EP0001993B1 - Fluorhaltige Alkyl-sulfato-betaine und Verfahren zu deren Herstellung - Google Patents

Fluorhaltige Alkyl-sulfato-betaine und Verfahren zu deren Herstellung Download PDF

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Publication number
EP0001993B1
EP0001993B1 EP78101238A EP78101238A EP0001993B1 EP 0001993 B1 EP0001993 B1 EP 0001993B1 EP 78101238 A EP78101238 A EP 78101238A EP 78101238 A EP78101238 A EP 78101238A EP 0001993 B1 EP0001993 B1 EP 0001993B1
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EP
European Patent Office
Prior art keywords
denotes
atoms
formula
sulfato
betaines
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.)
Expired
Application number
EP78101238A
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German (de)
English (en)
French (fr)
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EP0001993A1 (de
Inventor
Siegfried Dr. Billenstein
Winfried Dr. Ehrl
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Hoechst AG
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Hoechst AG
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Publication date
Application filed by Hoechst AG filed Critical Hoechst AG
Publication of EP0001993A1 publication Critical patent/EP0001993A1/de
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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.
  • 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.
  • 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-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.
  • 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
  • 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.
  • 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 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.
  • 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, 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.
  • 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, 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.
  • 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.
  • 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 whose IR and NMR spectra match the product obtained in Example 1.
  • Example 4 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.
  • 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.
  • 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.

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Business, Economics & Management (AREA)
  • Emergency Management (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (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)
EP78101238A 1977-11-04 1978-10-27 Fluorhaltige Alkyl-sulfato-betaine und Verfahren zu deren Herstellung Expired EP0001993B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19772749329 DE2749329A1 (de) 1977-11-04 1977-11-04 Fluorhaltige alkyl-sulfato-betaine und verfahren zu deren herstellung
DE2749329 1977-11-04

Publications (2)

Publication Number Publication Date
EP0001993A1 EP0001993A1 (de) 1979-05-30
EP0001993B1 true EP0001993B1 (de) 1981-01-07

Family

ID=6022976

Family Applications (1)

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EP78101238A Expired EP0001993B1 (de) 1977-11-04 1978-10-27 Fluorhaltige Alkyl-sulfato-betaine und Verfahren zu deren Herstellung

Country Status (6)

Country Link
US (1) US4209456A (enrdf_load_stackoverflow)
EP (1) EP0001993B1 (enrdf_load_stackoverflow)
JP (1) JPS5473731A (enrdf_load_stackoverflow)
CA (1) CA1112661A (enrdf_load_stackoverflow)
DE (2) DE2749329A1 (enrdf_load_stackoverflow)
ES (1) ES474666A1 (enrdf_load_stackoverflow)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0100180A1 (en) * 1982-07-22 1984-02-08 The British Petroleum Company p.l.c. A method for producing polymerisable monomers containing a sulphate group

Families Citing this family (16)

* Cited by examiner, † Cited by third party
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
US4408043A (en) * 1982-03-08 1983-10-04 Nalco Chemical Company Fluorocarbon surfactants
US4377710A (en) * 1982-03-08 1983-03-22 Nalco Chemical Company Quaternized epichlorohydrin adducts of perfluoro substituted ethanols
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
CA2271379A1 (en) 1996-11-22 1998-05-28 David W. Owens Halogen exchange reactions and uses thereof
CA2554293A1 (en) 2004-01-30 2005-08-18 Great Lakes Chemical Corporation Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams, and foam stabilizers
US20070161537A1 (en) * 2004-01-30 2007-07-12 Great Lakes Chemical Corporation Production processes and systems, compositions, surfactants, monomer units, metal complexes, phosphate esters, glycols, aqueous film forming foams and foam stabilizers
CN1938414A (zh) * 2004-01-30 2007-03-28 大湖化学公司 生产方法和系统、组分、表面活性剂、单体单元、金属配合物、磷酸酯、二元醇、水性成膜泡沫以及泡沫稳定剂
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
RU2007149322A (ru) * 2005-07-28 2009-07-10 Грейт Лэкс Кемикал Корпорэйшн (Us) Способы и системы получения, композиции, поверхностно-активные вещества, мономерные звенья, комплексы металлов, сложные эфиры фосфорной кислоты, гликоли, водные пленкообразующие пены и стабилизаторы пен
US20070027349A1 (en) * 2005-07-28 2007-02-01 Stephan Brandstadter Halogenated Compositions
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

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2803656A (en) * 1956-01-23 1957-08-20 Minnesota Mining & Mfg Fluorocarbonsulfonamidoalkanols and sulfates thereof
DE1159957B (de) * 1960-11-08 1963-12-27 Bayer Ag Verfahren zur Herstellung von quaternaeren Ammoniumverbindungen
NL299140A (enrdf_load_stackoverflow) * 1962-10-12
US3257407A (en) * 1963-09-27 1966-06-21 Du Pont Perfluoroalkyl substituted ammonium salts
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
DE2310426C2 (de) * 1973-03-02 1975-03-06 Farbwerke Hoechst Ag, Vormals Meister Lucius & Bruening, 6000 Frankfurt Hochfluorierte Xthersulfate und deren Verwendung als Egalisiermittel

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0100180A1 (en) * 1982-07-22 1984-02-08 The British Petroleum Company p.l.c. A method for producing polymerisable monomers containing a sulphate group

Also Published As

Publication number Publication date
JPS629108B2 (enrdf_load_stackoverflow) 1987-02-26
CA1112661A (en) 1981-11-17
JPS5473731A (en) 1979-06-13
US4209456A (en) 1980-06-24
DE2860437D1 (en) 1981-02-26
DE2749329A1 (de) 1979-05-10
EP0001993A1 (de) 1979-05-30
ES474666A1 (es) 1980-12-16

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