EP0001993B1 - Fluorinated alkyl-sulfato-betaines and process for their preparation - Google Patents

Description

The invention relates to fluorine-containing alkyl sulfato betaine and processes for their production.

The production of non-fluorine-containing sulfato-ethyl- or sulfatopropyl-betaines which have one longer-chain and two short-chain alkyl groups on the nitrogen atom is known. Such compounds are obtained if the tertiary amine, which contains one long-chain and two short-chain alkyl groups, is first reacted with ethylene chlorohydrin or with 3-chloro-1-propanol and the 2-hydroxy-trialkylammonium chloride thus formed is reacted with chlorosulfonic acid, analogously also the 3-hydroxypropyl trialkylammonium chloride can be used. In the same way, trialkylamines are attempted which contain a longer-chain fluorine-containing alkyl or alkenyl radical (for example a 1,1,2,2-tetrahydro-perfluorodecyl or a 1,1,2-trihydro-perfluoro-2-decenyl radical ), a mixture of the most diverse, partly polymeric compounds is obtained, from which it is difficult to isolate individual substances. Difficulties also arise since the fluorine-containing amines, for example reacted with chloroethanol, dissolve only inadequately in solvents which are suitable for sulfation.

It is also known to react tertiary, non-fluorine-containing alkylamines with, for example, the sodium salt of acidic 1-chlorobutyl sulfate (4) with elimination of NaCl to give sulfobetaine. When this process is applied to fluorine-containing, tertiary alkylamines, however, poor yields and difficulties are found due to the easily decomposable nature of the compounds formed, so that only highly contaminated products can be obtained.

worin bedeuten R_f einen Perfluoralkylrest mit 3 bis 16, vorzugsweise 5 bis 12 C-Atomen, R¹ einen Alkylrest mit 1 bis 4, vorzugsweise mit 1 oder 2 C-Atomen, R² einen Alkylrest mit 1 bis 4, vorzugsweise 1 oder 2 C-Atomen, Q die Alkylenreste -CH₂CH₂ - oder

vorzugsweise den Alkylenrest -CH₂CH₂-, m die Zahlen 0 oder 1, wobei, wenn m=0, p eine ganze Zahl von 1 bis 4, vorzugsweise die Zahl 2 bis 4 und, wenn m = 1, p die Zahl 1 ist.The present invention relates to fluorine-containing alkyl sulfato betaine of the formula

in which R _{f is} a perfluoroalkyl radical with 3 to 16, preferably 5 to 12, carbon atoms, R ^{1 is} an alkyl radical with 1 to 4, preferably with 1 or 2, carbon atoms, R ^{2 is} an alkyl radical with 1 to 4, preferably 1 or 2 C atoms, Q the alkylene radicals -CH ₂ CH ₂ - or

preferably the alkylene radical -CH ₂ CH ₂ -, m is the number 0 or 1, where if m = 0, p is an integer from 1 to 4, preferably the number 2 to 4 and if m = 1, p is the number 1 is.

Particular preference is given to those compounds of the formula (I) in which R _f , R ¹ , R ² and Q have the above-mentioned meaning or preferably meaning and m = 1 and p = 1.

worin R_f; Q; m und p die obengenannte Bedeutung haben, zuerst mit mindestens einem bekannten Sulfatierungsmittel in Gegenwart von mindestens einem Lösungsmittel (a), das obengenannte Amine löst und mit dem Sulfatierungsmittel nicht reagiert, bei -30 bis +60°C umgesetzt wird, nach Entfernung des Lösungsmittels (a) das erhaltene Produkt in mindestens einem polaren Lösungsmittel (b) gelöst, mit mindestens einem bekannten Alkali neutralisiert und danach die neutrale Lösung bei 40 bis 130°C und einem Druck von ca. 1 bis ca. 6 bar mit einer Verbindung der Formel R₂Z, worin Z=Cl; Br; J oder -OSO_ZOR^Z ist und R² die obengenannte Bedeutung hat, umgesetzt wird.The invention further relates to a process for the preparation of the compounds described above, which is characterized in that a compound of the formula

wherein R _f ; Q; m and p have the meaning given above, first with at least one known sulfating agent in the presence of at least one solvent (a) which dissolves the above amines and does not react with the sulfating agent, at -30 to + 60 ° C, after removal of the solvent (a) the product obtained dissolved in at least one polar solvent (b), neutralized with at least one known alkali and then the neutral solution at 40 to 130 ° C and a pressure of about 1 to about 6 bar with a compound of the formula R ₂ Z, where Z = Cl; Br; J or -OSO _Z OR ^Z and R ^{2 has} the meaning given above, is implemented.

The fluorinated amines used as starting compounds can be prepared, for example, by the processes described in US Pat. No. 3,535,381, DE-OS 1141542.

Suitable sulfating agents are, for example, concentrated sulfuric acid, solutions of sulfur trioxide in concentrated sulfuric acid (oleum) and in particular chlorosulfonic acid and sulfur trioxide. The latter is advantageously used as a gaseous admixture to inert gases, such as nitrogen or air. These gas mixtures can contain about 0.5 to 10 vol .-% S0 ₃ . The sulfation is advantageously carried out at temperatures between 0 and 30 ° C. The pressure applied is not critical. In general, work is carried out at atmospheric pressure, but a lower excess pressure of up to approx. 2 bar can also be used. The use of a lower negative pressure of up to about 0.3 bar is also possible, provided the solvent (a) used has not yet boiled under the chosen reaction conditions.

Suitable solvents (a) are halogenated hydrocarbons with 1 to 2 carbon atoms, in particular carbon tetrachloride, chloroform, methylene chloride; or chlorofluorocarbons of 1 to about 3 carbon atoms, in particular 1,1,2-trifluoro-1,2,2-trichloroethane; furthermore in particular acetonitrile or liquid sulfur dioxide. Of the solvents mentioned, both a single and a mixture of them can be used.

Depending on the temperature used and the reaction components used, the sulfation generally takes between 1 and 10 hours. A slight excess of the sulfating agent over the stoichiometrically calculated amount is generally desirable.

The solvent (a) is conveniently used se chosen so that the sulfated amine is largely insoluble in it. After the sulfation reaction has ended, the resulting insoluble product is filtered off, washed with solvent (a) and expediently dried under reduced pressure from about 1 to about 990 mbar and somewhat elevated temperature from 25 to about 80 ° C.

• Aliphatische Monoalkohole mit 1 bis 6 C-Atomen, vorzugsweise Methanol, Äthanol, Isopropanol, n-Butanol oder aliphatische Ätheralkohole mit 3 bis 6 C-Atomen wie Dimethylglykol, Äthylglykol, Butylglykol, Diglykol, Methyldiglykol oder Glykol oder Wasser. Von den genannten Lösungsmitteln können sowohl ein einzelnes sowie auch mehrere in Mischung miteinander verwendet werden. Zur Neutralisation werden bekannte Alkalien eingesetzt, vorzugsweise Natriumhydroxid, Kaliumhydroxid oder die Natrium- oder Kaliumalkoholate von einwertigen aliphatischen Alkoholen mit 1 bis 4 C-Atomen. Die Hydroxide werden vorzugsweise in Wasser, die Alkoholate in dem Alkohol, der die Alkoholatkomponente bildet, gelöst angewendet. Die Neutralisation wird mit bekannten Säure-Basen-Indikatoren wie beispielsweise Phenolphthalein oder Methylorange überwacht.

The product thus obtained is dissolved in a polar solvent (b) and optionally neutralized with cooling. The following are suitable as polar solvents (b):

• Aliphatic monoalcohols with 1 to 6 C atoms, preferably methanol, ethanol, isopropanol, n-butanol or aliphatic ether alcohols with 3 to 6 C atoms such as dimethyl glycol, ethyl glycol, butyl glycol, diglycol, methyl diglycol or glycol or water. Of the solvents mentioned, both a single one and several in a mixture with one another can be used. Known alkalis are used for neutralization, preferably sodium hydroxide, potassium hydroxide or the sodium or potassium alcoholates of monohydric aliphatic alcohols having 1 to 4 carbon atoms. The hydroxides are preferably used in water, the alcoholates dissolved in the alcohol which forms the alcoholate component. The neutralization is monitored with known acid-base indicators such as phenolphthalein or methyl orange.

The neutralized solution is then reacted with known alkylating agents at a temperature of 40 to 130 ° C. and a pressure of about 1 to about 6 bar. The temperature and pressure are preferably set so that the solvent (b) or solvent mixture boils.

Compounds of the formula R ² Z are used as alkylating agents, in which R ^{2 has} the meaning given above and Z = C1: Br; J or -OS0 ₂ 0R ² . Methyl iodide, methyl chloride and dimethyl sulfate are preferably used. In the case of alkylating agents which are gaseous at atmospheric pressure, such as methyl chloride, methyl bromide and ethyl chloride, elevated pressure is expediently used. The time required for the alkylation varies, depending on the temperature used and the starting materials used, in general it is finished after about 2 to 4 hours. The alkylating agent is expediently used in stoichiometric amounts, a slight excess is sometimes advantageous.

For some purposes, the solution obtained after the alkylation, if appropriate after removal of the excess alkylating agent, can be used as such. If the pure, solid, fluorinated alkyl sulfato betaine of the formula is desired, the solvent (b) is distilled off after the alkylation, working under reduced pressure and slightly elevated temperature (conditions as indicated above) if necessary. Either before or after a certain amount of solvent (b) has been separated off, the remaining liquid can be separated off from some of the salts therein, such as sodium chloride, sodium iodide or sodium methyl sulfate, by filtration. For the final purification of the crude product freed from solvent (b), it is recrystallized from solvents (c) such as, for example, methanol, ethanol, isopropanol, water or mixtures thereof.

The process according to the invention enables the production of fluorine-containing alkyl sulfato betaines of the formula with good purity in high yields. The process parameters to be used enable the process to be carried out without complex special equipment. The sulfation, alkylation and solvents to be used are cheap and enable a technically uncomplicated and economically interesting procedure.

The fluorine-containing alkyl sulfato betaine of the formula are distinguished by high surface-active activity. Together with the compatibility with cationic, nonionic or anionic surfactants, they are suitable for use in the production of polytetrafluoroethylene dispersions, in particular dispersions of polytetrafluoroethylene with low or medium molecular weight (so-called polytetrafluoroethylene waxes), as leveling agents for waxes, as cleaning enhancers in the chemical industry Cleaning and especially as mixture components in fire extinguishing agents.

The following examples are intended to explain the invention in more detail:

example 1

496 (N-1,1,2-trihydroperfluoro-2-decenyl -) - N-methylethanolamine are dissolved in one liter of carbon tetrachloride (a) and dissolved in the solution with stirring and temperature control at 30 ° C 165 of a sulfur trioxide-air mixture, the 9th Vol .-% S0 ₃ contains, initiated within 2 hours. The acidic sulfuric acid ester formed separates out as a solid. It is filtered off, dried at 20 mbar and 50 ° C., then dissolved in one liter of isopropanol (b) and neutralized with 127 g of a 30% by weight sodium methylate solution in methanol. 126 g of dimethyl sulfate are added to the neutral solution, the mixture is stirred at 60 ° C. for 4 hours and then filtered at approx. 50 ° C. The filtrate is cooled to 0 ° C., the precipitated solid is filtered off and recrystallized from isopropanol (c). 478 g of product of the formula below are isolated, which corresponds to a yield of 81% of the theoretical value. The elementary analysis gave the following values (calculated theoretical values in brackets): C 27.9% (28.4%), H 2.1% (2.2%), N 2.4% (2.4%), S 5.2%, (5.4%). This corresponds to the formula

Example 2

The procedure is as described in Example 1, but 142 g of methyl iodide are added instead of the dimethyl sulfate. After recrystallization, 348 g, corresponding to a yield of 67% of the theoretical value, are obtained from a compound whose values determined in the elemental analysis and whose IR and NMR spectra match the product obtained in Example 1.

Example 3

• a) 496 g (N-1,1,2-trihydroperfluoro-2-decenyl -) - N-methylethanolamine are dissolved in 0.5 liters of acetonitrile (a) and 116.5 g of chlorosulfonic acid are mixed with stirring at 30 to 40 ° C within 30 Dripped minutes. It is then filtered and the filter cake obtained is washed twice with 100 ml of acetonitrile and then dried at 20 mbar and 50 ° C. In this way, 507 g, corresponding to a yield of 88% of the theoretical value, of the inner salt of ethanolamine sulfate are obtained with the following formula:
  
  The elementary analysis showed the following values (theoretical values in brackets):
  • C26.6% (26.9%); H 2.2% (1.6%); S 5.6% (5.5%); N 2.4% (2.4%); C1 <0.1% (0%).
• b) 507 g of the sulfation product obtained as described above are dissolved in 1.35 liters of isopropanol (b) and neutralized with 38.8 g of a 50% strength by weight aqueous solution of sodium hydroxide with stirring. The mixture is then heated to 60 ° C. for a few minutes and then filtered at 50 ° C., and the filtrate obtained is concentrated to ¼ of its volume. After the concentrated filtrate has cooled to 0 ° C., the crystals formed are suction filtered and dried. 412 g corresponding to 79% of the theoretical value are obtained from a compound of the following formula:
  
  The elementary analysis showed the following values (theoretical values in brackets):
  • C25.4% (25.9%); H2.2% (1.7%); N2.2% (2.3%); Na 3.6% (3.8%); S 5.0% (5.3%); CI <0.1% (0%).
• c) 412 g of the neutralized sulfation product obtained as described under b) are dissolved in 500 ml of isopropanol (b) and 94 g of dimethyl sulfate are added dropwise with stirring over the course of 30 minutes. The mixture is then refluxed for 4 hours and then filtered at 50 ° C. After the filtrate has cooled to 0 ° C., the separated product is filtered off and dried at 20 mbar and 50 ° C. 250 g, corresponding to 62% of the theoretical value of a compound of the formula are obtained:
  
  The elementary analysis showed the following values (theoretical values in brackets):
  • C28.1% (28.4%); H 2.2% (2.2%); N2.4% (2.4%); S 5.2% (5.4%).

Example 4

• 41 Gew.-% C₅F₁₁-
• 40 Gew.-% C₇F₁₅-
• 14 Gew.-% C₉F₁₉-
• 5 Gew.-% C₁₁F₂₃-.

A (N-1,1,2-trihydroperfluoro-2-alkenyl -) - N-methylethanolamine is used, the perfluorinated alkyl radicals R _{f of which} consist of a mixture of different perfluorinated alkyls of the following composition:

• 41% by weight C ₅ F ₁₁ -
• 40% by weight C ₇ F ₁₅ -
• 14% by weight C ₉ F ₁₉ -
• 5% by weight of C ₁₁ F ₂₃ -.

worin R_f dem weiter oben angegebenen Gemisch perfluorierter Alkylgruppen entspricht.948 g of the above-described compound with an amine number of 20.2 are dissolved in 1.61 carbon tetrachloride (a) and 1656 of an S0 ₃ air mixture which contains 9% by volume S0 _{3 is} introduced at 20 ° C. and atmospheric pressure , whereupon the acidic sulfuric acid ester formed separates as a solid. After filtering and drying at 20 mbar and 50 ° C., the solid product is dissolved in 1.51 methanol (b) and neutralized with 570 g of a 30% by weight methanolic solution of sodium methylate. 250 g of methyl sulfate are then added dropwise to the neutralized solution while stirring and boiling under reflux, and the mixture is then heated to 60 ° C. for 4 hours. After evaporation of the solvent at approx. 80 ° C, drying is carried out at 20 mbar and 50 ° C. 1085 g of a product are obtained which contains 123 g of sodium methyl sulfate (= 11.4% by weight). A sample of this product is purified by the column chromatography method described below. The amount of pure fluorine-containing alkyl sulfato betaines determined in this way corresponds to 85% of the theoretical value. The compound mixture obtained corresponds to the formula

wherein R _f corresponds to the mixture of perfluorinated alkyl groups given above.

Example 5

The procedure is as in Example 4, but 232 g of chlorosulfonic acid and 1.51 of chloroform (a) are used instead of the S0 ₃ air mixture and the carbon tetrachloride. After evaporation of the solvent and drying, 1100 g Obtain product containing 125 g of sodium methyl sulfate. The amount determined by column chromatography of the mixture of the purified fluorine-containing alkyl sulfato betaine with the formula given in Example 4 corresponds to 84% of the theoretical value.

Example 6

948 g of (N-1,1,2-trihydroperfluoro-2-alkenyl -) - N-methylethanolamine (amine number 20.2) in which the perfluoroalkenyl radical represents the same mixture of perfluorinated alkylene as described in Example 4 are described in 1.5 Liter of chloroform (a) dissolved and 232 g of chlorosulfonic acid added dropwise at 30 ° C. with stirring.

The mixture is then slowly heated to boiling and refluxed for one hour in order to expel the hydrogen chloride gas formed. After the chloroform has been evaporated off at 20 mbar and 50 ° C., the product is dissolved in 660 g of isopropanol (b), neutralized with 166 g of a 50% strength by weight aqueous solution of sodium hydroxide and with stirring with 250 g of dimethyl sulfate within about 30 minutes transferred. The mixture is then held at 60 ° C. for four hours, then cooled to room temperature and 577 g of water are added. This gives a solution in isopropanol water which has a solids content of 50% by weight. The solid consists of 12% by weight of sodium methyl sulfate and 88% by weight of a mixture of fluorine-containing alkyl sulfato betaines of the formula given in Example 4. The content of fluorine-containing alkyl sulfato betaines was determined by column chromatography.

Example 7

Die Elementaranalyse ergab folgende Werte (theoretische Werte in Klammern):

• C29,3% (29,6%); H2,4% (2,5%); N 2,3% (2,3%); S 5,2% (5,3%).

515 g (N-1,1,2-trihydroperfluoro-2-decenyl -) - N-ethyl-ethanolamine are dissolved in 1 liter carbon tetrachloride (a) and 165 liters of an SO ₃ air mixture are stirred at 30 ° C. for 2 hours , which contains 9 vol .-% S0 ₃ introduced, the acidic sulfuric acid formed separates as a solid. After filtering and drying at 20 mbar and 50 ° C., the solid product is dissolved in one liter of isopropanol (b) and neutralized with 180 g of a 30% by weight methanolic sodium methylate solution. After adding 126 g of dimethyl sulfate within about 30 minutes, the mixture is stirred for a further 4 hours at 60 ° C., then filtered at 50 ° C. and the filtrate is cooled to 0 ° C., a crystalline product precipitating. The precipitated solid is filtered off and recrystallized from isopropanol (c). 450 g, corresponding to 74% of the theoretical value of a product, are obtained using the following formula:

The elementary analysis showed the following values (theoretical values in brackets):

• C29.3% (29.6%); H2.4% (2.5%); N 2.3% (2.3%); S 5.2% (5.3%).

Example 8

Die Elementaranalyse ergab folgende Werte (theoretische Werte in Klammern):

• C27,4% (27,3%); H 2,5% (2,3%); N 2,2% (2,3%); S 5,0% (5,2%).

520 g (N-1,1,2,2-tetrahydroperfluorodecyl) -N-methylethanolamine are dissolved in one liter of carbon tetrachloride (a), and 165 liters of an S0 ₃ air mixture are dissolved in the solution at 30 ° C. in two hours, that contains 9 vol.% S0 ₃ , the acidic sulfuric acid ester separating out as a solid. After filtering and drying at 20 mbar and 50 ° C., the solid product is dissolved in one liter of methanol (b) and neutralized with 180% of a 30% by weight methanolic sodium methylate solution. 126 g of dimethyl sulfate are added to this solution within 30 minutes and then stirred for a further 4 hours at 60 ° C., then filtered at 50 ° C. and the filtrate is cooled to 0 ° C. The solid which precipitates out is filtered off and recrystallized from isopropanol (c). 522 g, corresponding to 85% of the theoretical value, of a compound of the following formula are obtained:

The elementary analysis showed the following values (theoretical values in brackets):

• C27.4% (27.3%); H 2.5% (2.3%); N 2.2% (2.3%); S 5.0% (5.2%).

• Ein senkrecht stehendes Glasrohr mit einem inneren Durchmesser von 30 mm ist an seinem unteren Ende mit einer Glasfritte verschlossen. Das Rohr wird 130 mm hoch mit ca. 30 g eines Kieselgels der Korngrösse 0,1-0,2 mm, das ca. 6% Wasser enthält, (zum Beispiel der Typ MN der Firma Macherey und Nagel), gefüllt. Als Probe werden 300 bis 500 mg des zu reinigenden Sulfobetains abgewogen und in 5 ml Methanol pro analysi gelöst, auf die mit Kieselgel gefüllte Säule aufgegeben und dann mit weiterem Methanol pro analysi nachgewaschen. Die ersten 150 ml methanolischer Lösung, die unten aus der Säule austreten, werden gesammelt, zur Trockenen eingedampft, erneut in Methanol aufgenommen und durch eine Glasfritte, die mit Filterflockenmasse beschickt wurde, filtriert. Das Filtrat wird eingedampft und 60 Minuten bei 105°C in Luft getrocknet. Das so erhaltene Produkt stellt praktisch die Gesamtmenge des in der Probe erhaltenen Sulfatobetains dar. Eine Kontrolle des so erhaltenen Sulfatobetains bezüglich Reinheit und chemischer Zusammensetzung ist vermittels IR-oder NMR-Spektren sowie vermittels Dünnschichtchromatographie möglich.

The purification of the fluorine-containing alkyl sulfato betaine of the formula from impurities by column chromatography is carried out as follows:

• A vertical glass tube with an inner diameter of 30 mm is closed at its lower end with a glass frit. The tube is filled 130 mm high with approx. 30 g of a silica gel with a grain size of 0.1-0.2 mm, which contains approx. 6% water (for example the type MN from Macherey and Nagel). As a sample, 300 to 500 mg of the sulfobetaine to be purified are weighed out and dissolved in 5 ml of methanol per analysis, applied to the column filled with silica gel and then washed with additional methanol per analysis. The first 150 ml of methanolic solution which emerges from the bottom of the column are collected, evaporated to dryness, taken up again in methanol and filtered through a glass frit which has been loaded with filter flake mass. The filtrate is evaporated and dried in air at 105 ° C. for 60 minutes. The product obtained in this way represents practically the total amount of the sulfatobetaine obtained in the sample. The purity and chemical composition of the sulfatobetaine obtained in this way can be checked by means of IR or NMR spectra and by means of thin-layer chromatography.

• ¹H-NMR-Spektren in D₃COD (mit Tetramethylsilan als interner Standard)
  
  Als Beispiel für die gute oberflächenaktive Wirksamkeit der Verbindungen gemäss Formel I wird nachfolgend eine Vergleichsmessung der Oberflächenspannung der erfindungsgemässen Verbindung nach Beispiel 1 im Vergleich zu einem marktüblichen fluorhaltigen Tensid mit der Formel
  
  worin R_f ein Gemisch von perfluorierten Alkylresten mit 6 bis 12 Kohlenstoffatomen ist, angegeben. Die Messung erfolgte nach der Ringabreiss-Methode (DIN-Entwurf 53914) an den wässrigen Lösungen der Substanzen bei 20°C. Die Oberflächenspannung ist in mN/m angegeben, die Konzentration des Tensids in Gramm pro Liter (g/I).

The following NMR spectra were determined on the fluorinated alkyl sulfato betaines of the formula prepared according to Examples 1 and 3 c:

• ¹ H-NMR spectra in D ₃ COD (with tetramethylsilane as internal standard)
  
  As an example of the good surface-active activity of the compounds according to formula I, a comparison measurement of the surface tension of the compound according to the invention according to example 1 in comparison with a commercially available fluorine-containing surfactant with the formula is given below
  
  wherein R _{f is} a mixture of perfluorinated alkyl radicals having 6 to 12 carbon atoms. The measurement was carried out according to the ring tear-off method (DIN draft 53914) on the aqueous solutions of the substances at 20 ° C. The surface tension is given in mN / m, the concentration of the surfactant in grams per liter (g / I).

Compatibility with anionic and cationic surfactants was also determined. The measured values are given in the table below, with a plus sign indicating compatibility and a minus sign indicating incompatibility.

Claims (10)

1. Fluorine-containing alkyl-sulfato-betaines of the formula

in which R_f denotes a perfluoroalkyl radical with 3 to 16 C atoms, R^I denotes an alkyl radical with 1 to 4 C atoms, R² denotes an alkyl radical with 1 to 4 C atoms, Q denotes the alkylene radicals -CH₂CH₂-or -CH₂-CH-, CH₃ m denotes the numbers 0 or 1 and, if m is 0, p is an integer from 1 to 4 and, if m is I, p is the number 1.

2. Fluorine-containing alkyl-sulfato-betaines as claimed in claim 1, wherein, in the formula indicated in the said claim, R_f denotes a perfluoroalkyl radical with 5 to 12 C atoms, R¹ denotes an alkyl radical with 1 or 2 C atoms, R² denotes an alkyl radical with 1 or 2 C atoms, Q denotes the alkylene radical -CH₂CH₂-, m denotes the numbers 0 or 1 and, if m is 0, p is an integer from 2 to 4 and, if m is I, p is the number 1.

3. Process for the manufacture of fluorine-containing alkyl-sulfato-betaines as claimed in claim 1, which comprises first reacting a compound of the formula

in which R_f, R^I, Q, m and p are as defined in claim 1, with at least one known sulfating agent at -30 to +60°C in the presence of at least one solvent (a) which dissolves the abovementioned amine and does not react with the sulfating agent, dissolving the resulting product, after removing the solvent (a), in at least one polar solvent (b), neutralizing the solution with at least one known alkali and then reacting the neutral solution at 40 to 130°C and under a pressure of about 1 to about 6 bars with a compound of the formula R₂Z, in which Z is Cl, Br, I or -OS0₂OR² and R² is as defined in claim 1.

4. Process as claimed in claim 3, wherein the sulfating agent employed is sulfur trioxide or chlorosulfonic acid.

5. Process as claimed in claims 3 and 4, wherein the sulfation is carried out at 0 to 30°C.

6. Process as claimed in claims 3 to 5, wherein one or more of the following solvents (a) are employed in the sulfation: carbon tetrachloride, chloroform, methylene chloride, 1,2,2-trichloro-1,1,2-trifluoroethane, acetonitrile and liquid sulfur dioxide.

7. Process as claimed in claims 3 to 6, wherein at least one of the following compounds is employed as the polar solvent (b): aliphatic monoalcohols with 1 to 6 C atoms, aliphatic ether-alcohols with 3 to 6 C atoms, glycol or water.

8. Process as claimed in claims 3 to 7, wherein at least one of the following compounds is employed as the alkali: alcoholates of aliphatic monoalcohols with 1 to 4 C atoms or hydroxides of sodium or potassium.

9. Process as claimed in claims 3 to 8, wherein the neutral solution is reacted with methyl iodide, methyl chloride or dimethyl sulfate.

10. Process as claimed in claims 3 to 9, wherein the temperature and pressure for the reaction with a compound of the formula R²Z are so adjusted that the polar solvent (b) boils.