JP5643065B2 - Process for producing purified polyglyceryl monoether - Google Patents

Description

  The present invention relates to a method for producing purified polyglyceryl monoether.

  Polyglyceryl ether has an excellent function as a nonionic surfactant. For example, for the purposes of emulsification, solubilization, dispersion, washing, foaming, defoaming, penetration, antibacterial, food, cosmetics, agricultural chemicals, Widely used in the field of pharmaceuticals.

As a general method for producing polyglyceryl ether, a method is known in which glycidol is addition-polymerized in the presence of a catalyst in an aliphatic alcohol.
In addition, as a method for controlling the composition of polyglyceryl ether, an operation of adding 1 mol of epichlorohydrin to an aliphatic alcohol, dehydrochlorinating under alkaline conditions, and then opening with dilute sulfuric acid is performed. A method of repeating until the degree of polymerization is reached, a method of addition polymerization of a glycidyl ester to an aliphatic alcohol, followed by saponification with an alkali (Patent Document 1), a reaction of alkyl glycidyl ether with glycerin A method in which an alkyldiglyceryl ether is synthesized, an allyl halide is condensed on the hydroxyl group, and then the allyl group is converted to two hydroxyl groups until the desired degree of polymerization is reached (Patent Document 2), etc. Are known.

On the other hand, a method for selectively separating a compound having a narrow molecular weight distribution from a polymer having a wide molecular weight distribution using high performance liquid chromatography is known.
For example, molecular distillation or liquid chromatography using a column packed with a cation exchange resin to remove a low-molecular-weight reactant from a polyglycerol reactant (Patent Document 3), or a column filled with silica gel with polyglycerol There is a method of extracting a component having high emulsifying performance by adsorbing a fatty acid ester and then eluting with hexane / ethyl acetate (Patent Document 4).

JP-A-9-188755 JP 2001-114720 A JP 7-308560 A JP 2006-169159 A

  Polyglyceryl monoethers have different properties and different functions when the degree of polymerization of glycerin is different. In general, industrially obtained polyglyceryl monoether is a mixture of a plurality of compounds having different degrees of polymerization of glycerin, and thus the required function is not always sufficiently exhibited. For this reason, a composition containing a necessary amount of polyglyceryl monoether having a specific degree of glycerol polymerization is required.

When the composition is controlled by reaction, when an acid is used as a catalyst, a polymerization reaction between glycidol proceeds to produce an equivalent amount of polyglycerin. On the other hand, when a base is used, it is difficult to control the molecular weight distribution and the polyglyceryl ether has a wide molecular weight distribution. Produces. Therefore, it is necessary to suppress these reactions using a large excess of alcohol with respect to glycidol, and there is a problem that productivity is low.
Moreover, although the method of patent document 1 and patent document 2 controls the composition of polyglyceryl ether by reaction operation, there exists a problem that a reaction process becomes complicated etc., and efficient composition control is difficult. .
In addition, when the composition is adjusted by distillation, unreacted raw materials such as alcohol and compounds having a glycerin polymerization degree of 1 in polyglyceryl monoether can be distilled off by distillation under reduced pressure, but the glycerin polymerization degree is 2 or more. Could not be easily separated.
On the other hand, the techniques described in Patent Document 3 and Patent Document 4 are compounds in which the former is polyglycerin and the latter is a polyglyceryl fatty acid ester as a component to be separated, and is different from polyglyceryl monoether. In general, separation by an adsorbent is greatly influenced by the balance of a solvent, a solute, and an adsorbent, and contained trace components, and the knowledge of the separation method described above cannot always be applied when the solute components are different.

  Accordingly, an object of the present invention is to provide a method for producing a purified polyglyceryl monoether containing a polyglyceryl monoether having a narrow polymerization degree distribution at a high concentration from a polyglyceryl monoether having a wide polymerization degree distribution of polyglyceryl groups at a high recovery rate. It is in.

The present inventor has conducted extensive studies, and after adsorbing polyglyceryl monoether on silica gel, an organic solvent having an SP value in the range of 9.2 to 12 [(cal / cm ³ ) ^1/2 ]. It has been found that when polyglyceryl ether is eluted by passing it through, polyglyceryl ether can be eluted and separated according to the degree of polymerization of glycerin, and polyglyceryl monoether having a narrow polyglyceryl group polymerization degree distribution can be recovered at a high recovery rate.

That is, the present invention includes an adsorption step in which the raw material polyglyceryl monoether represented by the general formula (1) is adsorbed on silica gel, and an SP value of 9.2 to 12 [(cal / cm ³ ) ^1/2 ] on the silica gel. The present invention provides a method for producing purified polyglyceryl monoether, which comprises an elution step in which an organic solvent in the range is brought into contact with the silica gel to elute the polyglyceryl monoether from the silica gel.

_{RO- (C 3 H 6 O 2} ) n -H (1)

(In formula, R shows a C6-C22 hydrocarbon group, n is the polymerization degree of glycerol, and shows the number of 1-9.)

  According to the method of the present invention, since polyglyceryl ether can be eluted and separated according to the polymerization degree of glycerin, purified polyglyceryl monoether having a high concentration of polyglyceryl monoether having a narrow polyglyceryl group polymerization degree distribution can be easily obtained at a high recovery rate. be able to.

It is a figure which shows schematic structure of a simulated moving bed separation apparatus.

  In the present invention, the polyglyceryl monoether is a glyceryl monoether in which one of the hydrogen atoms of the hydroxyl group in the polyglycerol which is glycerin or a polymer thereof is substituted with a hydrocarbon group having 6 to 22 carbon atoms to form an ether bond, and This is a general term for polyglyceryl monoether.

(Raw material polyglyceryl monoether)
The raw material polyglyceryl monoether used in the present invention has the following general formula (1):

_{RO- (C 3 H 6 O 2} ) n -H (1)

(In formula, R shows a C6-C22 hydrocarbon group, n is the polymerization degree of glycerol, and shows the number of 1-9.)
It is represented by That is, it is a mixture of polyglyceryl monoethers having a polymerization degree of glycerin of 1 to 9.

  In the formula (1), the hydrocarbon group having 6 to 22 carbon atoms represented by R is a hydrocarbon group having 8 to 18 carbon atoms, and further carbonized with 10 to 16 carbon atoms from the viewpoint of detergency and foamability. A hydrogen group, particularly a hydrocarbon group having 12 to 14 carbon atoms is preferred. Here, examples of the hydrocarbon group include an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group. From the viewpoint of detergency and foamability, an aliphatic hydrocarbon group, A cyclic hydrocarbon group is preferred. Specific examples include a linear, branched, or cyclic alkyl group or alkenyl group.

In the formula (1), —C ₃ H ₆ O ₂ — can include one or more structures selected from the group consisting of the following formulas (2a) and (2b).

_{-CH 2 -CH (OH) -CH 2} O- (2a)
—CH ₂ —CH (CH ₂ OH) —O— (2b)

  In the raw material polyglyceryl monoether, in the formula (1), the compound having a polymerization degree of glycerol of 1 is 0 to 40% by mass (hereinafter simply referred to as “%”), and the compound having a polymerization degree of 2 is 5 to 40%, a compound having a degree of polymerization of 3 is 5 to 35%, a compound having a degree of polymerization of 4 is 0 to 25%, a compound having a degree of polymerization of 5 is 0 to 20%, and the degree of polymerization is 6 or more. Certain compounds are preferably in the range of 0-20%. From the viewpoint of detergency, the polymerization degree of glycerin is preferably 2 to 6, more preferably 2 to 5, and particularly preferably 3 to 5. In the production method of the present invention, the preferred range can be appropriately changed according to the desired performance by changing the conditions.

  The raw material polyglyceryl monoether is not particularly limited, and can be obtained, for example, by reacting an alcohol and 2,3-epoxy-1-propanol (glycidol) in the presence of a catalyst such as an alkali or a simple metal salt of a rare earth element. It can also be obtained by the method described in paragraphs 0007-0011 of JP-A-2000-160190.

  After completion of the reaction, the reaction solution can be subjected to the following adsorption step as it is. However, since there may be unreacted raw materials such as alcohol remaining in the reaction solution, an operation for reducing these may be performed in advance. . Examples of the operation include filtration, distillation, extraction and the like, and the distillation operation is particularly preferable. By reducing unreacted raw materials, the load in the present invention can be reduced, and the recovery rate and selectivity of purified polyglyceryl monoether can be improved.

  The content of the alcohol in the raw material polyglyceryl monoether is preferably 0 to 60%, more preferably 0.1 to 40%, and particularly preferably 1 to 30%.

  The viscosity (50 ° C.) of the raw material polyglyceryl monoether is 10 to 500 mPa · s, particularly 20 to 300 mPa · s, more preferably 50 to 50% from the viewpoint of improving the solubility or diffusibility in the solvent and increasing the separation efficiency. It is preferably 200 mPa · s.

  From such raw material polyglyceryl monoether, purified polyglyceryl monoether having an increased content of polyglyceryl monoether having a specific degree of glycerol polymerization is obtained through the following adsorption step and elution step.

  The adsorption step and elution step of the present invention can be carried out in either a batch type or a continuous type.

  In the case of the batch type, the raw material polyglyceryl monoether is brought into contact with silica gel, then a necessary amount of an organic solvent described later is added, and then the organic solvent is discharged. In order to improve the separation efficiency, the raw material polyglyceryl monoether is passed through a column packed with silica gel, and then the necessary amount of an organic solvent described later is passed through the column to obtain fractions obtained over time. Good. Thereby, the purified polyglyceryl monoether having the desired composition can be obtained. Here, the ratio of the flow rate of the organic solvent with respect to the column capacity is referred to as bed volume (BV).

  In the case of a continuous type, a plurality of inlets are provided in a plurality of columns filled with silica gel, and raw material polyglyceryl monoether is continuously passed from the raw material inlet, and an organic solvent described later is continuously passed from the solvent inlet. . In addition to them, you may have the other inlet for circulating a liquid from arbitrary discharge ports. Moreover, the column can be provided with a plurality of outlets to obtain purified polyglyceryl monoethers having different compositions. In order to perform this operation continuously, the locations of the raw material inlet, the solvent inlet, and each outlet are changed over time. This method is generally called a simulated moving bed method.

(Adsorption process)
In the present invention, the adsorption step is a step of adsorbing the raw material polyglyceryl monoether on silica gel.
The average pore diameter of the silica gel is preferably 3 to 20 nm, more preferably 5 to 15 nm, particularly 6 to 12 nm, and particularly preferably 7 to 10 nm from the viewpoint of good separability, operation and improvement of the recovery rate.

The average particle diameter of the silica gel is preferably 150 to 600 μm, more preferably 180 to 500 μm, particularly 200 to 400 μm, and particularly preferably 242 to 263 μm from the same point. The maximum and minimum particle size widths (also referred to as particle size distribution widths) are preferably 100 to 800 μm, more preferably 150 to 600 μm, and particularly preferably 180 to 500 μm.
The average pore diameter can be determined by mercury porosimetry or nitrogen adsorption. The average particle diameter can be determined by a laser diffraction scattering method particle size distribution measuring apparatus.

The amount of silica gel used can be defined by the ratio of the total capacity (m ³ / hr) of the raw material polyglyceryl monoether per operation time to the total capacity (m ³ ) of the silica gel (hereinafter referred to as the raw material load). .
Raw material load ((m ³ / hr) / m ³ ) = {total capacity of raw material polyglyceryl monoether per operating time (m ³ / hr)} / total capacity of silica gel (m ³ )

"Total volume of raw material polyglyceryl monoether per operation time" means, in the case of a batch system, the total volume of raw material polyglyceryl monoether, after the introduction of the raw material polyglyceryl monoether, until the necessary amount of organic solvent has been introduced. The thing divided by time. In the case of the continuous type, it refers to the introduction capacity of the raw material polyglyceryl monoether per hour.
The raw material load is preferably 0.005 to 1.0 (m ³ / hr) / m ³ , more preferably 0.01 to 0.8 (m ³ / hr) / m ³ , from the separability and productivity of each component. It is preferred, preferably in particular ^{0.015~0.5 (m 3 / hr) /} m 3, especially 0.02 to 0.3 is ^{(m 3 / hr) / m} 3 preferred.

(Elution process)
In the present invention, the elution step is a step of eluting polyglyceryl monoether adsorbed on silica gel with a specific organic solvent.
The organic solvent used in the present invention is an organic solvent having an SP value in the range of 9.2 to 12 [(cal / cm ³ ) ^1/2 ]. Here, the SP value indicates a solubility parameter. For example, “SP value basics / applications and calculation methods” (Information Organization, 2005), Polymer handbook Third edition (A Wiley-Interscience publication, 1989), etc. Have been described. For solvents whose specific SP values are not described in the above-mentioned documents, see, for example, “SP Value Basics / Applications and Calculation Methods” or Polymer Engineering and Science, Vol. 14, no. 2, 147-154 (1974) and the like, the SP value can be obtained by using the Fedors method. When a plurality of solvents are used in combination, the volume average value of SP values of each solvent is calculated.

  Examples of organic solvents (indicated by SP values in parentheses) are methyl ethyl ketone (9.3), chloroform (9.3), chlorobenzene (9.5), acetone (9.8), acetic acid (10.5), 2-methyl-1-propanol (10.5), t-butyl alcohol (10.6), 1-pentanol (10.6), hexanol (10.7), 2-butanol (10.8), 2 -Methoxyethanol (11.4), cyclohexanol (11.4), isopropyl alcohol (11.5), allyl alcohol (11.8), propanol (12.0) and the like. These can be used alone or in combination of two or more.

  In addition, so that the SP value of the solvent after mixing is in the above range, solvents that are outside the range of SP value of 9.2 to 12 are appropriately combined to prepare and use the SP value in the above range. Also good. Examples of such a solvent include hexane (7.2), ethanol (13.0), and methanol (14.5).

  The SP value of the solvent after mixing is in the above range, and an organic solvent containing one or more selected from hexane, acetone, and ethanol is preferable. Preferable combinations include hexane-ethanol, hexane-acetone, acetone-ethanol and the like. Further, an organic solvent containing acetone is preferable, and acetone is particularly preferable.

The organic solvent is preferably 9.2 or more from the viewpoint that it can be eluted and desorbed without leaving a component having a high degree of polymerization on the silica gel, and a solvent having an SP value of 9.2 to 11 is preferable from the viewpoint of good separability. It is preferably used, more preferably 9.2 to 10.6, and particularly preferably 9.5 to 10.5.
In order to prevent remaining on the silica gel, it is preferable that the polyglyceryl monoether having a polymerization degree of glycerin of 6 or more can be discharged substantially in an amount of BV = 6.1, preferably 95% or more.

The amount of the organic solvent used is preferably 3 to 45 times by mass, more preferably 4 to 35 times by mass, particularly 5 to 25 times by mass, especially 6 to 15 times by mass with respect to the total mass of the raw material polyglyceryl monoether. Preferably there is.
When employing the simulated moving bed method, the ratio of the organic solvent supply rate to the raw polyglyceryl monoether supply rate (Ud / Uf) is 3 to 45, more preferably 4 to 35, particularly from the viewpoint of separability and production efficiency. It is preferably 5 to 25, more preferably 6 to 15.

  By removing the organic solvent from the eluted fraction, a purified polyglyceryl monoether having a desired composition can be obtained.

Polyglyceryl monoether having a degree of polymerization of glycerin of 2 to 5, particularly 3 to 5, exhibits high cleaning performance (Japanese Patent Laid-Open No. 2008-255258), and has good foaming as shown in Examples below. Therefore, in the present invention, it is preferable to collect a fraction containing such polyglyceryl monoether at a high concentration.
In the purified polyglyceryl monoether, the content of polyglyceryl monoether having a polymerization degree of glycerin of 2 to 5 is preferably 43% or more, more preferably 45% or more, particularly 50% or more, and particularly 55% or more. The upper limit is not particularly defined, but is preferably 99% or less, more preferably 95% or less from the viewpoint of economy.
In the purified polyglyceryl monoether, the content of the polyglyceryl monoether having a polymerization degree of glycerin of 3 to 5 is 25% or more in total, more preferably 40% or more, particularly 50% or more, particularly 60% or more. preferable. The upper limit is not particularly defined, but is preferably 99% or less, more preferably 95% or less from the viewpoint of economy.

The sum of the content of alcohol and glyceryl monoether having a degree of glycerol polymerization of 1 in this purified polyglyceryl monoether is 50% or less, more preferably 0 to 40%, especially 0 to 35%, especially 0 to 15%. Preferably there is.
The sum of the content of the alcohol and the glyceryl monoether having a glycerol polymerization degree of 1 and 2 in the purified polyglyceryl monoether is 60% or less, more preferably 0 to 30%, particularly 0 to 25%, and especially 0 to 20%. % Is preferred.
Further, the polyglyceryl monoether having a polymerization degree of glycerin of 6 or more is preferably 35% or less, more preferably 0 to 30%, particularly preferably 0 to 25%, and particularly preferably 0 to 20%.

  Obtaining a polyglyceryl monoether having a specific degree of glycerin polymerization contained in a purified polyglyceryl monoether with a recovery rate of 50% or more with respect to a polyglyceryl monoether having a specific degree of glycerin polymerization contained in the raw material polyglyceryl monoether In particular, it is preferable to obtain 60% or more, further 75% or more, and particularly 85% or more.

The purified polyglyceryl monoether obtained by the method of the present invention is useful as a nonionic surfactant, and can be used for purposes such as emulsification, solubilization, dispersion, washing, foaming, defoaming, permeation, and antibacterial. it can.
In particular, a purified polyglyceryl monoether containing a high concentration of polyglyceryl monoether having a degree of polymerization of glycerin of 2 to 5 is useful for detergents that require high foaming properties such as clothes detergents and dishwashing detergents. .

[Analytical method of polyglyceryl monoether]
The dried residue obtained by drying the sample for 3 hours with an electric constant temperature dryer at 40 ° C. was analyzed by gas chromatography (GC).
(GC analysis conditions)
<Pretreatment>
After adding about 1 mL of a TMS agent (TMS-I manufactured by GL Sciences Inc.) to about 50 mg of sample and stirring, a measurement sample was obtained through a syringe filter (PTFE 0.2 mm) and then analyzed with the following analyzer.
<Analyzer> Model: Gas Chromatograph (HEWRET PACKARD 6850) manufactured by Agilent Technologies
Detector: FID
Column: DB-1HT column (length 15 m, inner diameter 0.25 mm, film thickness 0.1 μm)
Analysis temperature: 350 ° C
Gas flow rate: 1 ml / min
Injection volume: 1 μl

[Measurement of average particle size]
For the measurement of the average particle size of the adsorbent, a laser diffraction / scattering particle size distribution measuring device (LS 13 320, BECKMAN COULTER) was used.

[Measurement of viscosity]
The viscosity at 50 ° C. was measured using a rheometer: MCR300 (manufactured by Anton-Paar).

[Evaluation of foaming]
After diluting the sample with acetone to a solid content concentration of about 1%, put 5 mL into a 9 mL vial (height 3.5 cm), stir for 1 minute, measure the amount of foaming with a ruler, and continue the foam The property was confirmed visually. The score was determined according to the following evaluation criteria.
3: Good (there was foaming of 2 mm or more immediately after shining, and foam remained after 30 minutes)
2: Slightly good (there was foaming of 2 mm or more immediately after the end, and the foam disappeared after 30 minutes)
1: Slightly poor (foaming immediately after shining was less than 2 mm)

Production Example 1
95.1 g (0.50 mol) of lauryl alcohol and 2.94 g (0.0050 mol) of lanthanum triflate were placed in a 300 mL four-necked flask and heated to 90 ° C. with stirring under a nitrogen stream. Next, 55.56 g (0.75 mol) of glycidol was added dropwise over 24 hours while maintaining the temperature, and stirring was continued for 2 hours as it was to obtain 153.6 g of a reaction product.
This reaction product was used as a raw material 1 for the following adsorption process. The composition of “raw material 1” is shown in Table 1.
Further, the viscosity of the raw material 1 at 50 ° C. was 108 mPa · s.

Production Example 2
Raw material 1 was subjected to distillation operation to reduce lauryl alcohol and glyceryl monoether having a glycerol polymerization degree of 1 to obtain a distilled purified product. The viscosity of the distilled purified product at 50 ° C. was 3040 mPa · s. Furthermore, acetone was added so that the solvent concentration in the distilled purified product was 20 wt%, and a raw material 2 having a viscosity at 50 ° C. of 110 mPa · s was obtained. The composition of “Raw Material 2” is shown in Table 1.

From Table 1, the content ratio of the glyceryl monoether (“ROH + 1GE”) having a polymerization degree of alcohol and glycerin of “raw material 1” of 1 is 51.8%, and the polyglyceryl monoether having a polymerization degree of glycerin of 2 to 5 ( The content ratio of “2GE to 5GE”) was 41.7%, and the content ratio of polyglyceryl monoether (“6GE”) having a polymerization degree of glycerin of 6 or more was 6.5%.
The content ratio of the glyceryl monoether (“ROH + 1GE”) having a polymerization degree of alcohol and glycerin of “raw material 2” of 0.4% and a polyglyceryl monoether (“2GE˜ The content ratio of 5GE ") was 85.2%, and the content ratio of polyglyceryl monoether (" 6GE ") having a polymerization degree of glycerin of 6 or more was 14.5%.

Example 1
The desired silica gel (average particle size 263 μm) was obtained by sieving silica gel 4B (manufactured by Fuji Silysia Chemical Ltd .: average pore diameter 7 nm) with a sieve (494 μm · 180 μm). This was packed in a column (inner diameter 1.0 cm × height 50 cm, volume 39.3 mL).
Next, 1.67 mL of “raw material 1” (volume ratio of raw material 1 / silica gel 0.0425) was passed through the column.

Subsequently, acetone (SP value: 9.8 (cal / cm ³ ) ^1/2 ) was used as an eluent, and the solution was passed at 2 mL / min for 120 minutes. The total flow rate of the eluate is 240 mL, which corresponds to 6.1 BV.
The effluent was collected every hour, and the outflow amounts of “ROH + 1GE”, “2GE to 5GE”, and “6GE to” were integrated.
The fraction with a recovery rate of “2GE to 5GE” of 0 to less than 29% is “fraction 1”, the fraction with a recovery rate of “2GE to 5GE” of 29% to 99% is “fraction 2”, and “2GE” The fraction with a recovery rate of “˜5GE” exceeding 99% was designated as “Fraction 3”. That is, the recovery rate of “2GE to 5GE” in fraction 2 is 70%.

Example 2
The same method as in Example 1 except that silica gel (average particle size 242 μm) obtained by sieving silica gel 5D (manufactured by Fuji Silysia Chemical Ltd .: average pore size 10 nm) with a sieve (410 μm and 180 μm) was used. To obtain "Fraction 2".

Comparative Example 1
The same as in Example 1 except that an adsorbent having an average particle size of 303 μm obtained by sieving a synthetic adsorbent SP70 (Mitsubishi Chemical Corporation: average pore diameter 7 nm) with a sieve (373 μm and 257 μm) was used. The method gave "Fraction 2".

Comparative Example 2
Except for using octadecylsilyl-treated silica gel ODSFS-1830FMT (manufactured by Organo Corp .: particle size range 0.4 μm to 147 μm, average particle size 95 μm, average pore size 10 nm), the same procedure as in Example 1 was performed. Minute 2 ”was obtained.

Example 3
“Fraction 2” was obtained in the same manner as in Example 1 except that a mixed solvent consisting of 66% by volume of hexane and 34% by volume of ethanol (SP value 9.2 (cal / cm ³ ) ^1/2 ) was used. It was.

Example 4
“Fraction 2” was obtained in the same manner as in Example 1 except that a mixed solvent consisting of 61% by volume of hexane and 39% by volume of ethanol (SP value 9.5 (cal / cm ³ ) ^1/2 ) was used. It was.

Example 5
“Fraction 2” was obtained in the same manner as in Example 1 except that a mixed solvent (SP value 10.3 (cal / cm ³ ) ^1/2 ) composed of 47% by volume of hexane and 53% by volume of ethanol was used. It was.

Example 6
“Fraction 2” was obtained in the same manner as in Example 1 except that a mixed solvent consisting of 75% by volume of acetone and 25% by volume of ethanol (SP value 10.6 (cal / cm ³ ) ^1/2 ) was used. It was.

Comparative Example 3
“Fraction 2” was obtained in the same manner as in Example 1 except that ethanol (SP value: 13.0 (cal / cm ³ ) ^1/2 ) was used as the eluent.

Comparative Example 4
“Fraction 2” was obtained in the same manner as in Example 1 except that a mixed solvent consisting of 34% by volume of acetone and 66% by volume of hexane (SP value 8.1 (cal / cm ³ ) ^1/2 ) was used. It was.

Comparative Example 5
“Fraction 2” was obtained in the same manner as in Example 1 except that ethyl acetate (SP value: 9.0 (cal / cm ³ ) ^1/2 ) was used as the eluent.

  The composition of "fraction 2" obtained in Examples 1-6 and Comparative Examples 1-5, the result of foaming evaluation, and the result of having calculated | required the recovery rate of "6GE-" at the time of organic solvent 6.1BV flow-through. It is shown in 2.

From Table 2, after the polyglyceryl monoether having a wide polymerization degree distribution of the polyglyceryl group is adsorbed on silica gel and eluted with an organic solvent having a specific SP value, it is eluted and separated according to the degree of polymerization of glycerin. It was confirmed that purified foamed polyglyceryl monoether containing 2GE to 5GE "at a high concentration can be produced with a high recovery rate.
The recovery rate of “6GE˜” at the time when the eluate was passed through 6.1 BV was 100%. That is, no residue having a high degree of polymerization of glycerin was observed in the column, indicating that the operability was good.
On the other hand, in Comparative Example 1 using a synthetic adsorbent as the adsorbent, Comparative Example 2 using octadecylsilyl-treated silica gel, and Comparative Example 3 using a solvent having an SP value greater than 12, a high value of “2GE to 5GE” Concentration could not be achieved. Further, in Comparative Examples 4 and 5 using a solvent having an SP value of 9.0 or less, it was found that the recovery rates of “2GE to 5GE” and “6GE” were low, and the residue in the column was generated. For this reason, foaming evaluation was not performed for Comparative Examples 4 and 5.

Examples 7-15
Using the average residence time and dispersion value obtained from the chromatogram obtained in Example 1, the composition of the pseudo moving bed chromatograph was calculated using a chromatographic separation simulator (manufactured by Organo Corp.).
(Pseudo moving bed separator)
A simulated moving bed separator composed of 6 6m columns was constructed. The outline is shown in FIG.
The six columns are sequentially connected as shown in FIG. 1, with one zone 1, two zones 2, two zones 3, and one zone 4. The liquid passing speed of each zone is U1 to U4, respectively.
The raw material liquid is passed through zone 2 and its supply rate is Uf. The eluate is passed through zone 4 and its supply rate is Ud.
A part of the liquid flowing out from the zone 2 is made into a raffinate and the rest is collected into the zone 1. The raffinate discharge rate is Ua. The raffinate is a fraction containing many so-called unnecessary components. In this embodiment, the fraction is rich in “ROH”, “1GE”, “2GE”, and “6GE˜”.
The liquid flowing out from the zone 4 is partially extracted and the rest is recovered to the zone 3. Let the extract discharge speed be Uc. An extract is a fraction that contains many components to be sought. In this embodiment, the fraction is rich mainly in “3GE” to “5GE”.
In order to perform such operation continuously, the raw material introduction port, the solvent introduction port, and the location of each discharge port are switched every switching time Ts [hr].
In the following examples, U1, U3, U4, Ud, and Uc were made constant, and U2 and Ua were subordinately changed by changing Uf.

Example 7
The value of the variance and mean residence time calculated from the sample obtained in Example 1 with respect to the raw material 1 (Fraction 1: Mean residence time 16.5Min, dispersion 38.4Min ² / Fraction 2: Mean residence time 21. The composition of simulated moving bed chromatography was calculated using 5 min, dispersion 68.5 min ² / fraction 3: average residence time 47.3 min, dispersion 491.1 min ² ). The separation Rs [1] between fractions 1 and 2 determined from the average residence time and dispersion is 0.17, and the separation Rs [2] between fractions 2 and 3 is 0.42. The column switching period Ts was 0.55 hours.
The continuous operation was calculated under the separation conditions and operation conditions shown in Table 3. The raw material supply speed Uf was 0.69 m / h, U2 was 2.69 m / h, and Ua was 1.21 m / h. Ud / Uf = 3.0. The analysis values of the extract fractions are shown in Table 3, divided into “ROH + 1GE + 2GE”, “3GE-5GE”, and “6GE˜”. The recovery rate of the “3GE to 5GE” component contained in the extract fraction relative to the raw material was 50%.

Example 8
Extract under the same conditions as in Example 7 except that the feed rate Uf was 0.41 m / h, U2 was 2.41 m / h, Ua was 0.93 m / h, and Ud / Uf was changed to 5.0. The fraction composition and the recovery rate of the “3GE to 5GE” component with respect to the raw material were calculated.

Example 9
Extract under the same conditions as in Example 7 except that the feed rate Uf was 0.28 m / h, U2 was 2.28 m / h, Ua was 0.80 m / h, and Ud / Uf was changed to 7.5. The fraction composition and the recovery rate of the “3GE to 5GE” component with respect to the raw material were calculated.

Example 10
Extract fraction under the same conditions as in Example 7 except that the feed rate Uf is 0.21 m / h, U2 is 2.21 m / h, Ua is 0.73 m / h, and Ud / Uf = 10. The composition and the recovery of the “3GE to 5GE” component relative to the raw materials were calculated.

Example 11
Extract under the same conditions as in Example 7 except that the raw material supply speed Uf was 0.14 m / h, U2 was 2.14 m / h, Ua was 0.66 m / h, and Ud / Uf = 14.8 was changed. The fraction composition and the recovery rate of the “3GE to 5GE” component with respect to the raw material were calculated.

Example 12
Extract fraction under the same conditions as in Example 7 except that the feed rate Uf was 0.10 m / h, U2 was 2.10 m / h, Ua was 0.62 m / h, and Ud / Uf was changed to 20 The composition and the recovery of the “3GE to 5GE” component relative to the raw materials were calculated.

Example 13
Extract fraction under the same conditions as in Example 7, except that the feed rate Uf was 0.05 m / h, U2 was 2.05 m / h, Ua was 0.57 m / h, and Ud / Uf was changed to 40 The composition and the recovery of the “3GE to 5GE” component relative to the raw materials were calculated.

Example 14
The starting 2 obtains a value of the variance and the average residence time of the chromatogram in the same manner as in Example 1 (Fraction 1: Mean residence time 48.5Min, dispersion 1170.9Min ² / Fraction 2: Mean residence time 17.3 min, dispersion 62.0 min ² / fraction 3: average residence time 39.7 min, dispersion 441.6 min ² ), and the composition of simulated moving bed chromatography was calculated.
The separation Rs [1] between fractions 1 and 2 determined from the average residence time and dispersion is 0.37, and the separation Rs [2] between fractions 2 and 3 is 0.39. The calculation was performed under the same conditions as in Example 10 except that the column switching period Ts was changed to 0.44 hours.

  Table 3 shows the composition of the “extract fraction” and the recovery rate of “3GE to 5GE” calculated in Examples 7 to 14.

  From Table 3, when chromatographic purification was performed by the simulated moving bed method, it was confirmed that purified polyglyceryl monoether containing polyglyceryl monoether having a polymerization degree of glycerin of 3 to 5 at a high concentration can be produced at a higher recovery rate. Moreover, it was confirmed that the usage-amount of an organic solvent can be reduced.

Claims (9)

An adsorption step for adsorbing the raw material polyglyceryl monoether represented by the general formula (1) on silica gel, and the silica gel has an SP value of 9.2 to 10.6 [(cal / cm ³ ) ^1/2 ]. A method for producing purified polyglyceryl monoether, comprising an elution step of bringing polyglyceryl monoether into contact with an organic solvent to elute polyglyceryl monoether from the silica gel, wherein the organic solvent is acetone or a mixture of hexane and ethanol .
_{RO- (C 3 H 6 O 2} ) n -H (1)
(In formula, R shows a C6-C22 hydrocarbon group, n is the polymerization degree of glycerol, and shows the number of 1-9.)   The method for producing purified polyglyceryl monoether according to claim 1, wherein the silica has an average pore diameter of 3 to 20 nm.   The manufacturing method of the refined polyglyceryl monoether of Claim 1 or 2 whose average particle diameter of a silica gel is 150-600 micrometers.   The manufacturing method of the refinement | purification polyglyceryl monoether of any one of Claims 1-3 which uses the said organic solvent 3-45 mass times with respect to the total mass of raw material polyglyceryl monoether. The ratio of the total capacity (m ³ / hr) of the raw polyglyceryl monoether per operation time to the total capacity (m ³ ) of silica gel is 0.005 to 1.0 ((m ³ / hr) / m ³ ). The method for producing a purified polyglyceryl monoether according to any one of claims 1 to 4 . The method for producing purified polyglyceryl monoether according to any one of claims 1 to 5 , wherein the adsorption step and the elution step are performed by a simulated moving bed method. The method for producing a purified polyglyceryl monoether according to any one of claims 1 to 6 , wherein the content of the polyglyceryl monoether having a polymerization degree of glycerin of 2 to 5 in the purified polyglyceryl monoether is 43% by mass or more. The method for producing a purified polyglyceryl monoether according to any one of claims 1 to 7 , wherein the content of the polyglyceryl monoether having a polymerization degree of glycerin of 6 or more in the purified polyglyceryl monoether is 35% by mass or less. The method for producing purified polyglyceryl monoether according to any one of claims 1 to 8 , comprising a step of reducing alcohol in the raw material polyglyceryl ether before the adsorption step.

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