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WO1996008470A1 - Procede de production de monoglyceride-sulfates d'acides gras de couleur claire - Google Patents

Procede de production de monoglyceride-sulfates d'acides gras de couleur claire Download PDF

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Publication number
WO1996008470A1
WO1996008470A1 PCT/EP1995/003432 EP9503432W WO9608470A1 WO 1996008470 A1 WO1996008470 A1 WO 1996008470A1 EP 9503432 W EP9503432 W EP 9503432W WO 9608470 A1 WO9608470 A1 WO 9608470A1
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WO
WIPO (PCT)
Prior art keywords
acid
partial glycerides
fatty acid
products
glycerol
Prior art date
Application number
PCT/EP1995/003432
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German (de)
English (en)
Inventor
Ansgar Behler
Frank Clasen
Michael Coché
Christoph Breucker
Original Assignee
Henkel Kommanditgesellschaft Auf Aktien
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Henkel Kommanditgesellschaft Auf Aktien filed Critical Henkel Kommanditgesellschaft Auf Aktien
Publication of WO1996008470A1 publication Critical patent/WO1996008470A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C303/00—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides
    • C07C303/24—Preparation of esters or amides of sulfuric acids; Preparation of sulfonic acids or of their esters, halides, anhydrides or amides of esters of sulfuric acids

Definitions

  • the invention relates to a method for producing light-colored fatty acid monoglyceride sulfates, in which partial glycerides of a defined purity are used in the sulfation.
  • Sulphated partial glycerides especially monoglyceride sulphates, are anionic surfactants which are characterized by high foaming power, good cleaning performance and excellent dermatological compatibility [Anionic Surfactants, Pt.I, Surfactant science series Vol.7, .M. Linfield (Ed.), Marcel Dekker Inc., New York, 1976, p. 219].
  • the production of monoglyceride sulfates is usually based on glycerol, which is first reacted with oleum [DS 2693479] or chlorosulfonic acid [JP 78/77014] to form glycerol sulfate and then transesterified with the addition of a triglyceride to monoglyceride sulfate [ipidos J26, 19 ( 1966)].
  • the German Patent application DE-Al 3821446 further discloses a process for the preparation of monoglyceride sulfates by reacting glycerol with chlorosulfonic acid in an organic solvent, in which fatty acids or fatty acid esters are used for the transesterification.
  • the sulfonation with oleum or chlorosulfonic acid leads to products with a high electrolyte load and is therefore disadvantageous.
  • fatty acid monoglyceride sulfates are obtained without exception, which are so darkly colored that a bleaching step is necessary before commercial use in order to meet aesthetic requirements for the products.
  • the object of the invention is therefore to provide a process for the production of fatty acid monoglyceride sulfates with improved bleachability.
  • the invention relates to a process for the preparation of light-colored fatty acid monoglyceride sulfates by continuous reaction of technical partial glycerides with gaseous sulfur trioxide, aging of the acidic sulfonation products and neutralization with aqueous bases in the presence of a buffer, which is characterized in that partial glyceryl uses ride that have an iodine number in the range from 0 to 0.5, preferably 0.05 to 0.2 and / or an acid number in the range from 0 to 1.5, preferably 0.05 to 0.5 and in particular 0.05 have up to 0.2.
  • Partial glycerides are preferably used in the sulfation which fulfill both conditions with regard to iodine and acid number.
  • Partial glycerides are known chemical substances which can be obtained by the relevant methods of organic preparative chemistry, for example by transesterification of triglycerides with glycerol.
  • Mono- and difatty acid glycerol esters and their technical mixtures based on aliphatic carboxylic acids with 6 to 22 carbon atoms and 0, 1, 2 or 3 double bonds are suitable for producing the fatty acid monoglyceride sulfates.
  • lauric acid mono- and / or diglyceride is preferred.
  • the fatty acid components of the partial glycerides can in turn also represent technical mixtures, such as those obtained in the pressure splitting of natural fats and oils, such as coconut oil, palm oil, palm kernel oil, rapeseed oil, sunflower oil, coriander oil or beef tallow.
  • natural fats and oils such as coconut oil, palm oil, palm kernel oil, rapeseed oil, sunflower oil, coriander oil or beef tallow.
  • hardened coconut fatty acid mono- and / or diglyceride is preferred.
  • Partial glycerides of fatty acids with 8 to 18 and in particular 12 to 14 carbon atoms, which have a monoglyceride content in the range from 40 to 90% by weight, are preferably used.
  • partial glycerides are used in the reaction which have been prepared by transesterification of corresponding triglycerides with glycerol in the presence of lithium salts, in particular lithium hydroxide.
  • lithium salts in particular lithium hydroxide.
  • the products prepared by lithium salt catalysis are distinguished by a lower iodine number.
  • the sulfation of the partial glycerides with gaseous sulfur trioxide can be carried out in the manner known for fatty acid lower alkyl esters [J. Falbe (ed.), "Surfactants in consumer products", Springer Verlag, Berlin-Heidelberg, 1987, p. 61] ⁇ follow, with reactors working according to the falling film principle being preferred.
  • the sulfur trioxide is diluted with an inert gas, preferably air or nitrogen, and used in the form of a gas mixture which contains the sulfonating agent in a concentration of 1 to 8, in particular 2 to 5,% by volume.
  • the sulfonation can be carried out with 0.95 to 1.8 mol of gaseous sulfur trioxide per mole of the hydroxyl groups contained in the partial ester mixtures.
  • gaseous sulfur trioxide per mole of the hydroxyl groups contained in the partial ester mixtures.
  • the sulfonation can take place at temperatures of 70 to 98 ° C. With regard to the production of products with a high degree of sulfonation, it has proven optimal to choose a temperature of 90 to 95 ° C.
  • the crude sulfonation product is subjected to aging.
  • This step can be lent, for example in a pipe coil, or discontinuously, for example in a boiler.
  • the aging can take place over a period of 1 to 240 minutes, preferably 5 to 30 minutes and at temperatures of 70 to 98, preferably 90 to 95 ° C. If aging occurs within the specified limits at low temperatures, long dwell times are required to achieve high degrees of sulfonation and vice versa.
  • the acidic sulfonation products obtained during the sulfonation are stirred together with aqueous bases in an aqueous buffer solution and neutralized after aging, a pH of 5.5 to 9, preferably 6.5 to 8 being maintained, since otherwise hydrolysis of the Ester bond or cleavage of the sulfate group can take place.
  • a 1 to 5% by weight aqueous solution of sodium triphosphate, sodium hydrogen carbonate or citric acid can be considered as a buffer.
  • the bases for the neutralization are alkali metal hydroxides such as sodium, potassium and lithium hydroxide, alkaline earth metal oxides and hydroxides such as magnesium oxide, magnesium hydroxide, calcium oxide and calcium hydroxide, ammonia, mono-, di- and tri-C2-.4-alkanolamines, for example, mono-, di- and triethanolamine and also primary, secondary or tertiary C 4 alkylamines and glucamines.
  • the neutralization bases are preferably in the form of 5 to 55% by weight aqueous ger solutions are used, with 5 to 25 wt .-% aqueous sodium hydroxide solutions are preferred.
  • the sulfonation products are complex mixtures which contain more than 50% by weight sulfation products of the primary and secondary hydroxyl groups of the partial glycerides, ie mono- and diglyceride sulfates.
  • open-chain and cyclic glycerol sulfates as well as alpha-glycerol ester sulfonates, products with sulfate and sulfonate groups, soaps, sulfated soaps and glycerol can be contained in the reaction mixture. If one starts from unsaturated partial glycerides, the sulfur trioxide is also added to the double bond of the fatty acid component to form internal glycerol ester sulfonates.
  • aqueous solutions with solids contents of 5 to 15 or pastes with solids contents of 25 to 60% by weight are obtained. If desired, these can be subjected to additional bleaching and, if appropriate, processed to solids by spray drying, superheated steam drying, SKET granulation or similar processes. It is also also possible to subject the crude sulfation products to spray neutralization after aging and thus to obtain solids directly.
  • the light-colored fatty acid monoglyceride sulfates obtainable by the process according to the invention are high-foaming and ecotoxicologically compatible anionic surfactants which are suitable for the production of surface-active agents such as detergents, dishwashing detergents and cleaning agents as well as products for skin, tooth and body care Are considered in which they can be contained in amounts of 1 to 50, preferably 3 to 25 wt .-% - based on the agent.
  • 1650 g (5 mol) of technical monoglycerides with different acid and iodine numbers at 95 ° C. with sulfur trioxide were placed in a continuously working falling film reactor (length 120 cm, cross section 1 cm, educt throughput 600 g / h) with jacket cooling and lateral gasification implemented.
  • the use ratio was 1.3 moles of SO3 per mole of hydroxyl groups contained in the partial ester.
  • the sulfur trioxide was driven off by heating from a corresponding amount of 65% by weight oleum, diluted to a concentration of 5% by volume with nitrogen and brought into contact with the monoglyceride film via a nozzle.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

Des monoglycéride-sulfates d'acides gras de couleur claire sont produits par sulfatation, vieillissement et neutralisation, des glycérides partiels présentant un indice d'iode compris entre 0 et 0,5 et/ou un indice d'acide de 0 à 1,5 étant utilisés comme matières premières.
PCT/EP1995/003432 1994-09-12 1995-09-01 Procede de production de monoglyceride-sulfates d'acides gras de couleur claire WO1996008470A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE19944432367 DE4432367B4 (de) 1994-09-12 1994-09-12 Verwendung von Partialglyceriden in einem Verfahren zur Herstellung von hellfarbigen Fettsäuremonoglyceridsulfaten
DEP4432367.0 1994-09-12

Publications (1)

Publication Number Publication Date
WO1996008470A1 true WO1996008470A1 (fr) 1996-03-21

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Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1995/003432 WO1996008470A1 (fr) 1994-09-12 1995-09-01 Procede de production de monoglyceride-sulfates d'acides gras de couleur claire

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DE (1) DE4432367B4 (fr)
WO (1) WO1996008470A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999010457A1 (fr) * 1997-08-25 1999-03-04 Cognis Deutschland Gmbh Procede de stabilisation de tensioactifs aqueux de sulfate d'ester
DE19911040A1 (de) * 1999-03-12 2000-09-21 Cognis Deutschland Gmbh Tensidgranulate

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992009570A1 (fr) * 1990-12-03 1992-06-11 Henkel Kommanditgesellschaft Auf Aktien Procede de production de sulfates de glycerides partiels
WO1992009569A1 (fr) * 1990-12-03 1992-06-11 Henkel Kommanditgesellschaft Auf Aktien Procede de production en continu de sulfates de glycerides partiels
DE4204151A1 (de) * 1992-02-12 1993-08-19 Schneider Manfred Prof Dr Regioisomerenreine monoglyceride sowie ein verfahren zu ihrer herstellung durch enzymatische veresterung von glycerin in organischen loesungsmitteln

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3808427A1 (de) * 1988-03-14 1989-09-28 Henkel Kgaa Verfahren zur kontinuierlichen umesterung von fettsaeure-niedrigalkyl-estern

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1992009570A1 (fr) * 1990-12-03 1992-06-11 Henkel Kommanditgesellschaft Auf Aktien Procede de production de sulfates de glycerides partiels
WO1992009569A1 (fr) * 1990-12-03 1992-06-11 Henkel Kommanditgesellschaft Auf Aktien Procede de production en continu de sulfates de glycerides partiels
DE4204151A1 (de) * 1992-02-12 1993-08-19 Schneider Manfred Prof Dr Regioisomerenreine monoglyceride sowie ein verfahren zu ihrer herstellung durch enzymatische veresterung von glycerin in organischen loesungsmitteln

Also Published As

Publication number Publication date
DE4432367A1 (de) 1996-03-14
DE4432367B4 (de) 2006-04-20

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