WO1999037657A1 - Procede pour produire des oligoglucosides d'alkyle et/ou d'alcenyle a chaine courte - Google Patents

Procede pour produire des oligoglucosides d'alkyle et/ou d'alcenyle a chaine courte Download PDF

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Publication number
WO1999037657A1
WO1999037657A1 PCT/EP1999/000197 EP9900197W WO9937657A1 WO 1999037657 A1 WO1999037657 A1 WO 1999037657A1 EP 9900197 W EP9900197 W EP 9900197W WO 9937657 A1 WO9937657 A1 WO 9937657A1
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WO
WIPO (PCT)
Prior art keywords
water
alcohol
alkenyl
carbon atoms
alkyl
Prior art date
Application number
PCT/EP1999/000197
Other languages
German (de)
English (en)
Inventor
Rainer Eskuchen
Bernhard Gutsche
Jens Vier
Stephan Blum
Jörg KAHRE
Holger Tesmann
Original Assignee
Cognis Deutschland Gmbh
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 Cognis Deutschland Gmbh filed Critical Cognis Deutschland Gmbh
Publication of WO1999037657A1 publication Critical patent/WO1999037657A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical
    • C07H15/10—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical containing unsaturated carbon-to-carbon bonds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07H—SUGARS; DERIVATIVES THEREOF; NUCLEOSIDES; NUCLEOTIDES; NUCLEIC ACIDS
    • C07H15/00—Compounds containing hydrocarbon or substituted hydrocarbon radicals directly attached to hetero atoms of saccharide radicals
    • C07H15/02—Acyclic radicals, not substituted by cyclic structures
    • C07H15/04—Acyclic radicals, not substituted by cyclic structures attached to an oxygen atom of the saccharide radical

Definitions

  • the invention relates to a process for the production of short-chain glycosides by acid acetalization of glycoses with alcohols, in which the continuous removal of water from the reaction equilibrium is carried out with the aid of vapor permeation.
  • Alkyl glycosides are obtained by acid-catalyzed acetalization of aldo- or ketohexoses with alcohols or by transacetalization of short-chain glycosides with longer-chain alcohols.
  • the sugars can be used as solids or as aqueous starch breakdown products.
  • Also suitable as starting materials for the transacetalization are reaction mixtures of short-chain glucosides from starch degradation, which may contain water in addition to the alcohol.
  • the molar ratio of sugar to alcohol can influence the glycoside composition and thus the product properties.
  • Another important influencing factor is the amount of water that is present or formed during the reaction. In order to minimize the side reactions taking place in the presence of water and to achieve an acceptable reaction rate, the lowest possible water content is sought in the course of the reaction.
  • some of the alcohols, which often form azeotropes with water are also removed from the reaction mixture in the conventional removal of water by distillation, which leads to a reduction in the excess of alcohol.
  • fresh alcohol has hitherto been metered in continuously, which is associated with considerable technical outlay and additional costs.
  • Another problem is that the resulting alcohol / water mixture has to be worked up separately, which can be very expensive, particularly in the case of azeotropes. In addition, it is energetically unfavorable to first condense the steam flow and then to reheat it for the purpose of distillation separation.
  • the present invention is therefore based on the object of providing a process for the preparation of short-chain alkyl glycosides which is free from the disadvantages described.
  • the invention relates to a process for the preparation of short-chain alkyl and / or alkenyl oligoglycosides, in which glycoses are acetalized in the presence of acidic catalysts with an excess of saturated or unsaturated alcohols having 1 to 6 carbon atoms and water is continuously removed from the equilibrium, which is removed characterized in that the water in the form of a mixture with alcohol is drawn off in vapor form from the reaction space, passed through a membrane module, by applying a vacuum or flushing with a sweep gas stream, a partial pressure drop of the water to be separated off is generated from the feed side to the permeate side of the membrane, and in this way the water and small amounts of alcohol are separated off as permeate, while the concentrated retentate condenses outside the membrane module or as steam and is returned to the reactor.
  • both the water contained in the raw material and the water formed in the acetalization can be quantitatively removed from the equilibrium, and besides the low technical and energy expenditure, the particular advantage is that only very little alcohol passes through the membrane, so that there is no need to add fresh alcohol. This enables the glycoside composition to be set reliably without monitoring the concentration of the distillate stream.
  • R 1 is an alkyl and / or alkenyl radical having 1 to 8 carbon atoms
  • G is a sugar radical having 5 or 6 carbon atoms
  • p is a number from 1 to 10.
  • the alkyl and / or alkenyl oligogiycosides can be derived from aldoses or ketoses with 5 or 6 carbon atoms, preferably glucose. Anhydrous glucose or aqueous glucose syrup are particularly suitable as starting materials.
  • the preferred alkyl and / or alkenyl oligogiycosides are thus alkyl and / or alkenyl oligoglucosides.
  • alkyl and / or alkenyl oligogiycosides whose degree of oligomerization is less than 1.8 and is in particular between 1.4 and 1.6.
  • the alkyl or alkenyl radical R 1 can be derived from monohydric or polyhydric alcohols having 1 to 8, preferably 2 to 4, carbon atoms. Typical examples are methanol, ethanol, butanol, hexanol, allyl alcohol, 2-ethylhexyl alcohol, ethylene glycol, glycerin, trimethylolpropane and pentaerythritol.
  • the acetalization can be carried out in a manner known per se, as is described, for example, in the publications EP-A1 0301298 and WO 90/03977 (Henkel).
  • alcohol and catalyst for example, are initially introduced, heated to the reaction temperature and then the glycose, in this case preferably aqueous glucose syrup, is metered in. If one starts from anhydrous glucose, it is usually dispersed in the alcohol and the catalyst solution is introduced into the heated dispersion.
  • the molar use ratio of glycose to alcohol is generally in the range from 1: 1 to 1:10, preferably 1: 4 to 1: 8 and in particular 1: 5 to 1: 6.
  • mineral acids such as sulfuric acid
  • sulfocarboxylic acids such as sulfosuccinic acid or aromatic sulfonic acids such as p-toluenesulfonic acid or dodecylbenzenesulfonic acid are preferably used.
  • the choice of acid catalysts is for the success of the acetalization is not very critical, the amount used is 0.1 to 2, preferably 0.5 to 1% by weight, based on the starting materials.
  • the reaction temperature must be chosen so that no caramelization of the sugar can take place; it is usually in the range of 90 to 112 ° C.
  • the reaction time depends on the desired degree of conversion and polymerization; it is therefore also dependent on the excess alcohol used.
  • the reaction time is typically 3 to 4 hours, and after the end of the water separation, which indicates the end point of the acetalization, there is generally a subsequent stirring time of about 1 hour.
  • Both the water contained in the raw material (e.g. from aqueous glucose syrup) and the water formed in the acetalization as steam are continuously removed from the reactor in order to shift the reaction equilibrium to the side of the products.
  • the steam which essentially contains water and alcohol, is processed in the sense of the process according to the invention by connecting the reactor with the aid of a heatable line to a membrane module into which the vaporous alcohol / water mixture is passed.
  • a partial pressure drop of the water to be separated from the feed to the permeate side of the membrane is generated with the aid of a vacuum pump or by flushing with a sweep gas stream (for example air), which causes the smaller water molecules to pass through the membrane while the larger alcohol molecules remain on the retentate side.
  • a sweep gas stream for example air
  • the acidic catalyst is neutralized by adding a base, for example sodium hydroxide and / or magnesium oxide, and excess alcohol is removed quantitatively in vacuo, for example using a packed column, a falling-film or thin-layer evaporator.
  • a base for example sodium hydroxide and / or magnesium oxide
  • excess alcohol is removed quantitatively in vacuo, for example using a packed column, a falling-film or thin-layer evaporator.
  • the resulting glycoside can then be bleached with H2O2.
  • the short-chain alkyl or alkenyl glucosides obtainable by the process according to the invention are suitable, for example, as solubilizers (methyl glucosides, butyl glucosides) or as precursors for the preparation of organosilicon compounds (allyl glucosides) or for transacetalization with long-chain alcohols.
  • solubilizers methyl glucosides, butyl glucosides
  • organosilicon compounds allyl glucosides
  • transacetalization with long-chain alcohols for transacetalization with long-chain alcohols.
  • Comparative example V2 Comparative example V2. Comparative example V1 was repeated, but the alcohol-rich upper phase of the heterogeneous butanol / Vasser azeotrope was returned to the reactor. Details of the test procedure and the results can be found in Table 1.
  • Example 1 Analogous to Comparative Example V1, the experimental plant here also consisted of a 4-liter glass reactor provided with a double jacket, with a bottom drain and stirrer. The reactor was also equipped with a dropping funnel and connected via a heatable line to a membrane module from Langbein & Engelbracht, the permeate side of which was connected to a vacuum pump via a cooler and water separator. The temperature was controlled using a circulating thermostat with thermal oil. For acetalization, butanol and acid catalyst were placed in the reactor and heated to the reaction temperature, then liquid 70% by weight glucose syrup (99% by weight glucose) was again metered in with vigorous stirring.
  • Example 1 The water contained in the glucose syrup was withdrawn from the reactor together with the condensation water as a vaporous butanol / water mixture and passed through the heated line into the membrane module.
  • the vacuum created on the permeate side created a partial pressure drop in the water.
  • the water and small amounts of butanol passed through the membrane and were separated, while the concentrated retentate was condensed outside the membrane module and returned to the reactor.
  • the reaction mixture was neutralized by adding magnesium oxide. Details of the test procedure and the results can be found in Table 1.
  • Example 2 Example 1 was repeated using anhydrous glucose and allyl alcohol. For this purpose, the glucose was initially introduced together with the alcohol and the catalyst was metered in after the reaction temperature had been reached. The reaction was continued as in Example 1, but without stirring.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Biotechnology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Biochemistry (AREA)
  • Health & Medical Sciences (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Molecular Biology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention concerne un procédé pour produire des oligoglucosides d'alkyle et/ou d'alcényle à chaîne courte, dans lequel on acétalise des glucoses en présence de catalyseurs acides avec un excédent d'alcools saturés ou insaturés possédant 1 à 8 atomes de carbone, et on élimine en continu l'eau de l'équilibre chimique. L'eau qu'on mélange avec l'alcool est évacuée sous forme de vapeur de la chambre de réaction et passe par un module membranaire. Une chute de pression partielle de l'eau à séparer, entre le côté alimentation et le côté perméat de la membrane, est produite par application d'un vide ou par rinçage avec un courant gazeux de balayage. Ainsi, l'eau et de faibles quantités d'alcool sont séparées les unes des autres sous forme de perméat, tandis que le rétentat concentré est condensé à l'extérieur du module membranaire ou bien réacheminé au réacteur sous forme de vapeur.
PCT/EP1999/000197 1998-01-22 1999-01-15 Procede pour produire des oligoglucosides d'alkyle et/ou d'alcenyle a chaine courte WO1999037657A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE1998102277 DE19802277A1 (de) 1998-01-22 1998-01-22 Verfahren zur Herstellung von kurzkettigen Alkyl- und/oder Alkenyloligoglykosiden
DE19802277.8 1998-01-22

Publications (1)

Publication Number Publication Date
WO1999037657A1 true WO1999037657A1 (fr) 1999-07-29

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PCT/EP1999/000197 WO1999037657A1 (fr) 1998-01-22 1999-01-15 Procede pour produire des oligoglucosides d'alkyle et/ou d'alcenyle a chaine courte

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DE (1) DE19802277A1 (fr)
WO (1) WO1999037657A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP1300413A1 (fr) * 2001-10-05 2003-04-09 Haltermann GmbH Procédé de synthèse de glycosides
DE10218916A1 (de) * 2002-04-27 2003-11-06 Degussa Verfahren zur Herstellung von Acetalen und Ketalen mit Hilfe mehrstufiger Pervaporation oder Dampfpermeation

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839318A (en) * 1970-09-27 1974-10-01 Rohm & Haas Process for preparation of alkyl glucosides and alkyl oligosaccharides
EP0301298A1 (fr) * 1987-07-18 1989-02-01 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation de glucosides d'alkyle
WO1990003977A1 (fr) * 1988-10-05 1990-04-19 Henkel Kommanditgesellschaft Auf Aktien Procede de production directe d'alkylglucosides
EP0492397A1 (fr) * 1990-12-26 1992-07-01 Kao Corporation Procédé de préparation d'alcoylglycosides
WO1995007915A1 (fr) * 1993-09-17 1995-03-23 Unichema Chemie B.V. Procede de preparation des alkylglucosides

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8518575D0 (en) * 1985-07-23 1985-08-29 Bp Chem Int Ltd Esterification process
DE3610011A1 (de) * 1986-03-25 1987-10-08 Geesthacht Gkss Forschung Verfahren zur trennung der komponenten eines fluessigkeitsgemisches voneinander
JPH069645B2 (ja) * 1986-12-25 1994-02-09 リグナイト株式会社 混合溶液の分離方法
US4894163A (en) * 1987-06-12 1990-01-16 Kuraray Co., Ltd. Separation of liquid mixtures
DE4019170A1 (de) * 1990-06-15 1991-12-19 Henkel Kgaa Verfahren zum durchfuehren einer gleichgewichtsreaktion unter anwendung von daempfepermeation

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3839318A (en) * 1970-09-27 1974-10-01 Rohm & Haas Process for preparation of alkyl glucosides and alkyl oligosaccharides
EP0301298A1 (fr) * 1987-07-18 1989-02-01 Henkel Kommanditgesellschaft auf Aktien Procédé de préparation de glucosides d'alkyle
WO1990003977A1 (fr) * 1988-10-05 1990-04-19 Henkel Kommanditgesellschaft Auf Aktien Procede de production directe d'alkylglucosides
EP0492397A1 (fr) * 1990-12-26 1992-07-01 Kao Corporation Procédé de préparation d'alcoylglycosides
WO1995007915A1 (fr) * 1993-09-17 1995-03-23 Unichema Chemie B.V. Procede de preparation des alkylglucosides

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