JPH10327892A - Production of methylglycoside fatty acid ester - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a methylglycoside fatty acid ester in the presence of lipase, enabling to enhance the rate of the esterification reaction without increasing the amount of the enzyme, and enabling to efficiently and profitably produce the ester. SOLUTION: This method for producing a methylglycoside fatty acid ester comprises esterifying a fatty acid compound selected from saturated fatty acids, unsaturated fatty acids, and the esters of the fatty acids with lower alcohols with a methylglycoside such as a 5-7C monosaccharide in the presence of lipase. Therein, the methylglycoside comprises the β-isomer or a mixture of the β- isomer with the α-isomer.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to a method for producing a methylglycoside fatty acid ester by an esterification reaction using lipase.

[0002]

2. Description of the Related Art Hitherto, an alkylglycoside fatty acid ester of a monosaccharide has been produced by a chemical synthesis method in which a glycoside of a hexasaccharide is reacted with a fatty acid or a fatty acid derivative in the presence of a dehydrating condensing agent or a basic compound. (For example, US Pat. No. 4,716,152). However, in the chemical synthesis method in which the reaction is performed at a high temperature, it is difficult to obtain a high-quality fatty acid ester, and particularly, it is difficult to produce an ester containing a large amount of a monoester having a high surface activity. In contrast, under the absence of water, utilizing the properties of lipases that catalyze ester synthesis reactions and transesterification reactions,
Techniques for producing fatty acid esters of saccharides have been developed (JP-A-61-268192, JP-A-62-10779, J.
Am. Chem. Soc., 108, 5638 (1986), Japanese Patent Application
7-333191, Japanese Patent Application No. 8-35164). In the enzymatic method using this lipase, a fatty acid ester of a saccharide having a high monoester content can be produced depending on the selectivity of the enzyme. However, in this enzyme method, the solubility of saccharides in the presence of an organic solvent is considerably low, so that the rate of ester formation is slower than in the chemical synthesis method, and a large amount of enzyme must be used to increase the reaction rate. There was a problem from the side.

[0003]

DISCLOSURE OF THE INVENTION The present invention relates to a method for producing a methylglycoside fatty acid ester by a reaction using a lipase, whereby the rate of the esterification reaction is increased without increasing the amount of the enzyme, and it is efficient and economical. An object is to provide a method for producing the ester.

[0004]

Means for Solving the Problems The inventors of the present invention have found that the solubility of saccharides in an almost anhydrous state in the presence of an organic solvent is so low that the reaction rate of lipase is reduced. In order to solve the problem that the production efficiency of the ester is considerably lower than that of the above, an investigation was made. as a result,
When a mixture of α- and β-forms of methyl glycoside is used as the starting saccharide, the solubility of methyl glycoside in an organic solvent increases, so that the rate of the esterification reaction can be increased without increasing the amount of the enzyme. I learned that I can do it. Accordingly, the present invention provides a saturated and unsaturated fatty acid having 6 to 22 carbon atoms, at least one fatty acid compound selected from the group consisting of an ester of the fatty acid and a lower alcohol having 1 to 3 carbon atoms, A method for producing a methylglycoside fatty acid ester, comprising esterifying a monosaccharide having 5 to 7 carbon atoms and a methylglycoside of a saccharide selected from the group consisting of a disaccharide consisting of hexose or pentose with a lipase, The methyl glycoside is β
It is intended to provide a production method characterized by being a isomer or a mixture of an α-isomer and a β-isomer. Hereinafter, the present invention will be described in detail.

[0005] In the present invention, a methyl glycoside fatty acid ester is produced using a fatty acid compound and methyl glycoside as starting materials. Fatty acid compounds used in the present invention,
Compounds selected from the group consisting of saturated and unsaturated fatty acids having 6 to 22 carbon atoms and esters of the fatty acids and lower alcohols having 1 to 3 carbon atoms are preferable, and these compounds are used alone or in combination. Can be used. Examples of the fatty acid having 6 to 22 carbon atoms used in the present invention include:
Caproic acid, sorbic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, isostearic acid, oleic acid, linoleic acid, linoleic acid, eicosanoic acid, docosanoic acid, arachidonic acid, etc. Among the fatty acids having a hydroxyl group, those having a hydroxyl group include ricinoleic acid and dihydroxystearic acid, and those having a carboxyl group include malonic acid, maleic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid. And sebacic acid.

The fatty acid compounds of the present invention may be esters of these fatty acids with lower alcohols having 1 to 3 carbon atoms. Examples of the lower alcohol include methanol, ethanol, and propanol. Specific examples of the ester include methyl caproate, methyl caprylate, methyl caprate,
Methyl laurate, methyl myristate, methyl palmitate, methyl stearate, methyl oleate, ethyl caproate, ethyl caprylate, ethyl caprate,
Examples include ethyl laurate, ethyl myristate, ethyl palmitate, ethyl stearate, ethyl oleate, propyl laurate, propyl myristate, propyl palmitate, propyl stearate, propyl oleate, and the like. Incidentally, these specific fatty acid compounds,
They can be used alone or in combination.

The saccharide forming the methyl glycoside used in the present invention is selected from the group consisting of monosaccharides having 5 to 7 carbon atoms and disaccharides composed of hexose or pentose. Or in combination. To give specific examples of monosaccharides,
Monosaccharides having 5 carbon atoms include arabinose, ribose, xylose, lyxose, xylulose, and ribulose, and monosaccharides having 6 carbon atoms include glucose, galactose, fructose, mannose, sorbose, and talose. Examples of monosaccharides having 7 carbon atoms include alloheptulose, sedoheptulose and mannoheptulose. Examples of the disaccharide include maltose, lactose and sucrose. Of these, preferred examples of methyl glycosides include methyl arabinoside, methyl xylosid, methyl glucoside, methyl galactoside, methyl fructoside and the like.

In the present invention, the mixing ratio of the methyl glycoside to the fatty acid compound in the esterification reaction is preferably 0.1 to 100 mol, particularly 0.1 to 10 mol, per 1 mol of the methyl glycoside. The reason why the mixing ratio of the fatty acid compound is set to 0.1 mol or more is to facilitate stirring during the enzymatic reaction, and to set the mixing ratio to 100 mol or less to reduce the purification load when recovering the reaction product. . The lipase used in the present invention can be used without any limitation as long as it has been conventionally used in an esterification reaction. Examples of the lipase include porcine pancreatic lipase, yeast lipase derived from the genus Candida, aspergillus, cavilipase such as the genus Mucor, and bacterial lipase such as the genus Pseudomonas.
Neutral thermostable lipases derived from Candida antarctica and neutral thermostable lipases derived from Mucor miehei are preferred. Note that these
It is also possible to use an enzyme obtained by modifying the enzyme by genetic manipulation or the like.

[0009] The lipase may be in the form of either a purified enzyme or a crude enzyme, and is preferably used as a so-called immobilized enzyme immobilized on a carrier. The method for immobilizing the lipase includes a carrier binding method, a cross-linking method, and an entrapment method, and the carrier binding method is particularly preferred from the viewpoint of activity expression and the like. Examples of the immobilized carrier used here include activated carbon, porous glass,
Acid clay, bleaching clay, kaolinite, alumina, silica gel, bentonite, hydroxyapatite, calcium phosphate, inorganic substances such as metal oxides, natural polymers such as starch and gluten, polyethylene, polypropylene,
There are synthetic polymers such as phenol formaldehyde resin, acrylic resin, anion exchange resin, and cation exchange resin. In the present invention, porous synthetic polymers, such as porous polyethylene, porous polystyrene, porous polypropylene, porous phenol formaldehyde resin, and porous acrylic resin are particularly preferable. The amount of the lipase to be used in the present invention can be appropriately selected and is not particularly limited.
It is suitably from 01 to 500 parts by weight, preferably from 0.1 to 100 parts by weight. Further, when lipase is used as the immobilized enzyme, 0.1 part by weight of the methyl glycoside is used.
It is suitably from 1 to 10,000 parts by weight, preferably from 1 to 2000 parts by weight.

In the present invention, a reaction solvent is not necessarily required, but there is no problem in using it. Reaction solvents that can be used in the present invention include aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, ketones, nitrogen-containing solvents,
Examples include ethers, esters, halogenated hydrocarbons, sulfoxide solvents, and alcohols. Specific examples thereof include: aliphatic hydrocarbons such as n-heptane, n-hexane and isooctane; alicyclic hydrocarbons such as cyclopentane, cyclohexane and cyclobutane; benzene, toluene, xylene, Aromatic hydrocarbons such as phenol; ketones such as acetone, methyl isobutyl ketone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, mesityl oxide, cyclohexanone, methylcyclohexanone; acetonitrile; Morpholine, N-methylmorpholine, N-ethylmorpholine, 2-nitropropane, pyridine, 2-ethylpyridine, 2-methylpyridine,
3-methylpyridine, 4-methylpyridine, 2,4-lutidine, 2,6-lutidine, 2,4,6-collidine, pyrrole, N-methylpyrrole, piperidine, N-methylpiperidine, N-ethylpiperidine, piperazine , N-methylpiperazine, 1,4-
Dimethylpiperazine, pyrrolidine, 1-methylpyrrolidine, quinoline, butylamine, tributylamine, N, N,
N ', N'-tetramethyl-1,6-hexanediamine, N, N, N',
Nitrogen-containing solvents such as N'-pentamethyl-diethylene-triamine and dimethylformamide; ethers such as dimethyl ether, diethyl ether and dioxane; γ-butyrolactone, α-acetyl-γ-butyrolactone, diethyl carbonate, ethylene carbonate, propylene carbonate and the like Esters of carbon; halogenated hydrocarbons such as carbon tetrachloride, chloroform and methylene chloride; sulfoxide solvents such as dimethyl sulfoxide; 1-pentanol;
2-pentanol, 2-methyl-1-butanol, 2-methyl-1
-Pentanol, 1-heptanol, 2-heptanol,
Alcohols such as 2-ethyl-1-hexanol, 2,4-dimethyl-3-pentanol, 1,6-dimethyl-4-heptanol, tertiary-butyl alcohol, tertiary-amyl alcohol, diacetone alcohol Kind. In the present invention, these solvents can be used alone or in combination.

Although the reaction for the esterification of the present invention proceeds even at a low temperature, the reaction temperature is preferably set to 40 ° C. or higher in order to increase the reaction rate, and a range of 50 to 90 ° C. is particularly suitable. Enzymes whose activity is stable at higher temperatures, such as Candida antarctic described above.
a) When using neutral thermostable lipase derived from Mucor Miehei, considering the reaction rate and enzyme stability, the temperature particularly suitable for producing methylglycoside fatty acid ester is 65 to 80. It is in the range of ° C.

The present invention can be carried out by a continuous reaction or a batch reaction, and a batch reaction is particularly preferable. In the enzymatic reaction of the present invention, water or a lower alcohol having 1 to 3 carbon atoms is produced as a by-product, but it is necessary to remove this by-product in order to proceed the reaction efficiently. As a method for removing these by-products, for example, an adsorption removal method using zeolite, molecular sieves, silica gel, or the like, a method in which dry air or an inert gas is passed through a reaction vessel, and a method of evaporating and removing the gas in the gas, or There is a method of depressurizing and evaporating the inside of the reactor and discharging it out of the reaction system. In particular, a method of depressurizing and evaporating the inside of the reactor and discharging the reaction system is preferable. The pressure at this time is preferably not more than 10 mmHg higher than the vapor pressure of the solvent used at the reaction temperature. After completion of the reaction, thin-film distillation,
The fatty acid ester of a saccharide can be separated and collected from the reaction product by a conventional method such as crystallization. The thus obtained methylglycoside fatty acid ester is an excellent surfactant, and is used as a detergent, an emulsifier, and the like in a wide range of fields such as household products, cosmetics, cosmetics, foods, and pharmaceuticals.

[0013]

According to the method of the present invention, a methylglycoside fatty acid ester can be produced stably at a high conversion by a continuous reaction using lipase. Less than,
The present invention will be specifically described by showing Examples and Comparative Examples,
The following examples do not limit the scope of the invention.

[0014]

【Example】

[Example 1] 6.0 g of neutral heat-resistant immobilized lipase (Novozym435) derived from Candida antarctica and methyl glucoside (100% β-form) were placed in a stirred tank-type reactor using a 1000 ml four-necked flask. 31g, methyl caprate 44g
And 614 g of cyclohexanone, and an esterification reaction was carried out under the conditions of a reaction temperature of 70 ° C., a pressure of 40 mmHg, and a stirring speed of 300 rpm. Sampling over time, 0.1 ml of reaction solution
Into a screw tube, add 0.2 ml of pyridine, 50 μl of n-docosane and 0.4 ml of acetic anhydride as internal standard substances, and add
The reaction was carried out at 30 ° C for 30 minutes. 1 μl of the reaction solution was analyzed by gas chromatography to measure the amount of methyl glucoside caprate formed. After the measurement, the reaction rate was calculated using the following equation, and the results are shown in Table 1. Reaction rate (%) = A / B × 100 A = number of moles of fatty acid ester of generated saccharide B = number of moles of residual saccharide raw material + number of moles of fatty acid ester of generated saccharide

Example 2 Methyl glucoside capric acid ester was produced in the same manner as in Example 1 except that methyl glucoside having a mixing ratio of α-form: β-form = 6: 4 was used. The results are shown in Table 1. [Example 3] Methyl glucoside having a mixture ratio of α-form: β-form = 7: 3 was used, and the other conditions were the same as in Example 1.
Production of methyl glucoside caprate was performed.
The results are shown in Table 1. Comparative Example 1 Methyl glucoside capric ester was produced using 100% methyl glucoside in α-form and under the same conditions as in Example 1. The results are shown in Table 1. Comparative Example 2 Methyl glucoside caprate was produced using methyl glucoside in a mixture ratio of α-form: β-form = 9: 1 and the other conditions were the same as in Example 1. The results are shown in Table 1.

[0016]

[Table 1]

As is clear from the results shown in Table 1, β
Examples 1 to 3 using methyl glycosides containing 30% or more
3, a high conversion was obtained, while Comparative Example 1 using 100% methyl glycoside in α-form and Comparative Example 2 using 10% methyl glycoside in β-form showed a considerably low reaction rate. . Therefore, according to the present invention, it can be understood that a high-quality methylglycoside fatty acid ester having a large monoester content can be efficiently and economically produced without increasing the amount of lipase.

Claims (2)

[Claims] 1. At least one fatty acid compound selected from the group consisting of saturated and unsaturated fatty acids having 6 to 22 carbon atoms, esters of said fatty acids and lower alcohols having 1 to 3 carbon atoms, A method for producing a methylglycoside fatty acid ester comprising esterifying a monosaccharide having 5 to 7 atoms and a methylglycoside of a saccharide selected from the group consisting of a disaccharide consisting of hexose or pentose with a lipase, A production method, wherein the methyl glycoside is a β-form or a mixture of an α-form and a β-form. 2. The method for producing a methylglycoside fatty acid ester according to claim 1, wherein the mixture of the methyl glycoside α-form and β-form contains 30% or more of the β-form.