JPH0416194A - Production of ester mixture - Google Patents

Abstract

PURPOSE:To enable simple obtaining of an ester mixture in high yield by reacting fatty acids, etc., sugars, etc., and sugar ethers, etc., with a hydrolase in the presence of an organic solvent without containing water. CONSTITUTION:(A) One more fatty acids are obtained by selection from 6-22C (un)saturated fatty acids, esters of the aforementioned fatty acids with 1-3C lower alcohols and glycerol esters of the above-mentioned fatty acids. (B) One or more sugars are obtained by selection from 5-7C monosaccharides without any substituent groups, disaccharides composed of hexoses and 4-6C sugar alcohols. (C) One or more sugar ethers are obtained by forming ether bonds of one or more hydroxyl groups in the sugars (B) to 1-12C (un)saturated monohydric alcohols. The ingredients (B) and (C) are then blended so as to provide (98:2)-(2:98) ratio thereof and 2-8mol ingredient (A), based on the total 1mol of the ingredients (B) and (C). A porcine pancreatic lipase, etc., are subsequently added thereto, and reaction is carried out in the presence of tertiary butyl alcohol, etc., at 50-120 deg.C for about 24hr to produce an ester mixture of the sugar esters of the fatty acids with the sugar ethers of the fatty acids.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing an ester mixture of a sugar fatty acid ester and a sugar ether fatty acid ester.

Recently, as the world's surfactant continues to grow, sugar fatty acid esters and sugar ether fatty acid esters, which have sugars and sugar ethers as parent groups such as glucose and gelatin, are attracting attention as natural surfactants. However, when sugar fatty acid esters or sugar ether fatty acid esters are used alone, they may not be able to sufficiently exhibit the required surfactant properties. Therefore, in order to obtain the desired surfactant properties, sugars with various surfactant properties are used. It is desirable to use a mixture of fatty acid ester and sugar ether fatty acid ester.

When obtaining such an ester mixture, conventionally, the reactivity of fatty acids or their lower esters with respect to sugars and sugar ethers is different, and even if a mixture of sugars and sugar ethers is reacted with a fatty acid or a lower ester thereof, one of the sugars and sugar ethers It is thought that the ester synthesis or transesterification reaction with sugar proceeds preferentially, making it impossible to obtain a mixture of sugar fatty acid ester and sugar ether fatty acid ester commensurate with the mixing ratio of sugar and sugar ether. After separately synthesizing fatty acid ester and sugar ether fatty acid ester,
It has been surmised that a method of mixing these in a desired ratio is desirable.

However, instead of producing the sugar fatty acid ester and the sugar ether fatty acid ester separately and mixing them together in this way, the sugar fatty acid ester and the sugar ether fatty acid ester are produced at the desired mixing ratio from a mixture of sugar and sugar ether. It would be more advantageous if a mixture of

In view of the above circumstances, the present inventors conducted intensive studies on a method for advantageously synthesizing a mixture of a sugar fatty acid ester and a sugar ether fatty acid ester.
(B) one or more fatty acids selected from saturated and unsaturated fatty acids of 2, esters of the fatty acids with lower alcohols having 1 to 3 carbon atoms, and glycerin esters of the fatty acids, and (B) a number of carbon atoms with no substituents; one or more saccharides selected from 5 to 7 monosaccharides, disaccharides consisting of hexoses, and sugar alcohols having 4 to 6 carbon atoms; and (C) at least one hydroxyl group of the saccharide in (B) above has 1 carbon number. ~12 saturated or unsaturated monohydric alcohols and one or more sugar ethers forming an ether bond are treated with an organic solvent such as a tertiary alcohol that does not contain substantially water using a hydrolase. When the ester synthesis or transesterification reaction is carried out in the presence of esters, sugar fatty acid esters and sugar ether fatty acid esters are produced at a ratio corresponding to the mixing ratio of the above-mentioned saccharides (B) and sugar ethers (C), and with high production efficiency. The inventors discovered that a mixture can be synthesized all at once, leading to the present invention.

Therefore, the present invention is characterized in that the above components (A), (B), and (C) are subjected to ester synthesis or transesterification using a hydrolase in the presence of an organic solvent substantially free of water. Provided is a method for producing an ester mixture comprising a mixture of a sugar fatty acid ester and a sugar ether fatty acid ester.

The present invention will be explained in more detail below.

In the method for producing an ester mixture of the present invention, the first raw material is (A): saturated and unsaturated fatty acids having 6 to 22 carbon atoms;
These fatty acids are selected from esters of the fatty acids and lower alcohols having 1 to 3 carbon atoms, and glycerin esters of the fatty acids, and these can be used alone or in a mixture of two or more in a desired ratio. It will be done.

Here, the fatty acid used in the present invention is a saturated or unsaturated linear or branched fatty acid having 6 to 22 carbon atoms, and such a fatty acid has a hydroxyl group, a carbonyl group,
It may also be substituted with a phenyl group or the like. in particular,
Fatty acids include caproic acid, sorbic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitoleic acid, palmitic acid, stearic acid, and isostearic acid.

Oleic acid, linoleic acid, linuric acid, pentadecanoic acid,
Eicosanoic acid, tocosanoic acid, tocosenoic acid.

Arachidonic acid, lysyllic acid, dihydroxystearic acid, etc. can be used.

Furthermore, as the fatty acid ester, the above-mentioned carbon number 6-22
It uses esters of fatty acids and lower alcohols having 1 to 3 carbon atoms, such as methanol, ethanol, and propatool, specifically methyl caproate, ethyl caproate, methyl caprate, ethyl caprate, and laurin. Methyl acid, ethyl laurate, propyl laurate, methyl myristate, ethyl myristate, propyl myristate, methyl palmitate, ethyl palmitate, propyl palmitate, methyl stearate, ethyl stearate, propyl stearate, methyl oleate , ethyl oleate.

Propyl oleate, methyl linoleate, ethyl linoleate, propyl linoleate, methyl linoleate, ethyl linoleate, propyl linoleate.

Examples include methyl eicosanoate, methyl arachidonate, methyl tocosanoate, and methyl tocosenoate.

In addition, glycerin ester of fatty acid is one of the above fatty acids.
, 3-diglyceride, 1,2-glyceride, and triglyceride are preferably used. In this case, the fatty acid residues may be the same or different, and monoglycerides of the above-mentioned fatty acids can also be used. Such glycerin esters include, for example, glycerin-1,3-
dipalmitate, glycerin-1,2-diolate, glycerin-1,2-distearate, glycerin-1,
3-dilaurate, glycerin tricaprylate, glycerin trimyristate, palm oil.

Coconut oil, glycerin monocaprate, glycerin monostearate, etc. are mentioned.

Next, the second raw material is (B): a saccharide selected from unsubstituted monosaccharides having 5 to 7 carbon atoms, disaccharides consisting of hexoses, and sugar alcohols having 4 to 6 carbon atoms; Saccharides can also be used singly or in combination of two or more.

Here, examples of monosaccharides having 5 carbon atoms include arabinose, ribose, xylose, lyxose, xylulose, ribulose, 2-deoxyribose, etc., and monosaccharides having 6 carbon atoms such as glucose, galactose, and fructose. , mannose, sorbose, talose,
Examples include 2-deoxyglucose, 2-deoxygalactose, etc. Alloheptulose is a monosaccharide having 7 carbon atoms.

Examples include sedoheptulose, mannoheptulose, glucoheptulose, and the like.

In addition, examples of disaccharides consisting of hexose include maltose, sucrose, sophorose, and the like.

Furthermore, as a sugar alcohol, erythritol.

Examples include ribitol, xylitol, allitol, sorbitol, mannitol, galactitol, and the like.

The third raw material of the present invention is (C) a sugar ether in which at least one hydroxyl group of the sugar of (B) above forms an ether bond with a saturated or unsaturated monohydric alcohol having 1 to 12 carbon atoms. One kind or a combination of two or more kinds thereof can be used.

In this case, the position of the ether bond between the saccharide and the monohydric alcohol is not particularly limited, and may be at any position. Further, the monohydric alcohol may be a straight chain or a branched alcohol. Specific examples include methyl glucozide,
Ethyl glucodide.

Examples include glycosides such as propyl glucodide, methyl fructoside, methyl mannoside, methyl maltoside, and methyl lactoside, and sugar ethers such as 6-0-methylglucose and 6-0-methylfructose.

The present invention uses the above raw materials (A), (B), and (C), but in this case, the saccharides of (B) and the sugar ethers of (C) are adjusted to the desired mixing ratio of the product. selected accordingly. This mixture is prepared by reacting a saccharide (e.g. glucose) and a monohydric alcohol (e.g. methanol) using the method of Helferich et al. (Organic Synthesis, 1956, p. 366).
A mixture of sugar ether (glucose) and sugar ether (methyl glucodide) can also be prepared and used. The mixing ratio of the saccharide (B) to the sugar ether (C) can be present in the reaction system in the range of 98:2 to 2:98, but it is approximately the same as the desired ratio of the ester mixture. Used by mixing in proportion. In addition, the usage ratio of fatty acids in (A) is the same as that in raw material (B).

The amount of fatty acids may be equal to or less than 1 mole of the total amount of (C), but the molar ratio of fatty acids is more than 1 mole, preferably more than 1 mole and less than 50 moles, more preferably 1.5 to 50 moles. It is desirable to use 20 mol, especially in the range of 2 to 8 mol, so that the monoester can be obtained in high yield and selectively.

When performing ester synthesis or transesterification using a hydrolase using the above raw materials, examples of the hydrolase include porcine pancreatic lipase, yeast lipase derived from the genus Candida, and bacterial cell lipase derived from the genus Aspergillus, Mucor, and Pseudomonas. Lipases such as Pig liver-derived esterase, proteases such as trypsin, chymotrypsin, subtilisin, etc. are used.As these hydrolytic enzymes, any conventionally used enzyme reaction for this type of enzyme reaction may be used. Heat-resistant ones are preferred from the standpoint of selectively obtaining monoesters in high yield. For example, when using lipase, it is recommended to use the immobilized heat-stable lipase disclosed in Japanese Patent Application No. 1-210495.

Here, as a heat-stable hydrolytic enzyme, 50μ of enzyme powder was mixed with 0.4uQ(7)11/acid buffer (0.1M).

Various materials can be used as long as they have a heat resistance of 40% or more, preferably 80% or more, and more preferably 95% or more of residual activity after being dissolved in pH 7) and heated at 70° C. for 30 minutes. For example, Candida antarctica
thermostable lipase (sp-382, manufactured by NoVO)
, a thermostable lipase derived from Mucor mlehei (Lipozyme, manufactured by NoVO), etc. are preferably used. In addition, as thermostable proteases, those derived from Bacillus thermobroteorixus (Thermolysin ■) and those derived from Thermus aquaticus YT-G (Aqualysin ■) are used, but of course they are not limited to these. do not have.

In addition, the above-mentioned hydrolase may be a purified product or a crude product,
Furthermore, dried bacterial cells (treated bacterial cells, resting or stationary bacterial cells) that produce hydrolytic enzymes can also be used.

Furthermore, as a method for immobilizing the hydrolase, any of the carrier binding method, crosslinking method, and entrapping method may be employed, and the carrier binding method is particularly preferably employed. In this case, specific examples of the immobilization carrier include activated carbon, porous glass, acid clay, and bleaching clay.

Kaolinite, alumina, silica gel, bentonite,
Hydroxyapatite, calcium phosphate.

Inorganic substances such as metal oxides, natural polymer compounds such as starch and gluten, polyethylene, polypropylene, phenol formalin resin, acrylic resin.

Synthetic polymer substances such as anion exchange resins and cation exchange resins can be mentioned, but in the present invention, synthetic polymer substances that have porosity as a physical form, such as porous polyethylene, porous polypropylene, porous phenol, etc. Formalin resin.

Porous acrylic resin is most preferably used.

In the present invention, various immobilization carriers other than those described above may be used without any problem as long as they do not inhibit the expression of enzyme activity. Furthermore, the amount of hydrolytic enzyme immobilized on the immobilization carrier is usually 0.1 to 50% per 1 g of the immobilization carrier.
The amount of protein is 0, especially the amount of hydrolase in the protein is 2 to 5.
It is preferable to use immobilized proteins containing about 0% of the protein.

In the present invention, the amount of the hydrolase used is not particularly limited, but is 0.1 to 10,000 parts by weight, preferably 1 to 20 parts by weight, per 100 parts by weight of the fatty acid or ester thereof.
00 parts by weight.

In the present invention, the enzymatic reaction of the fatty acid or its ester with a saccharide or sugar ether using a hydrolase is carried out in the presence of an organic solvent substantially free of water.

The organic solvent is preferably a secondary or tertiary alcohol, such as 2,4-dimethyl-3-pentanol, 2,4-dimethyl-3-pentanol,
, 6-dimethyl-4-heptatool, tertiary butyl alcohol, tertiary amyl alcohol, diacetone alcohol, 3-methyl-3-pentanol, 3-ethyl-3-
Pentanol.

3-propyl-3-pentanol, 2-methyl-2-hexanol, 2-ethyl-2-hexanol, etc. can be used. In addition, pyridine, which is a good solvent for sugars,
Nitrogen-containing solvents such as dimethylformamide, dimethylacetamide, and quinoline, sulfur-containing solvents such as dimethyl sulfoxide, etc. can also be used in combination. However, ketones,
When saturated hydrocarbons and ethers are used, esterification of sugar ethers progresses, but esterification of sugars may not progress sufficiently. Note that these solvents may be used alone or as a mixed solvent of two or more.

The amount of the organic solvent used depends on the type of organic solvent, the carbon chain length of the fatty acid or its ester, the reaction temperature, etc., but is preferably 10 to 99% by weight of the entire reaction system, especially 6% by weight of the entire reaction system.
It is 0 to 80% by weight.

When the above raw materials (A) to (C) are subjected to an enzymatic reaction using a hydrolase, the reaction conditions can be adjusted as appropriate, and the reaction proceeds even at low temperatures, but it is particularly preferable to perform a heat-resistant immobilization reaction. If the reaction is carried out under temperature conditions, the reaction can be completed in about 24 hours.

Furthermore, when producing an ester mixture by the method of the present invention, for example, a method of filling a column with a hydrolase and passing the substrate solution (packed column method), introducing the substrate solution and the hydrolase into a reaction tank, stirring, The reaction can be carried out by employing a method in which the reaction is carried out by shaking (batch method), a method in which the reaction is carried out continuously in the batch method (continuous stirring tank method), and the like.

In addition, in the method of the present invention, water or carbon number 1
~3 lower alcohol is produced as a by-product, but in this case, the concentration of this by-product in the system is 0.5% by weight or less, particularly 0.1% by weight.
In order to proceed with the reaction efficiently, it is preferable to remove by-products as follows. Methods for removing these byproducts include, for example, zeolite, molecular sieves,
A method of adsorbing and removing Glauber's salt, etc. using outside and/or inside the reaction system, introducing dry air or inert gas into the reaction tank and removing it by evaporation into gas, or reducing the pressure inside the reaction tank. For example, the removal method may be evaporated, evaporated, and discharged out of the reaction tank.If these removal methods are appropriately combined with the above-mentioned enzyme reaction apparatus, the synthesis reaction can be carried out efficiently.

Note that the obtained reaction mixture can be purified according to a conventional method, and unreacted fatty acids contained in the reaction mixture can be separated, recovered, and reused.

The mixture of sugar fatty acid ester and sugar ether fatty acid ester obtained in this way has a high Krafft point and low solubility in a low temperature system when used alone, but by mixing the two, these drawbacks can be improved and various effects can be achieved. products,
In particular, it is easy to incorporate into liquid products.

〔Effect of the invention〕

According to the present invention, a mixture of a sugar fatty acid ester and a sugar ether fatty acid ester in a desired ratio can be produced at once and easily in high yield by ester synthesis or transesterification.

EXAMPLES Hereinafter, the present invention will be specifically explained with reference to examples, but the present invention is not limited to the following examples.

[Example 1] A mixture of 19.4 g (0.1 mol) of methyl glucodide and 18.0 g (0.1 mol) of glucose, 186 g (1 mol) of methyl decanoate, thermostable lipase derived from Candeda antarctica immobilized on acrylic resin (immobilized lipase sp-382, NoVO
18.5 g of tertiary butyl alcohol was added to 200 g of tertiary butyl alcohol, and then 50 g of Molecular Sieves SA was added as a demethanol agent, followed by stirring at 60° C. for 24 hours.

After the reaction, the reaction solution was acetylated by a conventional method, and the production rate was measured by gas chromatography. As a result, methyl glucozide decanoate ester was 98% (diester/monoester production ratio = 1/99) and glucose decanoate ester was 96% (jeltyl/monoester production ratio = 2/98).

It was confirmed that a reaction mixture was obtained at a ratio approximately corresponding to the mixing ratio of methyl glucodide and glucose as raw materials.

After the reaction mixture was filtered to remove the enzyme, the solvent was distilled off.
The resulting white solid was purified by washing with n-hexane to remove unreacted methyl decanoate.

[Examples 2 to 6] Ester mixtures were produced in the same manner as in Example 1 using the raw materials shown in Table 1 and under the conditions shown in the table. The results are shown in the same table.

Claims (1)

[Scope of Claims] 1. (A) Saturated and unsaturated fatty acids having 6 to 22 carbon atoms, esters of the fatty acids and lower alcohols having 1 to 3 carbon atoms;
and one or more fatty acids selected from glycerin esters of the fatty acids, and (B) monosaccharides having 5 to 7 carbon atoms without substituents, disaccharides consisting of hexoses, and sugar alcohols having 4 to 6 carbon atoms. One or more selected saccharides and (C) one sugar ether in which at least one hydroxyl group of the saccharide (B) above forms an ether bond with a saturated or unsaturated monohydric alcohol having 1 to 12 carbon atoms. A mixture of a sugar fatty acid ester and a sugar ether fatty acid ester, characterized in that ester synthesis or transesterification is carried out using a hydrolytic enzyme in the presence of a substantially water-free organic solvent. Method for producing ester mixtures.