JP6469989B2 - Method for fractionated production of sucrose fatty acid ester - Google Patents

Description

  The present invention relates to a method for fractionated production of sucrose fatty acid esters in which a mixture of a plurality of sucrose fatty acid esters having different degrees of esterification is fractionated into components having different degrees of esterification.

The sucrose fatty acid ester is obtained by esterifying an arbitrary hydroxyl group with a fatty acid among the eight hydroxyl groups contained in the sucrose molecule. The degree of esterification of a sucrose fatty acid ester is determined by the number of esterified hydroxyl groups. For example, a sucrose fatty acid ester having a degree of esterification of 2 means that two hydroxyl groups are esterified. Since sucrose fatty acid esters have good safety and biodegradability, they have been conventionally used as surfactants, emulsifiers, food additives, cosmetic materials and the like.
The sucrose fatty acid ester is usually produced by reacting sucrose with a fatty acid or an alkyl ester of the fatty acid, and is a mixture of a plurality of sucrose fatty acid esters having different esterification degrees. For example, in Non-Patent Document 1, sucrose fatty acid ester is produced by reacting sucrose with fatty acid methyl. Patent Document 1 discloses that sucrose is reacted with fatty acid methyl, and sucrose is further reacted to have a sucrose mono-fatty acid ester content of 38% by mass or more, and both sucrose di-fatty acid ester and sucrose tri-fatty acid ester content. It is described that a low sucrose fatty acid ester mixture was obtained (see Tables 1 and 3).
On the other hand, in Patent Document 2, lauric acid and a lipase enzyme derived from Candida cylindracea are added to a solution in which sucrose is dissolved in water and reacted, so that the monoester is about 20%, the diester is about 45%, and the triester is about It is described that a 35% sucrose fatty acid ester mixture was obtained (Example 3). Also, Example 2 of Patent Document 3 describes that a sucrose fatty acid ester mixture having about 20% monoester, about 45% diester, and about 35% triester was obtained.

  Since the characteristics of sucrose fatty acid esters vary depending on the degree of esterification, various methods for obtaining sucrose fatty acid ester mixtures rich in a specific degree of esterification have been proposed. For example, in the reference example of Patent Document 4, methyl ethyl ketone is used as an extraction solvent, and in Example 1, sucrose fatty acid ester is obtained from the reaction mixture by solid-liquid extraction with ethyl acetate and then liquid-liquid extraction with isobutanol. From the ratios of mono-, di- and triesters in Table 2 showing these results, it can be seen that the supernatant (B) is concentrated with a higher degree of esterification and the lower the temperature, the better the separation. On the other hand, Patent Document 5 discloses 5 to 14% by weight of a monoester component having an esterification degree of 1, 55 to 65% by weight of a diester component having an esterification degree of 2, and 26 to 35 of an ester component having an esterification degree of 3 or more. Although a sucrose fatty acid ester consisting of% by weight is disclosed, such a sucrose fatty acid ester mixture is fractionated from a reaction product obtained by an ordinary synthesis method using a column or the like, and the fraction is appropriately selected. By combining and mixing, a plurality of commercially available sucrose fatty acid esters may be mixed and mixed, or a commercially available sucrose fatty acid ester may be fractionated using a column or the like, and the fractions may be combined in an appropriate combination. It is described that it can be obtained. Also, Patent Document 6 discloses a sucrose fatty acid ester mixture containing 55 to 65% by weight of a diester component having a degree of esterification of 2, which is also divided into components using a column or the like, as in Patent Document 5. It is described that it was obtained by painting.

JP 2006-169237 A Japanese Patent Application Laid-Open No. 7-115983 JP-A-9-71594 JP-A 49-102609 JP 2009-214079 A JP 2009-215262 A

"Sugar ester story", published by Daiichi Kogyo Seiyaku Co., Ltd., 1984, pages 35 and 40-41

  An object of this invention is to provide the fractionation manufacturing method of the sucrose fatty acid ester which can be easily fractionated to the component from which esterification degree differs.

In the present invention, when a mixture of a plurality of sucrose fatty acid esters having different esterification degrees is subjected to solid-liquid separation by using 2-propyl alcohol as a fractionation solvent and cooled to a specific temperature, sucrose fatty acids having a desired esterification degree This is based on the knowledge that it can be separated into esters and the above-mentioned problems can be solved.
That is, the present invention is a high ester precipitated by dissolving a mixture of a plurality of sucrose fatty acid esters having different esterification degrees as raw materials in 2-propyl alcohol at a temperature of 50 ° C. or higher and then cooling to 38 to 45 ° C. Provided is a method for fractionated production of sucrose fatty acid ester, comprising solid-liquid separation of a solid content rich in the degree of conversion component, further cooling to 0 to 33 ° C., and separation and collection of a liquid content rich in the low esterification degree component .
The present invention also provides a high ester precipitated by dissolving a mixture of a plurality of sucrose fatty acid esters with different degrees of esterification as raw materials in 2-propyl alcohol at a temperature of 50 ° C. or higher and then cooling to 38 to 45 ° C. Provided is a method for fractionated production of a sucrose fatty acid ester, wherein a solid content rich in chemical components is separated and collected.
In the present invention, a mixture of a plurality of sucrose fatty acid esters having different esterification degrees as raw materials is dissolved in 2-propyl alcohol at a temperature of 50 ° C. or higher and then cooled to 0 to 33 ° C. A method for fractionated production of sucrose fatty acid ester, characterized by separating and collecting a liquid component rich in sucrose.
In the present invention, the high esterification component refers to a component in which a component having a relatively high degree of esterification is concentrated from a mixture of sucrose fatty acid esters as a raw material. The low esterification component refers to a component in which a component having a relatively low degree of esterification is concentrated from a mixture of sucrose fatty acid esters as a raw material.

  In the present invention, a solid content rich in a desired high ester component, a liquid content rich in a low esterification degree component, and the like can be easily obtained by adopting 38 to 45 ° C. and / or 0 to 33 ° C. as the temperature for solid-liquid separation. Can be manufactured.

(Example 1) which shows the distribution of the esterification degree in the deposit obtained by the fractionation manufacturing method of the sucrose fatty acid ester of this invention and a filtrate. (Example 2) which shows the distribution of the esterification degree in the deposit obtained by the fractionation manufacturing method of the sucrose fatty acid ester of this invention and a filtrate. (Example 3) which shows the distribution of the esterification degree in the deposit obtained by the fractionation manufacturing method of the sucrose fatty acid ester of this invention and a filtrate. The distribution of the degree of esterification in the precipitate obtained by the fractionated production method of Comparative Example 1 and the filtrate is shown.

  In the fractionation production method of the present invention, a mixture of a plurality of sucrose fatty acid esters having different degrees of esterification is used as a fractionation raw material. As such a raw material, among the eight hydroxyl groups contained in the sucrose molecule, a mixture of a plurality of sucrose fatty acid esters having different esterification degrees obtained by esterifying any one of the eight hydroxyl groups with a fatty acid. can give. Among these, a mixture of sucrose fatty acid esters containing 50% by mass or more, preferably 70% by mass or more, more preferably 80% by mass or more of a sucrose fatty acid ester having an esterification degree of 4 to 7 is preferable. Such a mixture of sucrose fatty acid esters can be produced by a conventional method, but can also be easily obtained as a commercial product. For example, commercial items, such as DK ester F-10 (Daiichi Kogyo Seiyaku Co., Ltd.) and DK ester F-50 (Daiichi Kogyo Seiyaku Co., Ltd.), are mentioned.

Here, aliphatic carboxylic acid is mentioned as a fatty acid which comprises sucrose fatty acid ester. As the aliphatic carboxylic acid, a linear saturated aliphatic carboxylic acid, a linear unsaturated aliphatic carboxylic acid, a branched chain of an aliphatic carboxylic acid having 2 to 22, preferably 8 to 22, and more preferably 14 to 22 carbon atoms is used. Chain saturated aliphatic carboxylic acids and mixtures thereof can be used. Examples include caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid, lignoceric acid, serotic acid, palmitooleic acid, oleic acid, elaidic acid, linoleic acid Linolenic acid, eicosapentaenoic acid, docosahexaenoic acid, arachidonic acid, erucic acid, acetic acid, isobutyric acid and the like, but are not limited thereto.
Preferred are palmitic acid, stearic acid, behenic acid, oleic acid, linoleic acid, linolenic acid and erucic acid.
In the present invention, it is particularly preferable that the constituent fatty acid of the total sucrose fatty acid ester is a linear saturated aliphatic carboxylic acid having 14 to 22 carbon atoms and a linear unsaturated fatty acid having 14 to 22 carbon atoms. Most preferred are palmitic acid, stearic acid, behenic acid, oleic acid, and erucic acid.

In the present invention, a mixture of a plurality of sucrose fatty acid esters having different esterification degrees as raw materials is dissolved in 2-propyl alcohol at a temperature of 50 ° C. or higher, preferably 55 to 80 ° C. At this time, it is preferable to make all of the raw material sucrose fatty acid ester mixture into 2-propyl alcohol, but the following solid-liquid separation may be performed in a state in which it is not partially dissolved.
The dissolution is preferably performed while stirring a mixture of sucrose fatty acid ester and 2-propyl alcohol under heating. Under the present circumstances, it is preferable to use 2-propyl alcohol in the ratio of 2-15 mass parts with respect to 1 mass part of sucrose fatty acid ester, More preferably, it is used in the ratio of 7-13 mass parts.

In the first aspect of the present invention, a solid content rich in high esterification degree components precipitated by dissolving a mixture of raw sucrose fatty acid esters in 2-propyl alcohol and then cooling to 38 to 45 ° C. is subjected to solid-liquid separation. (First solid-liquid separation).
The precipitation by cooling is preferably performed while stirring the solution. In order to ensure the precipitation of the desired component, it is preferable to continue stirring for 30 minutes to 3 hours, more preferably for 1 to 2 hours while maintaining the temperature at the final cooling temperature.
The solid-liquid separation is preferably performed by suction filtration or squeezing filtration while maintaining the temperature at the final cooling temperature.

  The solid part obtained by such separation has a higher content of sucrose fatty acid ester having a higher degree of esterification than before solid-liquid separation. In particular, when a mixture of sucrose fatty acid esters containing 50% by mass or more of sucrose fatty acid esters having an esterification degree of 4 to 7 is used as a raw material, the ratio of sucrose fatty acid esters having an esterification degree of 6 and 7 is improved. The total ratio of 5 to 7 sucrose fatty acid esters can be increased by 20 to 40% by mass compared to the ratio in the raw material. Moreover, about a liquid part, the ratio of the sucrose fatty acid ester of esterification degree 4 and 5 can be improved, and the total ratio of the sucrose fatty acid ester of esterification degree 7 and 8 is 60 mass compared with the ratio in a raw material. % Or less.

In the first aspect of the present invention, the liquid portion separated by the first solid-liquid separation is cooled to precipitate a solid, and subjected to further solid-liquid separation (second solid-liquid separation). That is, it cools to 0-33 degreeC, Preferably it is 15-30 degreeC, More preferably, it is 15-25 degreeC. Specifically, the separated liquid portion having the final cooling temperature in the first solid-liquid separation is preferably stirred while cooling the solution to precipitate a solid content rich in a desired low esterification degree component. In order to ensure the precipitation of the desired component, it is preferable to continue stirring for 30 minutes to 3 hours, more preferably for 1 to 2 hours while maintaining the temperature at the final cooling temperature.
The solid-liquid separation is preferably performed by suction filtration or squeezing filtration while maintaining the temperature at the final cooling temperature.

The solid part obtained by such separation has a higher content of sucrose fatty acid ester having a lower degree of esterification than before solid-liquid separation. In particular, when a mixture of sucrose fatty acid esters containing 50% by mass or more of sucrose fatty acid esters having an esterification degree of 4 to 7 is used as a raw material, the ratio of sucrose fatty acid esters having an esterification degree of 5 and 6 can be improved. Moreover, about the liquid part, the ratio of the sucrose fatty acid ester of esterification degree 4 and 5 can be improved. The total proportion of sucrose fatty acid esters having a degree of esterification of 3 to 5 can be increased by 40% by mass or more compared to the proportion in the raw material. Further, the total proportion of sucrose fatty acid esters having an esterification degree of 6 to 8 can be reduced to 50% by mass or less, preferably 35% by mass or less, compared to the proportion in the raw material.
In the second aspect of the present invention, the first solid-liquid separation in the first aspect can be performed alone. Moreover, in the 3rd aspect of this invention, the 2nd solid-liquid separation in the said 1st aspect can be performed independently. In this case, a solid part and a liquid part are obtained by solid-liquid separation, respectively.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to them at all.
<Ester composition evaluation method>
The composition analysis of the ester contained in the sucrose fatty acid ester mixture was performed using high performance liquid chromatography. Specifically, a GPC column and an ODS column were used. The analysis conditions using each column are shown below.
GPC column analysis condition detector: Shodex differential refractometer RI-74
Column (two connected columns 1 and 2): (Column 1) PL-gel (manufactured by Polymer Laboratories) Particle size 5 μm Pore diameter 10 nm 300 mm × 7.5 mm, (Column 2) PL-gel (Polymer Laboratories) Manufactured) particle size 5μm pore size 50nm 300mm × 7.5mm
Column temperature: 30 ° C
Eluent: Special grade tetrahydrofuran (containing stabilizer)
Flow rate: 0.6 mL / min Injection volume: 10 μL
Analysis time: 43 minutes

ODS column analysis condition detector Shodex differential refractometer RI-74
Column: ZORBAX Eclipse Plus C18 (manufactured by Agilent Technologies) Particle size 3.5 μm 150 mm × 4.6 mm
Column temperature: 25 ° C
Eluent: Special grade tetrahydrofuran (containing stabilizer): Special grade methanol = 55: 45
Flow rate: 0.8 mL / min Injection volume: 10 μL
Analysis time: 16 minutes First, the composition of sucrose fatty acid esters having an esterification degree of 1, 2, 3 and an esterification degree of 4 or more was measured using a GPC column. Next, using an ODS column, the composition ratio of sucrose fatty acid esters having esterification degrees of 4, 5, 6, 7 and 8 was measured. Each composition of esterification degree 1-8 was computed from the measurement result of the previous GPC column, and the composition ratio result of the ODS column.

[Example 1]
DK ester F-10 (HLB = 1, manufactured by Daiichi Kogyo Seiyaku Co., Ltd.) was prepared as a sucrose fatty acid ester mixture raw material. 30 g of F-10 sucrose fatty acid ester mixture raw material and 300 g of 2-propanol were added to a separable flask. The separable flask was immersed in a constant temperature bath at 60 ° C. and stirred using a three-one motor until the F-10 sucrose fatty acid ester mixture raw material was dissolved in 2-propanol. After dissolution, the temperature of the thermostatic bath was set to 40 ° C., and stirring was continued for 1 hour and 30 minutes. Thereafter, suction filtration was performed in a thermostat at 40 ° C. to obtain a precipitated sucrose fatty acid ester mixture and a filtrate. From the filtrate, 2-propanol was removed by an evaporator and freeze-drying to obtain a sucrose fatty acid ester mixture fractionated into a filtrate.
Table 1 and FIG. 1 show sucrose fatty acid ester contents (% by mass) having different esterification degrees in the sucrose fatty acid ester mixture thus precipitated and the sucrose fatty acid ester mixture separated into the filtrate.

この表の結果から、実施例１で得られた析出物（固体部）は、固液分離前に較べて、エステル化度の高い蔗糖脂肪酸エステルの含有割合が多くなっている。特に、エステル化度６及び７の蔗糖脂肪酸エステルの割合が向上し、エステル化度５〜７の蔗糖脂肪酸エステルの合計割合を、原料中の割合に比べて２０〜４０質量％増加させることができることがわかる。又、ろ液（液状部）については、エステル化度４及び５の蔗糖脂肪酸エステルの割合を向上させることができ、エステル化度７及び８の蔗糖脂肪酸エステルの合計割合を、原料中の割合に比べて６０質量％以下に減少させることができることがわかる。 Table 1

From the results in this table, the precipitate (solid part) obtained in Example 1 has a higher content of sucrose fatty acid ester having a higher degree of esterification than before solid-liquid separation. In particular, the ratio of sucrose fatty acid esters having an esterification degree of 6 and 7 is improved, and the total ratio of sucrose fatty acid esters having an esterification degree of 5 to 7 can be increased by 20 to 40% by mass compared to the ratio in the raw material. I understand. Moreover, about the filtrate (liquid part), the ratio of the sucrose fatty acid ester of esterification degree 4 and 5 can be improved, and the total ratio of the sucrose fatty acid ester of esterification degree 7 and 8 is made into the ratio in a raw material. It turns out that it can reduce to 60 mass% or less compared.

この表の結果から、この表の結果から、析出物（固体部）とろ液（液状部）を構成する蔗糖脂肪酸エステル混合物中のエステル化度の異なる成分の含有割合が大きく異なり、効率的な分別が行われていることがわかる。又、実施例２で得られた析出物は、固液分離前に較べて、エステル化度の低い蔗糖脂肪酸エステルの含有割合が多くなっている。特に、エステル化度５及び６の蔗糖脂肪酸エステルの割合を向上させることができることがわかる。又、ろ液については、エステル化度４及び５の蔗糖脂肪酸エステルの割合を向上させることができ、エステル化度３〜５の蔗糖脂肪酸エステルの合計割合を、原料中の割合に比べて４０質量％以上高めることができることがわかる。又、エステル化度６〜８の蔗糖脂肪酸エステルの合計割合を、原料中の割合に比べて１７質量％に減少させることができることがわかる。 [Example 2]
After the F-10 sucrose fatty acid ester mixture raw material was dissolved in 2-propanol, the sucrose separated into the filtrate and the sucrose fatty acid ester mixture precipitated in the same manner as in Example 1 except that the temperature of the thermostatic bath was set to 30 ° C. A fatty acid ester mixture was obtained.
Table 2 and FIG. 2 show sucrose fatty acid ester contents (% by mass) having different esterification degrees in the sucrose fatty acid ester mixture thus precipitated and the sucrose fatty acid ester mixture separated into the filtrate.
Table 2

From the results of this table, the content of components having different degrees of esterification in the mixture of sucrose fatty acid esters constituting the precipitate (solid part) and the filtrate (liquid part) are greatly different from the results of this table, and efficient separation Can be seen. Further, the precipitate obtained in Example 2 has a higher content of sucrose fatty acid ester having a lower degree of esterification than before the solid-liquid separation. In particular, it can be seen that the ratio of sucrose fatty acid esters having esterification degrees of 5 and 6 can be improved. Moreover, about a filtrate, the ratio of the sucrose fatty acid ester of esterification degree 4 and 5 can be improved, and the total ratio of the sucrose fatty acid ester of esterification degree 3-5 is 40 mass compared with the ratio in a raw material. It can be seen that it can be increased by more than%. Moreover, it turns out that the total ratio of the sucrose fatty acid ester of esterification degree 6-8 can be reduced to 17 mass% compared with the ratio in a raw material.

この表の結果から、析出物（固体部）とろ液（液状部）を構成する蔗糖脂肪酸エステル混合物中のエステル化度の異なる成分の含有割合が大きく異なり、効率的な分別が行われていることがわかる。又、実施例３で得られた析出物は、固液分離前に較べて、エステル化度の低い蔗糖脂肪酸エステルの含有割合が多くなっている。特に、エステル化度５及び６の蔗糖脂肪酸エステルの割合を向上させることができることがわかる。又、ろ液については、エステル化度４及び５の蔗糖脂肪酸エステルの割合を向上させることができ、エステル化度３〜５の蔗糖脂肪酸エステルの合計割合を、原料中の割合に比べて６０質量％以上高めることができることがわかる。又、エステル化度６〜８の蔗糖脂肪酸エステルの合計割合を、原料中の割合に比べて３１質量％に減少させることができることがわかる。 [Example 3]
After the F-10 sucrose fatty acid ester mixture raw material was dissolved in 2-propanol, the sucrose separated into a filtrate and a sucrose fatty acid ester mixture precipitated in the same manner as in Example 1 except that the temperature of the thermostatic bath was set to 20 ° C. A fatty acid ester mixture was obtained.
Table 3 and FIG. 3 show the sucrose fatty acid ester contents (% by mass) having different degrees of esterification in the sucrose fatty acid ester mixture thus precipitated and the sucrose fatty acid ester mixture separated into the filtrate.
Table 3

From the results in this table, the content ratios of components having different degrees of esterification in the mixture of sucrose fatty acid esters constituting the precipitate (solid part) and the filtrate (liquid part) are greatly different and efficient separation is performed. I understand. In addition, the precipitate obtained in Example 3 has a higher content of sucrose fatty acid ester having a lower degree of esterification than before the solid-liquid separation. In particular, it can be seen that the ratio of sucrose fatty acid esters having esterification degrees of 5 and 6 can be improved. Moreover, about a filtrate, the ratio of the sucrose fatty acid ester of esterification degree 4 and 5 can be improved, and the total ratio of the sucrose fatty acid ester of esterification degree 3-5 is 60 mass compared with the ratio in a raw material. It can be seen that it can be increased by more than%. Moreover, it turns out that the total ratio of the sucrose fatty acid ester of esterification degree 6-8 can be reduced to 31 mass% compared with the ratio in a raw material.

この表の結果から、析出物（固体部）とろ液（液状部）を構成する蔗糖脂肪酸エステル混合物中のエステル化度の異なる成分の含有割合は、ほぼ同じであり、分別溶媒として酢酸エチルを用いたのでは有効な分別を行うことができないことがわかる。 [Comparative Example 1]
The procedure was the same as in Example 1 except that 2-propanol was changed to ethyl acetate and the temperature of the thermostatic bath after dissolution was set to 40 ° C., but there was no precipitation of the sucrose fatty acid ester mixture.
[Comparative Example 2]
The sucrose fatty acid was separated by the precipitated sucrose fatty acid ester mixture and the filtrate by the same method as in Example 1 except that 2-propanol was changed to ethyl acetate and the temperature of the thermostat after dissolution was set to 30 ° C. An ester mixture was obtained.
The results of the sucrose fatty acid ester mixture thus precipitated and the sucrose fatty acid ester mixture separated into the filtrate are shown in Table 4 and FIG.
Table 4

From the results in this table, the content ratios of the components having different degrees of esterification in the mixture of sucrose fatty acid ester constituting the precipitate (solid part) and the filtrate (liquid part) are almost the same, and ethyl acetate is used as a fractionation solvent. It can be seen that effective separation cannot be performed.

Claims (4)

A mixture of a plurality of sucrose fatty acid esters having different esterification degrees as raw materials is dissolved in 2-propyl alcohol at a temperature of 50 ° C. or higher, and then cooled to 38 to 45 ° C. to precipitate a solid content rich in high ester components. Solid-liquid separation, further cooling to 0 to 33 ° C., separating and collecting a liquid component rich in low esterification degree components , and a mixture of a plurality of sucrose fatty acid esters having different esterification degrees as raw materials A method for fractionated production of a sucrose fatty acid ester, comprising 50% by mass or more of 4-7 sucrose fatty acid ester . Solids rich in highly esterified components precipitated by dissolving a mixture of a plurality of sucrose fatty acid esters having different esterification degrees as raw materials in 2-propyl alcohol at a temperature of 50 ° C. or higher and then cooling to 38 to 45 ° C. A mixture of a plurality of sucrose fatty acid esters having different esterification degrees as a raw material contains 50% by mass or more of a sucrose fatty acid ester having an esterification degree of 4 to 7 A method for fractionated production of sucrose fatty acid esters. The method according to claim 1 or 2 , wherein 2-propyl alcohol is used at a ratio of 2 to 15 parts by mass with respect to 1 part by mass of the sucrose fatty acid ester. The method according to any one of claims 1 to 3 , wherein the solid-liquid separation is performed by suction filtration or pressure filtration.

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