylene oxide 9 g C10F21C2H4N (CH3) (C2H4O) 12H @ on average and aem molecular weight found 1090 received. The product had excellent emulsifying properties.

Be game 5 g of the surfactant prepared according to Example 22 were heated with methyl bromide in a double stoichiometric excess, 24 hours at 110C, and so the cationic surfactant obtain.

Example 24 The product from Example 23 was made with the same molar Amount of sodium acrylate in tetrahydrofuran after adding 20 mg of sodium hydroxide 400C heated for 5 hours. All solvent was then evaporated and a pasty, obtained salty product, which mainly consists of C10F21C2H4N # (CH3) 2- (C2H4O) 12-C2H4COO # duration. This surfactant was with surface tensions of 16 dynes / cm in all px areas effective. By analogous conversion with vinyl sulfonic acid, the surfactant was equally effective C10F21C2H4N # (CH3) 2- (C2H4O) 12-C2H4SO3 # obtain.

Example 25 To 7 g of C8F17C2H4NH.C2H4NH2 was added 4.5 g of acrylamide and the mixture was heated at 100 ° C. for 3 hours. There could be full sales too be achieved. After adding 10 g of 37% formaldehyde, this product was stirred at 70 ° C. for 2 hours. According to analysis, the compound could be methylolated on the amido nitrogen to the extent of 76% of theory. The product was soluble in water. A piece of filter paper and a piece of cotton were dipped in an aqueous solution of this product, dried at temperatures of 140 ° C. and heated for 2 minutes. These test pieces were then highly oil-repellent, but were hydrophilic.

Claims (1)

Claim 1 secondary and tertiary amines and quaternary ammonium fluorine compounds, characterized in that the compounds in ß - position to the nitrogen at least a perfluoroalkyl radical of 6 to 20, advantageously 7 to 16, especially 8 to 14 Carry carbon atoms and the at least one other, non-fluorinated organic Containing substituents bonded to nitrogen, the advantageous highly polar functional Groups carries. Claim 2 Amines according to Bnspruch 1, characterized by the general formula or ammonium compounds of the formula where Rf is a perfluoroalkyl radical of 6 to 25 carbon atoms, advantageously 7 to 18 carbon atoms, in particular CF3 (CF2 # 7, CF3 (CF2 # 9, CF3 (CF2 # 11, R1 is an aliphatic radical, advantageously a small alkyl radical with 1 to 3 0 atoms, in particular methyl, or advantageously an aliphatic radical that contains strongly polar functional groups, R2 is hydrogen or an organic radical, advantageously a non-alkyl radical from 1 to 3 C Atoms, in particular ethyl, or advantageously an organic radical which contains strongly polar functional groups, R3 is hydrogen or a smaller alkyl radical from 1 to; C atoms, A is an acid radical, advantageously the radical of a strong mineral acid, in particular chloride ion, bromide ion or a sulfate ion equivalent. Claim 3 Amines according to Claim 1 and / or 2, characterized in that the second fluorine-free nitrogen ligand R1 has the formula has, with n = 1 to 6, advantageously 1, Z1, Z2, Z3 and R2 (in claim 2) = hydrogen, or a small alkyl radical of 1 to 3 carbon atoms, advantageously a functional aliphatic radical of the formula: (C2H4O) mH with m = 1 to 20, advantageously 1, C2H4COOH, in which the carboxyl group can also be present as a salt, C2H4CONX1X2, in which X1, X2 is hydrogen or CH2OH. Claim 4 Amines or ammonium compounds according to Claim 2, characterized in that R1 and R2 are a contiguous cyclic ring of the formula form how or wherein Z1 is defined according to claim 3. Claim 5 Amines according to Claim 2 or 3, characterized in that the groups R2, Z, Z, in Claims 2 and 3, have the formula have, optionally in the form of the hydrochloride, in which X, X2, X3, X4 is hydrogen or -CH2OH, in particular xl and X3 = hydrogen and X2 and X4 = CE20H, the group CH2OH optionally also acetal-like to ethylene or polyethylene glycol or glycerine, can be bound according to the formula -CH2O (C2H4O) nR. Claim 6 amines according to claim 5, characterized in that the amines have the formula where n = 7 or 9, X1, X2, X3, X4 5 is hydrogen or CH2-0 (C2H4) pH with p = 0 to 20, preferably 0, where X1 and X3 are advantageously hydrogen and 7 and X4-CH20H is. Claim 7 Process for the preparation of fluorinated secondary and tertiary amines, according to the individual claims 1 to 6, characterized in that a.) 1-iodo-1,1,2,2-tetrahydroperfluoroalkanes having 8 to 27 carbon atoms with primary or secondary amines Qer general formula wherein R is a small alkyl radical, or a radical of the formula or-C2H4.NH.C2H4NH2 with R4, R5 = hydrogen, or a small alkyl radical of 1 to 3 carbon atoms, m = 2-6, R2 hydrogen or a small alkyl radical of 1 to 3 carbon atoms, but advantageously with HN (CH3) 2, H2NCH3, oler H2N.C2R4NH2, being in homogeneous solution, preferably at temperatures of 20 to 100 ° C, and in ethers, especially a mixture of 50% by weight of tetrahydrofuran and diisopropyl ether, with a molar excess working on Aiin provides residence times of 1 minute to 1 hour, b.) if necessary, the free amines formed with ethylene oxide, acrylic acid; or their derivatives or alkylating agents, c1.) and / or optionally the free amines formed which still contain at least 1 hydrogen atom bonded directly to nitrogen, advantageously the secondary amines with 2,4,6-chloro-amino-s-triazines or dicyanamide , if appropriate reacts at higher temperatures, and if 2,4,6-triaminos-triazines are used, the mineral acid salts of the fluoroalkylamines can also be used, c2.) and if appropriate reacts the amines obtained thereby with formaldehyde, preferably in alkaline aqueous media. Claim 8 Method according to Claim 7, characterized in that one, according to claim 7c, the free secondary fluoroalkylamines with 2-chloro-4,6-diamino-s-triazine or dicyanamide at temperatures from 80 to 160 ° C., if appropriate in a solvent reacts and, according to 7 c2.) with the 2-fluoroalkyl-4,6-diamino-s-triazines formed Formaldehyde or a formaldehyde donor, such as para @ ormaldehyde, hexamethylenetetramine, or hemiacetals of formaldehyde with ethylene glycol, or polyethylene glycol, preferably by means of alkaline catalysis between pH = 7.1 to 10.5 with the 1 to 8 molar amount of formaldehyde, at temperatures of 30 to 80 ° C. Ansrucn 9 Oil- and water-repellent impregnation of fibrous-porous Substrates, preferably of all kinds of textiles, paper and leather, by means of compounds, according to claims 5 and 6 ,. advantageously produced according to claim 7 or 8, characterized in that characterized in that the substrates in aqueous solutions or dispersions of the Fluoroalkylamino-ocier dethylolamino-s-triazines according to the invention, together with moisten or soak with an acid-releasing catalyst or magnesium chloride, The substrates are dried, then heated to 120 to 160 ° C and, if necessary @ achwäscht. Claim 10 method according to claim 9, characterized in that urea or lY1elamin-formaldehyde resins and known fluorine-free resins are used at the same time Hydrophobic impregnation agent also used.