JP3157038B2 - Estride manufacturing method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for synthesizing estolide from ricinoleic acid using an enzyme.

[0002]

2. Description of the Related Art Estride is a chain ester formed by dehydration condensation of a hydroxyl group and a carboxyl group between two molecules of oxy fatty acid, and is a useful substance having industrially very many uses. Conventionally, estolide uses ricinoleic acid
Manufactured by heating to 220 ° C for several hours,
Since ricinoleic acid is exposed to high temperatures, it has a problem that it has a color or odor that is unsuitable for use in foods and the like.

In order to solve this problem, Japanese Patent Laid-Open Publication No.
No. 1 and JP-A-2-13387 propose a method of dissolving lipase, which is a kind of enzyme, in water and dispersing it in ricinoleic acid to synthesize estolide having no color or odor. However, this method has a problem that a large amount of water is present in the reaction system, so that the proceeding speed of the dehydration condensation reaction is slowed down and that only estride having a low degree of polymerization can be obtained.

Accordingly, the present inventors have developed a method for obtaining estride having a high degree of polymerization at a high reaction rate by using lipase immobilized on a carrier and adjusting the water content in the carrier. Filed as No. 4-18902. However, subsequent studies have revealed that although it is possible in a laboratory to accurately measure and control the water content in a carrier, there is a problem that it is not industrially easy.

[0005]

DISCLOSURE OF THE INVENTION The present invention solves the above-mentioned conventional problems, and provides a process for producing an estolide having a high degree of polymerization at a high reaction rate by a method which is industrially easily controlled. It was completed to provide a method.

[0006]

Means for Solving the Problems The present invention made to solve the above-mentioned problems is directed to a method for producing estolide from ricinoleic acid using an enzyme, wherein immobilized lipase is used as the enzyme, Water content on the horizontal axis
Take the water content x (mg / kg) in the bulk, and plot the neutralization value y on the vertical axis.
In a graph taking (NV: dimensionless quantity), the following equation
To the range expressed as the area between
One reaction to get an estolide with NV of 40 or less
It is characterized by the following. y = 8.14 × 10 ⁻¹⁴ x ⁴ −1.22 × 10 ⁻⁹ x ³ + 4.92 × 10 ⁻⁶ x ² + 1.92 × 10 ⁻³ x +33.6 (0 ≦ x ≦ 8000) Formula y = 7.24 × 10 ⁻⁷ x ² + 2.28 × 10 ⁻² x +32.0 (provided that 0 ≦ x ≦ 1000) Formula Also, the present invention provides a method for preparing estinate from ricinoleic acid using an enzyme.
In the method for producing a ride, the enzyme is immobilized as
Using lipase, the amount of water in the bulk
The moisture content x (mg / kg) is taken, and the neutralization value y (NV:
In a graph that takes a dimensionless quantity),
The reaction while adjusting within the range expressed as an area between
Advance to get an estride with an NV of 40 or less.
It is a sign. y = 6.82 × 10 ^-8 x ² + 1.26 × 10 ^-2 x +32.1 (where 0 ≦ x ≦ 8000) ... formula y = −9.31 × 10 ^-6 x ² + 7.22 × 10 ^{− 2} x +32.0 (however, 0 ≦ x ≦ 2000) ······· Expression lipase is Candida-rug
osa) is preferably used, and a porous ceramic such as calcined sepiolite is used as the immobilization carrier.

[0007] In the present invention, the water content in the bulk circulated through the reaction vessel containing the lipase immobilized as described above and the neutralization value (NV) are continuously measured. Here, NV is used as an index indicating the progress of the dehydration condensation reaction from ricinoleic acid.
Although V is about 140 to 170, the NV of estolide obtained by a conventional heating method is about 40, and therefore, it is an object of the present invention to keep the NV at 40 or less in the present invention. The water content in the bulk measured in this way (mg /
kg) can be easily adjusted by means such as a flash evaporator. In the present invention, by adjusting the amount of water in the bulk according to the change in NV, an estolide having an NV of 40 or less can be obtained. .

[0008]

According to the present invention, estride is produced from ricinoleic acid using lipase which is a biocatalyst.
There is no need to expose ricinoleic acid to high temperatures as before,
An estolide without color or odor can be obtained. Further, according to the present invention, the reaction proceeds while adjusting the water content in the bulk according to the change in NV, so that the water content in the reaction system is maintained in a region where the activity of the enzyme is sufficiently exhibited, and the dehydration is performed. A condensation reaction can be performed, and a high reaction rate can be obtained. Further, according to the present invention, the reaction proceeds while adjusting the amount of water in the bulk, which is industrially easy to measure and control, so that stable process control is possible.

[0009]

EXAMPLES Examples of the present invention will be described below together with comparative examples. Figure 1 shows the water content x (mg / kg) in the bulk on the horizontal axis.
The vertical axis is a graph in which the neutralization value y (NV: dimensionless amount) is taken. In this graph, RUN1 is indicated by using ricinoleic acid containing a relatively large amount of water as a starting material and circulating it through a reaction vessel containing immobilized lipase, without adjusting the amount of water in the bulk at all. This is the case where the reaction was allowed to proceed. In this case, the dehydration / condensation reaction proceeds by the action of the immobilized lipase, but the reaction stops when the curve shown as CE is reached, and the NV cannot be reduced to 65 or less. This curve CE means a reaction equilibrium line, which is represented by 0 ≦ x
When expressed by an approximate expression within the range of ≦ 8000, the following expression is obtained. y = 8.14 × 10 ⁻¹⁴ x ⁴ −1.22 × 10 ⁻⁹ x ³ + 4.92 × 10 ⁻⁶ x ² + 1.92 × 10 ⁻³ x +33.6

In FIG. 1, RUN2 is a case where ricinoleic acid whose water content is adjusted is used as a starting material and the reaction proceeds without any adjustment of the water content in the bulk as in RUN1. . Also in this case, the reaction stops when the curve CE is reached, and the NV cannot be reduced to 65 or less. These RUN1 and RUN2 show a method of dissolving a conventional lipase in water, dispersing it in ricinoleic acid, and reacting it. As described above, only estride having a low degree of polymerization can be obtained.
The amount of moisture in the bulk at the point where the curve CE is reached corresponds to the humidity in the air. In addition, since the reaction rate becomes extremely low near the curve CE, it can be seen that these methods are not suitable for industrially producing estolide.

Next, as RUN3 and RUN4, the same ricinoleic acid as RUN2 is used as a starting material, and NV
This is the case where the reaction was allowed to proceed while adjusting the amount of water in the bulk in accordance with the change in. In this case, the reaction still proceeds even when the NV becomes 60 or less, and an estolide having an NV of 40 or less can be obtained as shown by the arrow. As described above, it is preferable to decrease the water content in the bulk as the reaction proceeds, because the hydrophilicity of the bulk is reduced by the polymerization,
This is because the optimum moisture region changes depending on each reaction step.

The curve shown as C4 in FIG. 1 is for showing a region where the lipase enzyme activity is not expressed when the amount of water in the bulk is lower than this. This curve C4 is 0
When expressed by an approximate expression within the range of ≦ x ≦ 1000, the following expression is obtained. y = 7.24 × 10 ⁻⁷ x ² + 2.28 × 10 ⁻² x +32.0 Therefore, when the method of manufacturing the estolide of the present invention is carried out, it is expressed as an area between the above equations. It is necessary to proceed the reaction while adjusting the amount of water in the bulk within a certain range to obtain an estolide having an NV of 40 or less. In the region below the curve CE represented by the equation, the reaction proceeds in reverse.

The curve shown as C2 in FIG. 1 and C3
The curve shown as indicates a region where the reaction can proceed with high efficiency, and is approximated by the following equations, respectively. y = 6.82 × 10 ^-8 x ² + 1.26 × 10 ^-2 x +32.1 (0
≤ x ≤ 8000) y = -9.31 x 10 ^-6 x ² +7.22 x 10 ^-2 x +32.0 (0
≦ x ≦ 2000) Therefore, in carrying out the method for producing an estolide of the present invention, the reaction is allowed to proceed while adjusting the amount of water in the bulk within a range expressed as a region between these curves C2 and C3. If so, more favorable results can be obtained. It should be noted that the curve CM is a line indicating the most preferable reaction progress, and in practice, the operation may be controlled using the curve CM as a target value.

Although not shown in FIG. 1, the desired NV depends on the route of the reaction.
The time it takes to get an estolide of 40 or less varies greatly. Table 1 shows the time required for NV to reach 40 for RUN1 to RUN4.

[0015]

[Table 1]

As described above, in the case of RUN4 in which the reaction proceeds along a route close to the curve CM, an estolide having an NV of 40 or less can be manufactured in a very short reaction time as compared with the prior art. The chromaticity of the estolide obtained according to the present invention was measured, and the results were as shown in Table 2. Almost no coloring of estolide due to the reaction was observed.

[0017]

[Table 2]

[0018]

As described above, according to the method for producing estolide of the present invention, estolide having a large degree of polymerization having an NV of 40 or less can be obtained at a high reaction rate, and can be industrially measured. The reaction proceeds while adjusting the amount of water in the bulk, which is easy to control, so that stable process control is possible. Therefore, the present invention is extremely significant as a method for manufacturing an estolide that solves the conventional problems and contributes to industrial development.

[Brief description of the drawings]

FIG. 1 is a graph showing a relationship between a water content x in a bulk and a neutralization value y during a dehydration condensation reaction of estolide.

────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Mitsuo Kawase 1-7-7 Nishitatsugaoka, Chita City, Aichi Prefecture (56) References JP-A-2-13387 (JP, A) JP-A-64-63385 (JP) (A) JP-A-1-120295 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C12P 7/62 CA (STN) REGISTRY (STN)

Claims (2)

(57) [Claims] (1) using an enzyme to convert estradiol from ricinoleic acid;
In the method for producing the lipid, an immobilized resin is used as the enzyme.
The amount of water in the bulk is measured using a
Of water x (mg / kg), and the vertical axis represents neutralization value y (NV: no
In the graph that takes the dimension amount),
The reaction progresses while adjusting within the range expressed as the area between
And producing an estolide having an NV of 40 or less . y = 8.14 × 10 ⁻¹⁴ x ⁴ −1.22 × 10 ⁻⁹ x ³ + 4.92 × 10 ⁻⁶ x ² + 1.92 × 10 ⁻³ x +33.6 (0 ≦ x ≦ 8000) Formula y = 7.24 × 10 ^-7 x ² + 2.28 × 10 ^-2 x +32.0 (However, 0 ≦ x ≦ 1000) ... formula 2. The method according to claim 2, wherein the enzyme is used to convert ricinoleic acid into estradiol.
In the method for producing the lipid, an immobilized resin is used as the enzyme.
The amount of water in the bulk is measured using a
Of water x (mg / kg), and the vertical axis represents neutralization value y (NV: no
In the graph that takes the dimension amount),
The reaction progresses while adjusting within the range expressed as the area between
And get an estride with an NV of 40 or less
Manufacturing method of estolide. y = 6.82 × 10 ^-8 x ² + 1.26 × 10 ^-2 x +32.1 (where 0 ≦ x ≦ 8000) ... formula y = −9.31 × 10 ^-6 x ² + 7.22 × 10 ^{− 2} x +32.0 (however, 0 ≦ x ≦ 2000) ... formula