JPH0753115B2 - Method for producing polyol fatty acid ester - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial application] The present invention relates to a method for producing a polyol fatty acid ester,
More specifically, it relates to a method for easily producing a polyol fatty acid ester having a mixed acid residue of a branched fatty acid and a linear fatty acid in one molecule with high purity by an enzymatic method.

[Conventional technology and its problems]

As a method which has been put into practical use as an industrial production method of fatty acid esters of polyols, there is generally a method of esterification or alcoholysis. However, the method for producing a polyol fatty acid ester having a mixed acid residue of a branched fatty acid and a linear fatty acid in one molecule, which is the objective of the production method of the present invention, with high purity is limited.

Mixed ester of branched and straight chain fatty acids When a fatty acid and a polyol are esterified in the presence or absence of a catalyst, the reactivity of the hydroxyl groups of the polyol is not selective and various forms of random ester bonds are formed. The above polyol fatty acid ester is synthesized.

For example, in the synthesis of a glycerin fatty acid ester of a branched fatty acid (B) and a linear fatty acid (S), glycerin is used for the purpose of triglyceride. When expressed by A mixture of 6 types of triglycerides is produced in a random distribution according to the fatty acid ratio. Also, if the purpose is diglyceride (However, 1,2-diglyceride and 1,3-diglyceride are not distinguished here), and a mixture of the above-mentioned triglycerides is formed.

Polyol ester having mixed acid residues of branched fatty acid and linear fatty acid (in the case of the above, in the case of triglyceride Or In the case of jigselide The method for obtaining is by solvent fractionation of the esterified mixture,
It is conceivable to concentrate the fraction of esters with mixed acid residues. However, if the difference in melting point and the difference in solubility are small, almost no concentration is possible, and even if the concentration is high, the yield is very low and it cannot be put to practical use.

As another method, a partial ester of a branched fatty acid or a linear fatty acid is previously synthesized by esterification, and the remaining fatty acid is added to this partial ester (for the branched fatty acid partial ester, a linear fatty acid or a linear fatty acid is used). It is considered that a fatty acid partial ester is reacted with a branched fatty acid) halide or the like. However, even in this method, the target product esterified regioselectively cannot be obtained efficiently because it does not show selectivity for the residual hydroxyl group of the partial ester. Further, it is difficult to obtain a product that is satisfactory in terms of quality and safety.

Like the ester targeted for the production method of the present invention, there are a few examples of polyol ester having a mixed acid residue of a branched fatty acid and a linear fatty acid in a molecule (for example, Japanese Patent Publication No.
Almost no studies have been made except for the publication (60-20362). Furthermore, no studies have been conducted on ester compositions having high concentrations of those esters.

However, the inventors' studies have revealed that these polyol esters have some characteristics not found in conventional linear fatty acid esters or branched fatty acid esters and mixtures thereof. For example, a branched / straight-chain mixed acid ester that is liquid and has viscosity and low temperature resistance,
In the solid state, remarkable characteristics such as extensibility and crystallinity are exhibited.

However, it is considered that the practical and economical production method has not been established in the past, because the polyol ester having a mixed acid residue of such branched fatty acid and linear fatty acid has not been noted. Moreover, even if the performance of the ester is actually recognized, it is only contained in a part of the mixture, and the sufficient effect cannot be exhibited.

As described above, in the method for producing a polyol ester having a mixed acid residue of a branched fatty acid and a linear fatty acid, the fatty acid distribution becomes random by conventional chemical methods such as esterification and alcoholysis, and even if distillation, fractionation, etc. Even if the above concentration method is used in combination, there is a limit in increasing the purity of the intended polyol ester having a mixed acid residue.

[Means for solving problems]

Therefore, as a result of intensive research to solve the above-mentioned problems, the present inventors have found that by using an enzymatic method (lipase), a mixed acid residue of highly branched branched fatty acid and linear fatty acid can be obtained with a high synthesis achievement rate. It was found that the polyol ester possessed was practically and economically obtained, and the present invention was completed.

Accordingly, the present invention provides a method for producing a polyol fatty acid ester having a mixed acid residue, which comprises reacting a partial ester of a polyol and a branched fatty acid with a linear fatty acid or a lower alcohol ester thereof in the presence of lipase. The purpose is to easily prepare a polyol ester having a mixed acid residue of a branched fatty acid and a linear fatty acid in one molecule at a high concentration, which was impossible by conventional chemical production methods. To provide a way to get to.

The feature of the method for producing a polyol ester having a mixed acid residue of a branched fatty acid and a linear fatty acid in one molecule in the present invention is that a polyol partial ester having a branched fatty acid is treated with a linear fatty acid or a direct fatty acid in the presence of lipase. It is to act a lower alcohol ester of a chain fatty acid. This utilizes the fact that lipase has extremely low reactivity with branched fatty acids. That is, the partial polyol ester having a branched fatty acid is not hydrolyzed or transesterified in the presence of lipase,
It is esterified or alcoholysed only with the linear fatty acid or its lower alcohol ester. Therefore,
A linear fatty acid is selectively esterified to the remaining hydroxyl groups of the branched fatty acid partial ester of the starting material, and the target product can be obtained with high purity and high yield. Thus, the present invention has been completed by maximizing the characteristics of lipase.

Hereinafter, the present invention will be described in detail.

Examples of the polyol used in the present invention include ethylene glycol, propylene glycol (1,2-propanediol), 1,3-propanediol, 1,2-butanediol,
1,3-Blandiol, 1,4-Blandiol, 2,3-Butanediol, 1,5-Pentanediol, 2,4-Pentanediol, 1,6-Hexanediol, 2,5-Hexanediol, 1 Typical examples include alkanediols such as 2,8-octanediol and 2,7-octanediol, alkanetriols such as 1,2,4-butaneditriol, glycerol, and 1,2,6-hexanetriol, and diglycerol. And dimers, trimers, and multimers thereof.

Examples of the branched and straight chain fatty acids used in the present invention include saturated or unsaturated fatty acids having 4 to 24 carbon atoms. For example, as a branched fatty acid,
Trialkyl acetic acid, 2-alkyl branched acid, methyl branched acid, multi-branched acid and the like disclosed in JP-A-60-27647 are used. Specific examples include 2-ethylhexanoic acid, isoperargonic acid, isomyristic acid, isostearic acid, and the like. As the linear fatty acid, valeric acid, caproic acid, enanthic acid, caprylic acid, pelargonic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, palmitoleic acid, olein. Examples thereof include acids, elaidic acid, erucic acid, selevic acid, and linoleic acid. Further, these linear fatty acids may form esters with lower alcohols having 1 to 3 carbon atoms, such as methanol, ethanol and propanol. Examples of the branched fatty acid and linear fatty acid or the lower alcohol ester thereof can be exemplified, but the selection of the fatty acid and the lower alcohol ester is not limited in the present invention.

Next, any lipase can be used as long as it has ester synthesizing ability as the lipase used for carrying out the present invention. For example, Rhizopus genus Aspergillus genus, Mucor genus , Geotrichum, Pseudomonas (Pseudo)
monas genus Penicillium genus, Chromobacterium genus, Candi
Specific examples thereof include lipases derived from microorganisms belonging to the genus da), the genus Achromobacter, or the genus Alcaligenes. Among these lipases, those which selectively act on the α-position of the polyol can synthesize particularly useful target products. For example, when glycerin fatty acid ester (diglyceride) containing 1 mol of branched fatty acid and 1 mol of linear fatty acid is synthesized, the glycerin monoester of branched fatty acid and the linear fatty acid are allowed to act in the presence of α-selective lipase. be able to. The stable form of branched fatty acid glycerin monoes is α-monoglyceride, and only at the other α ′ position,
Due to the action of the α-selective lipase, a diglyceride containing both highly pure branched fatty acid and linear fatty acid can be easily obtained. Examples of the α-position selective lipase effective for producing a diglyceride containing both such a branched fatty acid and a linear fatty acid include, for example, Rhizopus delemer and Rhizpus japonicas.
opus japonicus), Mucormiehe
i) and Mucorjavanicus.

In addition, the lipase may be used as it is after being isolated and purified as it is, but in consideration of economic efficiency, lipase immobilized on various carriers, so-called lipase preparation (immobilized lipase) It is better to use.

Further, the reaction system containing a partial fatty acid polyol ester of a branched fatty acid and a linear fatty acid or a lower alcohol ester thereof as a substrate, in which lipase is present, is substantially inert to water such as n-hexane and petroleum ether. It is effective to dehydrate in the presence or absence of an organic solvent (excluding the primary alcohol solvent).

The reaction temperature should be selected in the optimum range depending on the desired product and the fatty acid which is the raw material substrate, but it is preferably carried out at a temperature of 10 to 90 ° C. When the temperature is lower than 10 ° C, the system tends to become heterogeneous, and when the temperature is higher than 90 ° C, the lipase activity is lowered.

〔The invention's effect〕

According to the present invention, a polyol ester containing a branched fatty acid and a linear fatty acid in one molecule can be obtained with high purity and high yield. Moreover, this mixed acid type polyol ester has a characteristic performance. Therefore, the method of the present invention can be widely applied to the production of cosmetics, cosmetics, pharmaceuticals, and chemicals of lubricating oil plastic additives.

〔Example〕

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited to these Examples.

Example 1 1000 g of isostearic monoglyceride [2.79 mol, isostearic acid used is Nissan Chemical's 5,7,7-trimethyl-2- (1,3,3-trimethylbutyl) -octanoic acid],
Charge 640 g (2.81 mol) of myristic acid and 150 g of lipase 4S (Amano Pharmaceutical Co., Ltd. 2800 U / g) into a 4-necked flask of 5 and
Stirring reaction was performed at 0 ° C. and 100 Torr for 5 hours to prepare isostearo myristin diglyceride. The ester synthesis rate of this reaction-terminated product was 90%. The term "ester synthesis rate" as used herein refers to the amount of fatty acid consumed by esterification after the reaction with the fatty acid in the charged substrate in the reaction system, expressed as a percentage. The unreacted isostearyl monoglyceride and myristic acid were removed by passing the reaction-finished product through a thin-film distillation apparatus at 190 ° C. and 0.03 Torr to obtain 1310 g of the target isostearo-myristin diglyceride as a distillation residue.

This product was converted into a fused silica capillary (DB-
1, J & W) gas chromatography (GLC) composition analysis, monoglyceride 3%, diglyceride
It was 89% and triglyceride 8%. The ratio of the components of dichryceride is diisostearin glyceride 9%, isostearo myristin diglyceride 91%. The amount of dimyristin glyceride was 0%.

Example 2 1000 g (4.59 mol) of 2-ethylhexane monoglyceride, 1500 g (4.41 mol) of behenic acid, and a commercial lipase formulation Lipozyme 3A (Mucor miehei-immobilized lipase, immobilized on a covert ion exchange resin, Novo Industry). -A-S (manufactured by AS) 200 g was charged into a four-necked flask, and the mixture was stirred and reacted at 75 ° C and 220 Torr for 3 hours.
The reaction-terminated product obtained at an ester synthesis rate of 96% was treated at 185 ° C.
Pass it through a thin film distiller of 0.05 Torr to get the desired 2-ethylexano-behendiglyceride as a distillation residue.
I got 10g.

When this product was analyzed by the GLC method shown in Example 1, it was 0% monoglyceride, 88% diglyceride and 12% triglyceride. The component ratio of diglyceride is di-2-
Ethylhexaneglyceride 0%, 2-ethylhexano
The content of behediglyceride was 91% and that of dibehen glyceride was 9%.

Example 3 1000 g of isomyristic acid monoester of trimethylene glycol (3.50 mol, a monoester synthesized using isomyristic acid manufactured by Nissan Chemical Industries, Ltd.), 1100 g of behenic acid (3.24)
Mol) and 200 g of Lipozyme 3A used in Example 2
A 4-necked flask was charged, and 2000 ml of hexane was further added to dissolve behenic acid. A tube for separating and refluxing hexane / water was set in the flask, and a stirring reaction was performed at 55 ° C. for 6 hours under reduced pressure. The reaction-completed product obtained by removing the lipase preparation by filtration had an ester synthesis rate of 83%. This product is passed through a thin film distiller at 200 ° C. and 0.05 Torr in the same manner as in the above embodiment, and is intended. 1730 g of an isomilist behendiester of trimethylene glycol was obtained as a distillation residue.

GLC analysis of the resulting product showed that the trimester glycol diester was 100%. The composition ratio of diester is 2% for di-isomyristine ester, 94% for isomirist behendiester, and 4% for di-behenester.
Met.

Claims (6)

[Claims] 1. A method for producing a polyol fatty acid ester having a mixed acid residue, which comprises reacting a partial ester of a polyol and a branched fatty acid with a linear fatty acid or a lower alcohol ester thereof in the presence of lipase. 2. A lipase is allowed to act by dehydration in the presence or absence of an organic solvent (excluding a primary alcohol solvent) without substantially adding water to the reaction system. The manufacturing method according to claim 1. 3. The method according to claim 1, wherein the branched fatty acid and the linear fatty acid are saturated or unsaturated fatty acids having 4 to 24 carbon atoms. 4. The lipase is genus Rhizopus, genus Aspergillus, genus Mucor,
Geotrichum, Pseudomonas (Pseu)
genus domonas, Penicillium genus, Chromobacterium genus, Candida (C
The method according to claim 1, which is a lipase derived from a microorganism of the genus andida), the genus Acromobacter, or the genus Alcaligenes. 5. The method according to claim 1, wherein the polyol is alkanediol or alkanetriol. 6. The production method according to claim 1, wherein the lipase is a lipase selective to the α-position of a polyol.