EP0001993A1 - Alcoyle-sulfato-bétaines fluorées et leur procédé de préparation - Google Patents
Alcoyle-sulfato-bétaines fluorées et leur procédé de préparation Download PDFInfo
- Publication number
- EP0001993A1 EP0001993A1 EP78101238A EP78101238A EP0001993A1 EP 0001993 A1 EP0001993 A1 EP 0001993A1 EP 78101238 A EP78101238 A EP 78101238A EP 78101238 A EP78101238 A EP 78101238A EP 0001993 A1 EP0001993 A1 EP 0001993A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- formula
- carbon atoms
- sulfato
- fluorine
- radical
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/004—Surface-active compounds containing F
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D1/00—Fire-extinguishing compositions; Use of chemical substances in extinguishing fires
- A62D1/0071—Foams
- A62D1/0085—Foams containing perfluoroalkyl-terminated surfactant
Definitions
- the invention relates to fluorine-containing alkyl sulfato betaine and processes for their production.
- trialkylamines 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-tri-hydroperfluoro-2-decenyl radical ), a mixture of the most diverse, partially polymeric compounds is obtained, from which individual substances are difficult to isolate to let. Difficulties also arise because the fluorine-containing amines, for example reacted with chloroethanol, dissolve only insufficiently in solvents which are suitable for sulfation.
- a longer-chain fluorine-containing alkyl or alkenyl radical for example a 1,1,2,2-tetrahydro-perfluorodecyl or a 1,1,2-tri-hydroperfluoro-2-decenyl radical
- alkylamines containing tertiary non-fluorine with, for example, the sodium salt of acidic 1-chlorobutyl sulfate (4) with the elimination of NaCl to give sulfobetaine.
- 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.
- 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 1,768,939 or DE-OS 2,141,542
- 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.
- 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.
- solvents mentioned both a single and a mixture of them can be 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 advantageously 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 suitably dried under reduced pressure of about 1 to about 990 mbar and somewhat elevated temperature of 25 to about 80 ° C.
- 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.
- Methyl iodide, methyl chloride and dimethyl sulfate are preferably used.
- alkylating agents which are gaseous at atmospheric pressure such as methyl chloride, methyl bromide and ethyl chloride, it is advisable to use elevated pressure.
- 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 advantageously used in stoichiometric amounts, a slight excess is sometimes advantageous.
- the solution obtained after the alkylation if appropriate after removal of the excess alkylating agent, can be used as such.
- the solvent (b) is distilled off after the alkylation, where appropriate under reduced pressure and slightly elevated temperature (conditions as indicated above). Either before or after a certain amount of solvent (b) has been removed, the remaining liquid can be removed from one part the salts contained therein, such as sodium chloride, sodium iodide or sodium methyl sulfate, are separated off by filtration.
- 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 I 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 formula I are characterized 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.
- 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.
- 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 their IR and NMR spectra match the product obtained in Example 1.
- a (N-1, 1,2-trihydroperfluoro -2-alxenyl -) - N-methylethanolamine is used, the perfluorinated alkyl radical R f of which consists of a mixture of different perfluorinated alkyls of the following composition: 948 g of the compound described above with an amine number of 20.2 are dissolved in 1.6 l of carbon tetrachloride (a) and 165 l of an SO 3 - air mixture containing 9% by volume SO 3 for 2 hours at 20 ° C. and atmospheric pressure contains, initiated, wherein the acidic sulfuric acid ester separates as a solid.
- 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 4 The procedure is as in Example 4, but 232 g of chlorosulfonic acid and 1.5 l 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 of product are obtained, which contains 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.
- the mixture is then slowly heated to boiling and refluxed for one hour in order to expel the hydrogen chloride gas formed.
- 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.
- the 9% by volume contains SO 3 , the acidic sulfuric acid ester which separates out as a solid
- the solid product is dissolved in one liter of isopropanol (b) and mixed with 180 g of a 30
- 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., whereby a crystalline product precipitates
- the precipitated solid is filtered off and recrystallized from isopropanol (c), giving 450 g, corresponding to 74% of the theoretical value of a product with the following formula:
- Compatibility with anionic and cationic surfactants was also determined. The measured values are shown in the table below, with a plus sign indicating compatibility and a minus sign indicating incompatibility.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
- Detergent Compositions (AREA)
- Cosmetics (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE2749329 | 1977-11-04 | ||
DE19772749329 DE2749329A1 (de) | 1977-11-04 | 1977-11-04 | Fluorhaltige alkyl-sulfato-betaine und verfahren zu deren herstellung |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0001993A1 true EP0001993A1 (fr) | 1979-05-30 |
EP0001993B1 EP0001993B1 (fr) | 1981-01-07 |
Family
ID=6022976
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP78101238A Expired EP0001993B1 (fr) | 1977-11-04 | 1978-10-27 | Alcoyle-sulfato-bétaines fluorées et leur procédé de préparation |
Country Status (6)
Country | Link |
---|---|
US (1) | US4209456A (fr) |
EP (1) | EP0001993B1 (fr) |
JP (1) | JPS5473731A (fr) |
CA (1) | CA1112661A (fr) |
DE (2) | DE2749329A1 (fr) |
ES (1) | ES474666A1 (fr) |
Families Citing this family (17)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3104766A1 (de) | 1981-02-11 | 1982-09-02 | Hoechst Ag, 6000 Frankfurt | "fluorhaltige alkylsulfobetaine, verfahren zu deren herstellung sowie deren verwendung" |
US4404377A (en) * | 1982-03-08 | 1983-09-13 | Nalco Chemical Company | Heterocyclic/aromatic fluorocarbon surfactants |
US4377710A (en) * | 1982-03-08 | 1983-03-22 | Nalco Chemical Company | Quaternized epichlorohydrin adducts of perfluoro substituted ethanols |
US4408043A (en) * | 1982-03-08 | 1983-10-04 | Nalco Chemical Company | Fluorocarbon surfactants |
ZA835016B (en) * | 1982-07-22 | 1985-02-27 | British Petroleum Co Plc | A method for producing polymerisable monomers containing a sulphate group |
US4435330A (en) | 1982-12-29 | 1984-03-06 | Ciba-Geigy Corporation | Perfluoroalkyl-alkylene branched amphoteric sulfato betaines |
US4594200A (en) * | 1984-11-15 | 1986-06-10 | Halliburton Company | Compositions for increasing hydrocarbon production from subterranean formations |
US5616273A (en) * | 1994-08-11 | 1997-04-01 | Dynax Corporation | Synergistic surfactant compositions and fire fighting concentrates thereof |
EA199900485A1 (ru) | 1996-11-22 | 2000-02-28 | Альбемарл Корпорейшн | Реакция обмена галогена |
MXPA06008620A (es) * | 2004-01-30 | 2007-03-21 | Great Lakes Chemical Corp | Procedimientos de produccion y sistemas, composiciones, agentes tensioactivos, unidades monomericas, complejos metalicos, esteres de fosfato, glicoles, espumas que forman peliculas acuosas y estabilizantes de espuma. |
CA2553930A1 (fr) * | 2004-01-30 | 2005-08-18 | Great Lakes Chemical Corporation | Procedes et systemes de production, compositions, agents tensioactifs, unites monomeres, complexes metalliques, esters phosphoriques, glycols, mousses a formation de pellicule aqueuse (type afff) et stabilisateurs de mousse |
CA2554293A1 (fr) | 2004-01-30 | 2005-08-18 | Great Lakes Chemical Corporation | Procedes et systemes de production, compositions, agents tensioactifs, unites monomeres, complexes metalliques, esters phosphoriques, glycols, mousses a formation de pellicule aqueuse (type afff) et stabilisateurs de mousse |
KR20070001117A (ko) * | 2004-01-30 | 2007-01-03 | 그레이트 레이크스 케미칼 코퍼레이션 | 제조 방법 및 시스템, 조성물, 계면활성제, 모노머 유닛,금속 착체, 포스페이트 에스테르, 글리콜, 수성 막 형성발포제, 및 발포 안정제 |
US20070027349A1 (en) * | 2005-07-28 | 2007-02-01 | Stephan Brandstadter | Halogenated Compositions |
EP1907343A2 (fr) * | 2005-07-28 | 2008-04-09 | Great Lakes Chemical Corporation | Procedes de production et systemes, compositions, agents tensioactifs, motifs monomeres, complexes metalliques, esters de phosphate, glycols, mousse formant un film aqueux et stabilisateurs de mousse |
US20080076892A1 (en) * | 2006-08-03 | 2008-03-27 | Bruno Ameduri | Telomer compositions and production processes |
US8318656B2 (en) | 2007-07-03 | 2012-11-27 | E. I. Du Pont De Nemours And Company | Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1159957B (de) * | 1960-11-08 | 1963-12-27 | Bayer Ag | Verfahren zur Herstellung von quaternaeren Ammoniumverbindungen |
US3257407A (en) * | 1963-09-27 | 1966-06-21 | Du Pont | Perfluoroalkyl substituted ammonium salts |
DE1493300B2 (de) * | 1962-10-12 | 1973-07-26 | Unilever N.V., Rotterdam (Niederlande) | Verfahren zum sulfatiren von aliphatischen alkoholen und aetheralkoholen |
DE2310426B1 (de) * | 1973-03-02 | 1974-07-11 | Hoechst Ag | Hochfluorierte AEthersulfate und deren Verwendung als Egalisiermittel |
Family Cites Families (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2803656A (en) * | 1956-01-23 | 1957-08-20 | Minnesota Mining & Mfg | Fluorocarbonsulfonamidoalkanols and sulfates thereof |
US3390167A (en) * | 1965-03-30 | 1968-06-25 | Interchem Corp | Process for the preparation of 1-amino-2-alkylsulfuric acids |
US3839343A (en) * | 1969-11-10 | 1974-10-01 | Allied Chem | Symmetrical polyfluoroisoalkoxyalkyl quaternary ammonium sulfates |
-
1977
- 1977-11-04 DE DE19772749329 patent/DE2749329A1/de not_active Withdrawn
-
1978
- 1978-10-27 DE DE7878101238T patent/DE2860437D1/de not_active Expired
- 1978-10-27 EP EP78101238A patent/EP0001993B1/fr not_active Expired
- 1978-10-30 ES ES474666A patent/ES474666A1/es not_active Expired
- 1978-11-01 US US05/956,870 patent/US4209456A/en not_active Expired - Lifetime
- 1978-11-02 JP JP13464778A patent/JPS5473731A/ja active Granted
- 1978-11-06 CA CA315,842A patent/CA1112661A/fr not_active Expired
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1159957B (de) * | 1960-11-08 | 1963-12-27 | Bayer Ag | Verfahren zur Herstellung von quaternaeren Ammoniumverbindungen |
DE1493300B2 (de) * | 1962-10-12 | 1973-07-26 | Unilever N.V., Rotterdam (Niederlande) | Verfahren zum sulfatiren von aliphatischen alkoholen und aetheralkoholen |
US3257407A (en) * | 1963-09-27 | 1966-06-21 | Du Pont | Perfluoroalkyl substituted ammonium salts |
DE2310426B1 (de) * | 1973-03-02 | 1974-07-11 | Hoechst Ag | Hochfluorierte AEthersulfate und deren Verwendung als Egalisiermittel |
Also Published As
Publication number | Publication date |
---|---|
ES474666A1 (es) | 1980-12-16 |
EP0001993B1 (fr) | 1981-01-07 |
DE2860437D1 (en) | 1981-02-26 |
JPS5473731A (en) | 1979-06-13 |
DE2749329A1 (de) | 1979-05-10 |
CA1112661A (fr) | 1981-11-17 |
JPS629108B2 (fr) | 1987-02-26 |
US4209456A (en) | 1980-06-24 |
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