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WO1997036000A1 - Processus d'esterification - Google Patents

Processus d'esterification Download PDF

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Publication number
WO1997036000A1
WO1997036000A1 PCT/EP1997/000834 EP9700834W WO9736000A1 WO 1997036000 A1 WO1997036000 A1 WO 1997036000A1 EP 9700834 W EP9700834 W EP 9700834W WO 9736000 A1 WO9736000 A1 WO 9736000A1
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WO
WIPO (PCT)
Prior art keywords
process according
reaction
alkylglycoside
iii
fatty acid
Prior art date
Application number
PCT/EP1997/000834
Other languages
English (en)
Inventor
Pieter Axel Pel
Cornelis Van Der Sar
Cock Verboom
Original Assignee
Unichema Chemie B.V.
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 Unichema Chemie B.V. filed Critical Unichema Chemie B.V.
Publication of WO1997036000A1 publication Critical patent/WO1997036000A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P19/00—Preparation of compounds containing saccharide radicals
    • C12P19/44—Preparation of O-glycosides, e.g. glucosides
    • C—CHEMISTRY; METALLURGY
    • C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
    • C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
    • C12P7/00—Preparation of oxygen-containing organic compounds
    • C12P7/64—Fats; Fatty oils; Ester-type waxes; Higher fatty acids, i.e. having at least seven carbon atoms in an unbroken chain bound to a carboxyl group; Oxidised oils or fats

Definitions

  • the present invention relates to the preparation of fatty acid esters of alkylglycosides by enzymatically catalysed transesterification.
  • Fatty acid esters of alkyl glycosides form a group of compounds of which many have surface active properties. More specifically, they form a class of mild surfactants or emulsifiers, having
  • the reaction is an esterification of an alkylglycoside with a fatty acid.
  • Both direct esterification of an alkylglycoside with a fatty acid as well as transesterification (involving an ester exchange reaction between a lower alkyl ester of a fatty acid and an alkylglycoside) are reported.
  • Alkali or acid catalysed reactions as well as enzymatically catalysed reactions are known.
  • fatty acid esters of alkyl glycosides which have a high content of mono ⁇ esters and a low amount of side products such as alkyl glycoside di-, tri- and poly esters, cracked products etcetera, since these may lead to less favourable properties, in particular surface active properties, and/or a bad odour and/or colour of the product.
  • alkylglycoside esters meeting the demands as set out above, these compounds should be manufactured by transesterification of alkylglycosides with alkyl esters of fatty acids in an enzymatically catalysed process.
  • the products according to the invention are obtained by transesterification of alkylglycosides with an alkyl ester of the fatty acid using a lipase enzyme as a catalyst. Since the alkylglycoside and the alkyl ester of the fatty acid are not (well) miscible with each other, an organic solvent is added to the reaction mixture, in order to obtain a homogeneous reaction mixture. Such a homogeneous reaction mixture is needed in order to achieve an acceptable initial reaction rate, since heterogeneous reaction mixtures do not show an acceptable reactivity. Additionally, the solvent serves to lower the viscosity of the reaction system, which is desired for convenient processing, in particular in combination with a bed of immobilized enzymes so as to enable (semi-) continuous processing.
  • the alkylglycoside ester (III) resulting from the transesterification of (I) with (II), is contacted with an enzyme catalyst, wherein the relative amounts of the compounds (I) , (II) , and (III) at the start of the reaction are chosen such that the composition is located in the homogeneous phase region of the ternary system of components (I) , (II) and (III) .
  • the alkylglycoside ester (III) is the compound to obtain.
  • homogeneous phase in this respect it is meant a liquid which appears as one homogenous (or single) phase as observed by the person skilled in the art, without a visible separation surface (e.g. meniscus) between two or more phases, at the temperature and pressure given (generally those about equal to the temperature and pressure at the start of the reaction) .
  • the reaction mixture continues to be a single, homogeneous phase as the reaction proceeds. It was found that the present reaction system complies to that.
  • the relative amounts of the compounds (I) , (II) , and (III) at the start of the reaction are chosen such that the reaction is carried out in the homogeneous phase region of the ternary system of compounds (I) , (II) and (III) .
  • the starting composition is chosen such that the initial viscosity is not too high.
  • the viscosity is below 250 mPa.s, or even more preferably below 200 mPa.s.
  • the amount of alkylglycoside ester (III) in the starting mixture is preferably kept low, since this is the product to be obtained. Since (trans)esterification is a reaction around an equilibrium, it is advantageous to start with an excess of one of the starting compounds. It was found that if an excess of alkylester of a fatty acid (II) is used, good yields are obtained. As an additional benefit, the viscosity thereby remains within reasonable limits during the complete reaction from starting point to end point. It is surprising that the viscosity remains quite low, since it would be expected that it rises upon the formation of the alkyl glycoside ester (III) . Also, any excess fatty acid alkyl ester can easily be removed after the reaction.
  • alkylglycoside (I) The balance in relative amounts in the reaction system (i.e. in addition to compounds (II) and (III)) is made up by alkylglycoside (I) .
  • Typical relative amounts of the three compounds in the starting mixture are very much dependent on the actual compounds to be prepared.
  • the relative amount of alkylglycoside (I) is generally between 0.01 and 0.45, preferably between 0.05 and 0.25.
  • the relative amount of fatty acid alkylester (II) is typically between 0.20 and 0.98, preferably between 0.30 and 0.85.
  • the relative amount of alkylglycoside ester (III) is typically between 0.05 and 0.85, preferably between 0.1 and 0.45.
  • the enzyme catalyst in the process according to the invention is in an immobilized form (e.g. as known in the art of esterification) .
  • an enzyme catalyst comprises a lipase.
  • the lipase used is a thermostable lipase, such as derived from Candida antarctica (e.g. lipase A) as described in WO 88/02775, or derived from Muc_ ⁇ r miehei.
  • the process is carried out without the addition of a substantial amount of solvent.
  • some solvent e.g. lower alkyl alcohol such as ethanol
  • the alkylglycoside (I) employed generally contains a small amount of alkanol, following the manufacture of the alkylglycoside. Such a solvent is generally removed when lowering the pressure upon starting the reaction.
  • the alkyl group of the alkylglycoside (I) has 1-4 carbon atoms.
  • ethylglycosides and methyl glycosides are generally preferred.
  • the alkyl group of the alkylester of a fatty acid (II) has 1-4 carbon atoms. It is most preferred that the alkylester of fatty acid (II) comprises a methyl ester or an ethylester.
  • the alkylester of a fatty acid (II) comprises alkylesters of straight and branched chain, saturated or unsaturated fatty acids having a total number of carbon atoms of between 6 and 22. More preferred are alkyl esters of fatty acids which are selected from the group consisting of methyl laurate, ethyl laurate, methyl caprate, ethyl caprate, methyl oleate, ethyl oleate, methyl stearate, ethyl stearate, methyl iso-stearate and ethyl iso-stearate.
  • glycosides comprise glucosides.
  • the reaction may suitably be employed by introducing in a reaction vessel:
  • the compound (I) is a mixture comprising the alkylglycoside, oligoglycosides and the free sugar itself, depending upon the manufacture of this compound.
  • compound (III) is generally a mixture comprising the alkylglycoside ester itself, in admixture with other components such as alkylglycoside and oligoglycoside (and the fatty acid ester thereof) .
  • the amounts should be chosen such that the mixture appears a one single, homogenous phase, at reaction conditions.
  • a suitable (batch) process is carried out by lowering the pressure of the reactor vessel (after introducing the reaction compounds and the catalyst as described above) to below 100 mbar (typical) at the start of the reaction, so as to enable removal of the alcohols formed.
  • the temperature is elevated and maintained at a temperature at which the enzymatic catalyst performs well (normally between 40 and 70°C) .
  • the reaction may proceed for 5-100 hours, depending upon e.g. the temperature and the amount of catalyst.
  • the pressure is brought to atmospheric, and the mixture is allowed to cool to room temperature.
  • the mixture so obtained (now enriched in alkylglycoside ester content) may be employed directly, or it may be purified in any way known in the art, depending upon its future use.
  • the above process may be employed in a continuous manner, involving the continuous addition of starting compounds (I) and (II) to the reaction mixture, and the continuous removal of finalized product (III) .
  • the reaction mixture may be circulated over a fixed catalyst bed.
  • the ingredients used in the examples were prepared separately. Below a description is given of the preparation of Ethyl Glucoside, the Ethyl Esters of Capric, Why and Oleic acid and the Ethyl Glucoside esters, used as ingredients for the examples.
  • a certain amount of the alkylglycoside ester (III) which is the desired end product, should be used when starting the reaction.
  • the alkylglycoside ester (III) used for this purpose is obtained using the reaction according to the invention.
  • the alkylglycoside ester should be obtained first in another way, as known in the art, and as is set out below.
  • composition of the ethanol free product is: 75 wt% Ethyl Glucoside (substantially pure) , 4 wt% Glucose and 21 wt% Oligoglucosides.
  • EG product is considered to be the mixture with the aforementioned composition.
  • EC Ethyl Oleate
  • EO Ethyl Oleate
  • Lauroyl-, Caproyl and Oleyl-EGE's were made by direct esterification using the procedure as described in patent WO 94/01575, under vacuum at 60°C of respectively Whyley acid (PRIFRAC 2922 ex Unichema International) ,
  • Capric acid (PRIFRAC 2906 ex Unichema International) and Oleic acid (PRIFRAC 6905 ex Unichema International) with EG product (see above) using 5.0 wt% immobilized Candida antarctica lipase as the catalyst (7100 PLU/gram) .
  • the reactions were done with 20 molar% excess of the fatty acid. After the reaction the excess of fatty acid was removed by molecular distillation.
  • Lauroyl EGE product is to be understood a mixture comprising: 69 wt% Lauroyl EGE
  • Caproyl EGE product is to be understood a mixture comprising: 63 wt% Caproyl EGE (substantially pure) , 2 wt% Capric acid, 8 wt% EG, 27 wt% oligoglucoside (ester) likewise, "Oleoyl EGE product " is to be understood a mixture comprising: 75 wt% Oleoyl EGE (substantially pure) , 2 wt% Oleic acid, 1 wt% EG, 22 wt% oligoglucoside (ester) .
  • a mixture of 60.0 g dry EG, 65.8 g Ethyl Laurate and 0.60 g immobilized enzyme ( Candida antarctica lipase immobilized on Accurel, SP611, ex NOVO Nordisk; activity: 7100 PLU/g) were brought into a one-necked flask. The flask was continuously rotated in an oil-bath of 60 °C and vacuum of 20-25 mbar was applied. The Ethyl Laurate did not dissolve in the EG. After 27 hour, approximately 1.4 wt% Lauroyl EGE was found in the Ethyl Laurate layer. No Lauroyl EGE was found in the EG-layer.
  • reaction mixture In a 500 ml four-necked glass reaction vessel equipped with a mechanical stirrer, thermocouple and nitrogen supply, 205.05 gram reaction mixture was brought.
  • the initial composition of the reaction mixture was: 15.0 wt% EG product as above, 45.0 wt% Ethyl Laurate and 40.0 wt% Lauroyl EGE product as above.
  • the reaction was done at 60°C and a pressure of 28 mbar in the presence of 1.54 gram (0.75 wt%) immobilized enzyme ( Candida antarctica lipase immobilized on Accurel (SP611 ex Novo Nordisk; activity: 7100 PLU/gram) ) .
  • immobilized enzyme Candida antarctica lipase immobilized on Accurel (SP611 ex Novo Nordisk; activity: 7100 PLU/gram) .
  • 7.5 1/hr nitrogen was supplied using a dippipe.
  • Lauroyl EGE was synthesized using the procedure as described in example 1 above.
  • the initial composition of the reaction mixture was: 15.0 wt% EG product as above, 40.0 wt% Lauroyl EGE and 45.0 wt% Methyl Laurate as above (Methyl Laurate, ESTOL 1502 was supplied by Unichema International) .
  • the reaction was done at 70°C and a pressure of 21 mbar in the presence of 2.05 gram (1.00 wt%) immobilized enzyme ( Candida antarctica lipase immobilized on Accurel (SP611 ex Novo Nordisk; activity: 7100 PLU/gram) .
  • During the reaction 1.9 1/hr nitrogen was supplied using a dippipe.
  • the mixture was converted from a composition of 28.6 wt% EGE and 13.6 wt% EG to a mixture with 49.5 wt% EGE and 3.5 wt% EG (as analyzed by GC) .
  • the viscosity was 47 mPa.s, at the end of the reaction the viscosity appeared to be 55 mPa.s.
  • Caproyl EGE was synthesized using the procedure as described in example 1.
  • the initial composition of the reaction mixture was: 15.0 wt% EG product as above, 45.0 wt% Ethyl Caprate and 40.0 wt% Caproyl EGE product as above.
  • After a reaction time of 41 hours the mixture was converted from a composition of 27.0 wt% EGE and 14.5 wt% EG to a mixture with 41.0 wt% EGE and 3.8 wt% EG.
  • the viscosity was 150 mPa.s, at the end of the reaction the viscosity appeared to be 103 mPa.s. 4 ⁇ .
  • Oleoyl EGE was synthesized using the procedure as described in example 1.
  • the initial composition of the reaction mixture was: 14.0 wt% EG product as above, 45.0 wt% Ethyl Oleate and 41.0 wt% oleoyl EGE product as above.
  • After a reaction time of 66 hours the mixture was converted from a composition of 39.9 wt% EGE, and 10.7 wt% EG to a mixture with 57.4 wt% EGE and 4.6 wt% EG.
  • the viscosity was 94 mPa.s, at the end of the reaction the viscosity appeared to be 180 mPa.s.
  • a starting mixture with a composition of 40.0 wt% Lauroyl EGE product, 50.0 wt% Ethyl Laurate and 10.0 wt% Ethyl Glucoside product has a viscosity of 48 mPa.s at 60 °C.
  • the composition had changed from 26.5 wt% EGE and 8.2 wt% EG to 42.3 wt% EGE and 1.1 wt% EG.
  • the final viscosity was 55 mPa.s.
  • a starting mixture with a composition of 40.0 wt% Lauroyl EGE product, 40.0 wt% Ethyl Laurate and 20.0 wt% Ethyl Glucoside product has a viscosity 182 mPa.s at 60 °C.
  • the composition had changed from 26.5 wt% EGE and 14.2 wt% EG to 31.0 wt% EGE and 12.7 wt% EG.
  • the final viscosity was 475 mPa.s.

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Abstract

La présente invention concerne un processus permettant de préparer des esters d'acides gras d'alkylglucosides (III) par transestérification d'un alkylglucoside (I) avec un alkylester d'acide gras (II) en présence de l'ester d'alkylglucoside (III) produit par la transestérification de (I) avec (II). La réaction est catalysée par voie enzymatique. Les quantités relatives des composés (I), (II) et (III) au début de la réaction sont choisies de manière que ladite réaction se produise dans la région de phase homogène du système ternaire des composés (I), (II) et (III).
PCT/EP1997/000834 1996-03-27 1997-02-19 Processus d'esterification WO1997036000A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP96200832.2 1996-03-27
EP96200832 1996-03-27

Publications (1)

Publication Number Publication Date
WO1997036000A1 true WO1997036000A1 (fr) 1997-10-02

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6489468B1 (en) 1999-03-05 2002-12-03 Wolff Walsrode Ag Regioselectively substituted esters of oligo- and polysaccharides and a method of producing them

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988002775A1 (fr) * 1986-10-17 1988-04-21 Novo Industri A/S Lipase a position non specifique a base d'especes de candida, procede de production, utilisation et procede a l'adn recombinant de production de ladite lipase
WO1989001480A1 (fr) * 1987-08-21 1989-02-23 Novo-Nordisk A/S Nouveaux composes organiques et procede de preparation desdits composes
WO1990009451A1 (fr) * 1989-02-17 1990-08-23 Novo Nordisk A/S Procede de production d'esters de glucosides et compositions comprenant des esters de glucosides
WO1994001575A1 (fr) * 1992-07-07 1994-01-20 Unilever N.V. Procede de preparation d'esters glycosides alkyles
WO1994018290A1 (fr) * 1993-02-03 1994-08-18 Nabisco, Inc. Synthese de graisses d'acetoglycerides

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1988002775A1 (fr) * 1986-10-17 1988-04-21 Novo Industri A/S Lipase a position non specifique a base d'especes de candida, procede de production, utilisation et procede a l'adn recombinant de production de ladite lipase
WO1989001480A1 (fr) * 1987-08-21 1989-02-23 Novo-Nordisk A/S Nouveaux composes organiques et procede de preparation desdits composes
WO1990009451A1 (fr) * 1989-02-17 1990-08-23 Novo Nordisk A/S Procede de production d'esters de glucosides et compositions comprenant des esters de glucosides
WO1994001575A1 (fr) * 1992-07-07 1994-01-20 Unilever N.V. Procede de preparation d'esters glycosides alkyles
WO1994018290A1 (fr) * 1993-02-03 1994-08-18 Nabisco, Inc. Synthese de graisses d'acetoglycerides

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6489468B1 (en) 1999-03-05 2002-12-03 Wolff Walsrode Ag Regioselectively substituted esters of oligo- and polysaccharides and a method of producing them
US6852852B2 (en) 1999-03-05 2005-02-08 Wolff Walsrode Ag Method of producing regioselectively substituted esters of oligo- and polysaccharides

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