JP2014125474A - Method of producing alkyl glycoside - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method of producing an alkyl glycoside using an aqueous saccharide solution, the method capable of inhibiting the occurrence of bubbles and reducing by-products of polysaccharides.SOLUTION: This invention provides a method of producing an alkyl glycoside in which saccharides and higher alcohols are reacted with each other in the presence of an emulsifier and an acid catalyst, wherein an aqueous saccharide solution is used as saccharides, and the emulsifier is an alkyl glycoside including an alkyl pentoside.

Description

  The present invention relates to a method for producing an alkyl glycoside.

Nonionic surfactants are general-purpose materials used in a wide variety of products such as many cosmetics, cleaning agents, and chemicals. This nonionic surfactant is classified into ethylene oxide type, polyglycerin type, sugar type, etc. from the structure of a hydrophilic group. Among these, sugar-based surfactants are excellent in terms of low irritation to the skin, stable generation of foam, and stabilization of foam.
A typical alkyl glycoside as a sugar surfactant is obtained from a glycosylation reaction between a sugar and a higher alcohol, and is widely used as a cleaning agent, a wetting agent, a gelling agent, a lubricant, an emulsifier and the like.

One method for producing alkyl glycosides is a method in which a sugar and a higher alcohol are directly reacted in the presence of an acid catalyst. In this method, when sugar, moisture, and an acid catalyst coexist, the yield decreases and the hue deteriorates due to the by-production of a polysaccharide, which is a highly condensed product of sugars. For this reason, it is common to use an anhydrous sugar that does not contain water, such as crystal water, as the sugar source.
On the other hand, since sugar derived from biomass is obtained as an aqueous sugar solution, it is desired to effectively use the aqueous sugar solution without removing water. However, when an aqueous sugar solution is used for the production of alkylglycoside, there is a problem that the polysaccharide described above is produced as a by-product due to the coexistence of moisture.
Therefore, in order to solve the above problem, for example, in the production method of alkyl glycosides in which aqueous glycolose and an aliphatic primary alcohol are reacted, an anionic surfactant having an emulsifying property as an acid catalyst is used, A method of using an alkyl glycoside as another emulsifier has been proposed (see Patent Document 1).

Special table hei 7-505403

However, when using the alkyl glycoside obtained by the method of Patent Document 1 as a nonionic surfactant, it is not preferable to contain an anionic surfactant used as an acid catalyst. Furthermore, the method of Patent Document 1 requires special manufacturing equipment and complicated processes, and is industrially disadvantageous.
In addition, the present inventors have conducted research on a method for producing an alkyl glycoside using an aqueous sugar solution. When alkyl glucoside is used as an emulsifier, bubbles are generated in the reactor and the reaction cannot be continued. We faced new challenges that were not described in the literature.

  Therefore, the present invention provides a method for producing an alkyl glycoside that can suppress the generation of bubbles and reduce the by-product of a polysaccharide in the method for producing an alkyl glycoside using an aqueous sugar solution.

The present inventors have found that the above problem can be solved by allowing an alkylglycoside containing an alkylpentoside as an emulsifier to coexist in a reaction system together with a sugar and a higher alcohol.
That is, the present invention relates to a method for producing an alkyl glycoside in which a saccharide and a higher alcohol are reacted in the presence of an emulsifier and an acid catalyst, wherein the saccharide is an aqueous saccharide solution, and the emulsifier is an alkyl glycoside containing an alkyl pentoside. And a method for producing an alkyl glycoside (hereinafter, also referred to as “the production method of the present invention”).

  ADVANTAGE OF THE INVENTION According to this invention, in the manufacturing method of the alkyl glycoside using sugar aqueous solution, the manufacturing method of the alkyl glycoside which can suppress generation | occurrence | production of foam and can reduce the byproduct of polysaccharide can be provided.

  The production method of the present invention is a method for producing an alkyl glycoside in which a saccharide and a higher alcohol are reacted in the presence of an emulsifier and an acid catalyst, wherein the saccharide is an aqueous solution of sugar and the emulsifier is an alkyl glycoside containing an alkyl pentside. It is characterized by being.

<Aqueous sugar solution>
The production method of the present invention uses an aqueous sugar solution as the sugar.
Examples of the sugar contained in the aqueous sugar solution include one or more selected from monosaccharides, oligosaccharides, and polysaccharides.
Examples of monosaccharides include one or more aldoses selected from allose, altrose, glucose, mannose, gulose, idose, galactose, talose, ribose, arabinose, xylose and lyxose.
Examples of the oligosaccharide include one or more selected from maltose, cellobiose, lactose, sucrose, and maltotriose.
Examples of the polysaccharide include one or more selected from hemicellulose, inulin, dextrin, dextran, xylan, starch, and hydrolyzed starch.
One kind of sugar may be used alone, or two or more kinds of sugars may be used in combination.

Among the saccharides described above, from the viewpoint of improving reactivity, monosaccharides or oligosaccharides are preferable, monosaccharides are more preferable, monosaccharides having 5 or 6 carbon atoms are more preferable, and one kind selected from glucose, xylose, and arabinose Two or more are more preferable, and glucose and xylose are still more preferable.
It is preferable that the sugar contained in the aqueous sugar solution and the sugar constituting the alkyl glycoside used as an emulsifier have the same kind and composition ratio from the viewpoint of easily producing an alkyl glycoside having the target composition.

  The content of sugar in the aqueous sugar solution is preferably 10% by mass or more, and more preferably 50% by mass or more from the viewpoint of emulsification and dispersion. Further, from the viewpoint of handleability during production, it is preferably 80% by mass or less, and more preferably 70% by mass or less. As the aqueous sugar solution used in the present invention, an aqueous sugar solution obtained by hydrolysis of biomass can be used.

<Higher alcohol>
As the higher alcohol used in the production method of the present invention, a linear or branched saturated or unsaturated alcohol having 8 to 22 carbon atoms is preferably used. Of these, linear saturated alcohols are preferred from the viewpoints of reactivity, washing performance, and foam performance. The number of carbon atoms of the higher alcohol is preferably 8 or more, more preferably 10 or more, preferably 22 or less, more preferably 18 or less, and still more preferably 14 or less, from the viewpoints of reactivity, cleaning performance, and foam performance.
Specific examples of higher alcohols include octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl alcohol 1 type (s) or 2 or more types chosen from eicosyl alcohol and oleyl alcohol are mentioned. The higher alcohols can be used alone or in combination of two or more.

<Acid catalyst>
As the acid catalyst used in the production method of the present invention, a known catalyst can be used without particular limitation as long as it is usually used in a dehydration reaction. Examples of the acid catalyst include one or more selected from Bronsted acid and cation exchange resin. Specifically, p-toluenesulfonic acid, methanesulfonic acid, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid And one or more selected from strongly acidic cation exchange resins based on styrene-divinylbenzene copolymer and the like. Among these, Bronsted acid is preferable from the viewpoint of reactivity, and paratoluenesulfonic acid is preferable from the viewpoint of solubility in the higher alcohol.

<Emulsifier>
The emulsifier used in the production method of the present invention is an alkyl glycoside containing an alkyl pentoside. By using alkylpentoside as an emulsifier, the generation of foam can be suppressed and the by-product of polysaccharide can be reduced.
The content of alkylpentoside in the alkylglycoside used as an emulsifier is preferably 10% by mass or more, more preferably 33% by mass or more, from the viewpoint of suppressing the generation of foam and reducing the by-product of polysaccharides. is there. Moreover, it is preferable that content of this alkyl pentoside is 100 mass% or less from a viewpoint of suppressing generation | occurrence | production of a foam and reducing the byproduct of a polysaccharide.

The alkyl pentoside contained in the alkyl glycoside used as an emulsifier is preferably an alkyl xyloside and an alkyl arabinoside, more preferably an alkyl xyloside, from the viewpoint of reactivity. The alkylpentoside contained in the alkyl glycoside used as an emulsifier may be used alone or in combination of two or more.
The alkyl glycoside used as the emulsifier preferably has the same composition as the alkyl glycoside produced in the production method of the present invention from the viewpoint of easily producing an alkyl glycoside having the desired composition.
The alkylglycoside used as the emulsifier preferably contains an alkylpentoside and an alkylhexoside from the viewpoint of having the same composition as the produced alkylglycoside when using an aqueous sugar solution derived from biomass. As the alkyl hexoside, alkyl glucoside is preferable.

The sugar used as the raw material for the alkyl glycoside used in the emulsifier needs to contain pentose.
Examples of pentose include ribose, arabinose, xylose and lyxose. Among these, arabinose and xylose are preferable, and xylose is more preferable.

Monosaccharides, oligosaccharides and polysaccharides other than pentose can also be used as sugars other than pentose used as a raw material for alkyl glycosides used as emulsifiers.
Examples of monosaccharides other than pentose include one or more aldoses selected from allose, altrose, glucose, mannose, gulose, idose, galactose, and talose.
Specific examples of the oligosaccharide and the polysaccharide are the same as those listed in the above description.
Among these, from the viewpoint of reactivity, monosaccharides or oligosaccharides are preferable, monosaccharides having 6 carbon atoms are more preferable, and glucose is more preferable.
The sugar used as the raw material for the alkylglycoside used in the emulsifier may be water-containing or anhydrous. However, from the viewpoint of shortening the reaction time and reducing the by-product of the polysaccharide, anhydrous solid sugar or monohydrate solid sugar. Is preferably used. An anhydrous solid saccharide refers to a solid saccharide that does not contain water in the crystal structure, and has a water content of usually 0.5% by mass or less, preferably 0.2% by mass or less. Solid sugar refers to sugar in a solid state at normal temperature (25 ° C.).

A known production method can be applied to the production of the alkyl glycoside used for the emulsifier. For example, 1 mol or more and 10 mol or less of a higher alcohol and 0.001 mol or more and 0.1 mol or less of an acid catalyst are charged in a reactor with respect to 1 mol of sugar, and the temperature is 80 ° C. or more and 150 ° C. It can manufacture by making it react on the conditions below and pressure 1kPa or more and 10kPa or less. Specific examples and preferred examples of the higher alcohol and the acid catalyst are the same as those listed in the above description. The higher alcohol used in the production of the emulsifier is preferably the same as the higher alcohol used in the production method of the present invention.
After completion of the reaction, a higher alcohol solution containing an alkyl glycoside and an acid catalyst is obtained. It is preferable from the viewpoint of production efficiency that the higher alcohol solution obtained by the production of the emulsifier is used as an emulsifier, an acid catalyst and a higher alcohol in the production method of the present invention.

<Reaction conditions>
In the production method of the present invention, the amount of the alkylglycoside used as an emulsifier at the start of the reaction is based on the total amount of emulsifier, acid catalyst and higher alcohol from the viewpoint of improving production efficiency and reducing polysaccharide by-products. It is preferably 25% by mass or more, more preferably 30% by mass or more, preferably 70% by mass or less, and more preferably 60% by mass or less.

  In the production method of the present invention, the blending ratio of the higher alcohol is preferably 1 or more, more preferably 1.5 or more, and more preferably 2 or more in terms of the molar ratio to the sugar contained in the aqueous sugar solution, from the viewpoint of reducing the by-product of the polysaccharide. Further preferred. Further, from the viewpoint of improving production efficiency, the molar ratio with respect to the sugar contained in the aqueous sugar solution is preferably 7 or less, more preferably 6 or less, still more preferably 5 or less, and even more preferably 4 or less.

  From the viewpoint of improving the reaction rate, the amount of the acid catalyst used is preferably 0.001 or more, more preferably 0.002 or more, and still more preferably 0.003 or more in terms of a molar ratio to the sugar contained in the aqueous sugar solution. Further, from the viewpoint of reducing the coloring of the resulting alkyl glycoside, the molar ratio to the saccharide contained in the aqueous saccharide solution is preferably 0.1 or less, preferably 0.05 or less, and more preferably 0.01 or less.

  The reaction of the saccharide and the higher alcohol in the present invention is preferably a method in which the saccharide and the higher alcohol are reacted by adding an aqueous saccharide solution to a mixed solution containing an alkylglycoside used as an emulsifier, an acid catalyst and a higher alcohol. From the viewpoint of improving production efficiency and reducing by-products of polysaccharides, the sugar and higher alcohol contained in the aqueous sugar solution can be obtained by adding the aqueous sugar solution to the higher alcohol solution containing the emulsifier and acid catalyst obtained by the production of the emulsifier. A reaction method is preferred. As a method for adding the sugar aqueous solution, it is preferable to add dropwise from the viewpoint of suppressing the generation of bubbles and reducing the by-product of polysaccharides. Here, an inert gas atmosphere such as nitrogen or argon may be used as necessary, or a dehydration operation such as decompression may be performed. After the sugar aqueous solution is added, alkylglycoside can be obtained by dehydration reaction while removing by-product water.

The heating temperature during the reaction is preferably 90 ° C. or higher, more preferably 100 ° C. or higher from the viewpoint of reactivity, and 130 ° C. or lower is preferable from the viewpoint of improving production efficiency and suppressing the by-production of polysaccharides. More preferably, it is not higher than ° C.
The pressure during the reaction is preferably 1 kPa or more, more preferably 4 kPa or more, from the viewpoint of suppressing evaporation of the higher alcohol as a raw material. Moreover, 10 kPa or less is preferable from a viewpoint of the removal efficiency of the water byproduced by a dehydration reaction.

The reaction time is preferably 5 minutes or longer, more preferably 10 minutes or longer, and even more preferably 15 minutes or longer from the viewpoint of reactivity. In addition, from the viewpoint of improving production efficiency and suppressing sugar condensation, it is preferably 10 hours or shorter, more preferably 8 hours or shorter, and even more preferably 6 hours or shorter.
After completion of the reaction, unreacted sugar is removed, and further, unreacted higher alcohol, water and the like are removed by neutralization and solvent distillation to obtain an alkyl glycoside.

In addition to the embodiment described above, the present invention further discloses the following method for producing a glycoside compound.
<1> A method for producing an alkyl glycoside in which a sugar and a higher alcohol are reacted in the presence of an emulsifier and an acid catalyst, wherein an aqueous sugar solution is used as the sugar, and the emulsifier is an alkyl glycoside containing an alkyl pentoside. Manufacturing method.

<2> The sugar contained in the aqueous sugar solution is preferably one or more selected from monosaccharides, oligosaccharides, and polysaccharides, more preferably monosaccharides or oligosaccharides, more preferably monosaccharides, and even more. Preferably, it is a monosaccharide having 5 or 6 carbon atoms, more preferably one or more selected from glucose, xylose and arabinose, and still more preferably glucose and xylose. Production method.
<3> The sugar content in the aqueous sugar solution is preferably 10% by mass or more, more preferably 50% by mass or more, preferably 80% by mass or less, more preferably 70% by mass or less. The method for producing an alkyl glycoside according to <1> or <2>.

<4> The higher alcohol is preferably a linear or branched saturated or unsaturated alcohol having 8 to 22 carbon atoms, more preferably a linear saturated alcohol having 8 to 22 carbon atoms. The method for producing an alkyl glycoside according to any one of <1> to <3>.
<5> The carbon number of the higher alcohol is preferably 8 or more, more preferably 10 or more, preferably 22 or less, more preferably 18 or less, still more preferably 14 or less, <4> A method for producing an alkyl glycoside as described in 1. above.
<6> The higher alcohol is preferably octyl alcohol, nonyl alcohol, decyl alcohol, undecyl alcohol, dodecyl alcohol, tridecyl alcohol, tetradecyl alcohol, pentadecyl alcohol, hexadecyl alcohol, heptadecyl alcohol, octadecyl alcohol, nonadecyl The manufacturing method of the alkyl glycoside in any one of said <1>-<5> which is 1 type, or 2 or more types chosen from alcohol, eicosyl alcohol, and oleyl alcohol.

<7> The acid catalyst is preferably one or more selected from Bronsted acid and cation exchange resin, more preferably paratoluenesulfonic acid, methanesulfonic acid, sulfuric acid, hydrochloric acid, nitric acid, phosphoric acid, And one or more selected from strongly acidic cation exchange resins based on a styrene-divinylbenzene copolymer and the like, more preferably Bronsted acid, still more preferably paratoluenesulfonic acid, <1 The manufacturing method of the alkyl glycoside in any one of>-<6>.
<8> The alkylpentoside content in the alkyl glycoside used as an emulsifier is preferably 10% by mass or more, more preferably 33% by mass or more, and preferably 100% by mass or less. The manufacturing method of the alkyl glycoside in any one of>-<7>.

<9> The alkylpentoside contained in the alkyl glycoside used as an emulsifier is preferably one or more selected from alkyl xyloside and alkyl arabinoside, more preferably alkyl xyloside, < The manufacturing method of the alkyl glycoside in any one of 1>-<8>.
<10> The alkyl glycoside according to any one of <1> to <9>, wherein the sugar used as a raw material for the alkyl glycoside used in the emulsifier is preferably an anhydrous solid sugar or a monohydrate solid sugar. Production method.
<11> The amount of the alkylglycoside used as an emulsifier at the start of the reaction is preferably 25% by mass or more, more preferably 30% by mass or more, based on the total amount of the emulsifier, acid catalyst and higher alcohol. The method for producing an alkyl glycoside according to any one of <1> to <10>, preferably 70% by mass or less, more preferably 60% by mass or less.

<12> The mixing ratio of the higher alcohol is a molar ratio with respect to the sugar contained in the aqueous sugar solution, preferably 1 or more, more preferably 1.5 or more, still more preferably 2 or more, preferably 7 or less. More preferably, it is 6 or less, More preferably, it is 5 or less, More preferably, it is 4 or less, The manufacturing method of the alkyl glycoside in any one of said <1>-<11>.
<13> The amount of the acid catalyst used is preferably 0.001 or more, more preferably 0.002 or more, still more preferably 0.003 or more, and preferably 0 in terms of a molar ratio with respect to the sugar contained in the aqueous sugar solution. The alkylglycoside production method according to any one of <1> to <12>, which is 0.1 or less, more preferably 0.05 or less, and still more preferably 0.01 or less.

<14> The solution according to any one of <1> to <13>, wherein a sugar and a higher alcohol are reacted by adding an aqueous sugar solution to a mixed solution containing an alkyl glycoside used as an emulsifier, an acid catalyst, and a higher alcohol. A process for producing an alkyl glycoside.
<15> An alkyl glycoside used as an emulsifier is produced by reacting a sugar containing pentose and a higher alcohol in the presence of an acid catalyst, and an aqueous sugar solution is added to the higher alcohol solution containing the alkyl glycoside and the acid catalyst obtained by the reaction. The method for producing an alkyl glycoside according to any one of <1> to <14>, wherein a sugar and a higher alcohol are reacted with each other by adding.

<16> The heating temperature during the reaction is preferably 90 ° C. or higher, more preferably 100 ° C. or higher, preferably 130 ° C. or lower, more preferably 120 ° C. or lower, <1> to <15> The manufacturing method of the alkyl glycoside in any one of.
<17> The process for producing an alkyl glycoside according to any one of <1> to <16>, wherein the pressure during the reaction is preferably 1 kPa or more, more preferably 4 kPa or more, and preferably 10 kPa or less. .
<18> The reaction time is preferably 5 minutes or more, more preferably 10 minutes or more, still more preferably 15 minutes or more, preferably 10 hours or less, more preferably 8 hours or less, still more preferably 6 The method for producing an alkyl glycoside according to any one of <1> to <17>, wherein the time is not more than time.

In the following examples and comparative examples, the analysis of the anti-end solution was performed by the following method.
<Measurement method of sugar conversion, alkylglycoside concentration, polyglycose concentration>
Charge 4 mL of an aqueous solution (containing 5% by mass of the anti-end solution) prepared using a reaction solution containing alkylglycoside after the reaction (hereinafter referred to as “anti-end solution”) to a solid phase extraction kit (manufactured by GL Sciences Inc.). Then, a high-polar fraction was extracted using 7.5 mL of a 3% by mass acetonitrile aqueous solution, and a low-polar fraction was extracted using 7.5 mL of methanol.
Samples obtained by removing the solvent from each fraction were subjected to gas chromatography (GC) analysis under the following conditions, and the mass ratio of alkylglycoside, polyglycose (by-product sugar condensate) and sugar in the anti-end solution, And the sugar conversion was determined.
The concentrations of alkyl glycoside and polyglycose in the anti-end solution were calculated according to the following formula (1) and the following formula (2).
(1) Alkyl glycoside concentration (mass%) = alkyl glycoside mass / (alkyl glycoside mass + polyglycose mass + sugar mass) × 100
(2) Polyglycose concentration (mass%) = polyglycose mass ÷ (alkylglycoside mass + polyglycose mass + sugar mass) × 100

<Measurement conditions of gas chromatography (GC)>
To 50 mg of the above sample, 1 ml of a trimethylsilylating agent (manufactured by GL Sciences Inc.) was added and sonicated for 2 minutes. After standing for 5 minutes, the resulting pyridine salt was removed by filtration. The obtained filtrate was measured under the following conditions.
Column: DB-1HT (manufactured by Agilent, size: 15 m × 250 μm × 0.10 μm)
・ Temperature raising condition: Initial temperature 100 ° C. (2 minutes hold)
: Rate of temperature increase 10 ° C / min
: Final temperature 350 ° C (10 minutes hold)
・ Internal standard: Tetradecane (Wako Pure Chemical Industries, Ltd.)

<Example 1>
[Preparation of reaction mother liquor]
142.2 g (0.900 mol) of decyl alcohol and 33.8 g (0.225 mol) of anhydrous xylose were charged into a 500 mL five-necked flask. After stirring was started, the temperature was raised while nitrogen was blown into the mixture at 20 mL / min. After reaching 105 ° C., 0.15 g (0.788 mmol) of paratoluenesulfonic acid monohydrate was added as an acid catalyst, and the reaction was started under reduced pressure to 9.4 kPa. After 4 hours from the start of the reaction, the pressure was returned to atmospheric pressure and allowed to cool to room temperature. The sugar conversion reached 99%. As a result, it is calculated that the anti-end solution contains about 40% by mass of alkyl glycoside. This anti-end solution was used as a reaction mother liquor of an aqueous sugar solution.

[Reaction of sugar aqueous solution]
The reaction mother liquor (50 g) obtained above was charged into a 200 mL five-necked flask, and the temperature was raised while nitrogen was blown at 20 mL / min. After reaching 105 ° C., the pressure was reduced to 9.4 kPa. The reaction mother liquor contains 0.205 mol of alkylxyloside as an emulsifier, 0.219 mol of decyl alcohol as a higher alcohol, and 0.224 mmol of paratoluenesulfonic acid monohydrate as an acid catalyst. . After completion of the reduced pressure, 22 g of 50 mass% aqueous xylose solution (0.073 mol as sugar) was continuously added over 5 hours to carry out the reaction. No bubbling of the reaction solution occurred during the reaction. After completion of the dropwise addition of the aqueous sugar solution, the reaction was continued at 105 ° C. and 9.4 kPa for 1 hour. Then, it returned to atmospheric pressure and stood to cool to room temperature. The sugar conversion rate of the anti-end solution reached 99%, and the obtained anti-end solution did not contain solid matter. Table 1 shows the results of the analysis of the anti-end solution according to the analysis method described above.

<Example 2>
An alkyl glycoside was obtained in the same manner as in Example 1 except that the sugar used in the reaction mother liquor and the aqueous sugar solution was a mixed sugar of anhydrous glucose and anhydrous xylose (molar ratio 2: 1). There was no foaming during the reaction, and no solid matter was contained in the anti-end liquid. Table 1 shows the results of the analysis of the anti-end solution according to the analysis method described above.

<Example 3>
An alkyl glycoside was obtained in the same manner as in Example 1 except that the sugar used in the reaction mother liquor and the aqueous sugar solution was a mixed sugar of anhydrous glucose and anhydrous xylose (molar ratio 9: 1). There was no foaming during the reaction, and no solid matter was contained in the anti-end liquid. Table 1 shows the results of the analysis of the anti-end solution according to the analysis method described above.

<Example 4>
An alkyl glycoside was obtained in the same manner as in Example 2 except that tetradecyl alcohol was used as the higher alcohol used in the preparation of the reaction mother liquor. There was no foaming during the reaction, and no solid matter was contained in the anti-end liquid. Table 1 shows the results of the analysis of the anti-end solution according to the analysis method described above.

<Example 5>
An alkylglycoside was obtained in the same manner as in Example 2 except that the reaction mother liquor was prepared with a higher alcohol / sugar molar ratio of 8: 1. There was no foaming during the reaction, and no solid matter was contained in the anti-end liquid. Table 1 shows the results of the analysis of the anti-end solution according to the analysis method described above.

<Example 6>
An alkyl glycoside was obtained in the same manner as in Example 2 except that the concentration of the aqueous sugar solution added to the reaction mother liquor was 10% by mass. There was no foaming during the reaction, and no solid matter was contained in the anti-end liquid. Table 1 shows the results of the analysis of the anti-end solution according to the analysis method described above.

<Example 7>
An alkyl glycoside was obtained in the same manner as in Example 1 except that the sugar used in the preparation of the reaction mother liquor and the aqueous sugar solution was a mixed sugar of anhydrous glucose and anhydrous arabinose (molar ratio 2: 1). . There was no foaming during the reaction, and no solid matter was contained in the anti-end liquid. Table 1 shows the results of the analysis of the anti-end solution according to the analysis method described above.

<Comparative Example 1>
After charging 142.2 g (0.900 mol) of decyl alcohol into a 500 mL five-necked flask and starting stirring, the temperature was increased while blowing nitrogen at 20 mL / min. After reaching 105 ° C., 0.30 g (1.58 mmol) of paratoluenesulfonic acid monohydrate was added as an acid catalyst, and the pressure was reduced to 9.4 kPa. After completion of the decompression, 153.1 g of a 50 mass% mixed sugar aqueous solution (2: 1 molar ratio by mixing glucose and xylose) was continuously added over 5 hours to carry out the reaction. . No bubbling of the reaction solution occurred during the reaction. After completion of the dropwise addition of the aqueous sugar solution, the reaction was continued at 105 ° C. and 9.4 kPa for 1 hour. Then, it returned to atmospheric pressure and stood to cool to room temperature. The sugar conversion rate of the anti-end solution remained at 76%, and the obtained anti-end solution contained solid matter. Table 2 shows the results of the analysis of the anti-end solution according to the analysis method described above.

<Comparative example 2>
Except that the sugar used in the preparation of the reaction mother liquor and the sugar aqueous solution was anhydrous glucose, the same procedure as in Example 1 was carried out. Leaked from. For this reason, it was impossible to continue the reaction.

<Comparative Example 3>
As higher alcohol, 142.2 g (0.900 mol) of decyl alcohol and 94.8 g (0.375 mol) of 1-octadecene were charged into a 500 mL five-necked flask, and after stirring was started, nitrogen was added at 20 mL / min. The temperature was raised while blowing. After reaching 105 ° C., 0.15 g (0.788 mol) of paratoluenesulfonic acid monohydrate was added as an acid catalyst, and the pressure was reduced to 9.4 kPa. When the decompression was completed, 162.2 g of a 50% by mass aqueous glucose solution was continuously added at a rate of 5 hours. Vigorous foaming occurred and the reaction solution flowed out of the flask. For this reason, it was impossible to continue the reaction.

<Comparative example 4>
Except that tetraethylene glycol dimethyl ether was used instead of 1-octadecene, the same procedure as in Comparative Example 3 was performed. As a result, intense foaming occurred and the reaction solution flowed out of the flask. For this reason, it was impossible to continue the reaction.

  From Table 1 and Table 2, Examples 1 to 7 belonging to the production method of the present invention are compared with Comparative Examples 1 to 4 by allowing an alkyl glycoside containing an alkyl pentoside to coexist in the reaction system as an emulsifier. Generation | occurrence | production of a foam can be suppressed, the production amount of by-product of a polysaccharide can be reduced, and an alkyl glycoside can be manufactured simply and economically.

  According to the present invention, in the method for producing an alkyl glycoside using an aqueous saccharide solution, it is possible to suppress the generation of bubbles, reduce the by-product of polysaccharides, and to simplify the use of alkyl glycosides without mixing different types of surfactants into the product. And can be produced economically. The obtained alkyl glycoside can be widely used as a nonionic surfactant in detergents, wetting agents, gelling agents, lubricants and emulsifiers.

Claims (12)

  A method for producing an alkyl glycoside, wherein a sugar and a higher alcohol are reacted in the presence of an emulsifier and an acid catalyst, wherein an aqueous sugar solution is used as the sugar, and the emulsifier is an alkyl glycoside containing an alkyl pentoside. .   The amount of the alkyl glycoside according to claim 1, wherein the amount of the alkyl glycoside used as an emulsifier at the start of the reaction is 25% by mass or more and 70% by mass or less with respect to the total amount of the emulsifier, the acid catalyst and the higher alcohol. Production method.   The method for producing alkylglycoside according to claim 1 or 2, wherein the content of alkylpentoside in the alkylglycoside used as an emulsifier is 10% by mass or more.   The manufacturing method of the alkyl glycoside in any one of Claims 1-3 whose alkyl pentoside contained in the alkyl glycoside used as an emulsifier is an alkyl xyloside.   The manufacturing method of the alkyl glycoside in any one of Claims 1-4 whose compounding ratio of a higher alcohol is 1 or more and 7 or less by the molar ratio with respect to the saccharide | sugar contained in sugar aqueous solution.   The manufacturing method of the alkyl glycoside in any one of Claims 1-5 whose usage-amount of an acid catalyst is 0.001 or more and 0.1 or less by the molar ratio with respect to the saccharide | sugar contained in sugar aqueous solution.   The manufacturing method of the alkyl glycoside in any one of Claims 1-6 whose content of sugar in sugar aqueous solution is 10 mass% or more and 80 mass% or less.   The method for producing an alkyl glycoside according to any one of claims 1 to 7, wherein sugars contained in the aqueous sugar solution are glucose and xylose.   The method for producing an alkyl glycoside according to any one of claims 1 to 8, wherein a sugar and a higher alcohol are reacted by adding an aqueous sugar solution to a mixed solution containing an alkyl glycoside used as an emulsifier, an acid catalyst and a higher alcohol. .   The method for producing an alkyl glycoside according to any one of claims 1 to 9, wherein the sugar and the higher alcohol are reacted at a temperature of 90 ° C or higher and 130 ° C or lower and a pressure of 1 kPa or higher and 10 kPa or lower.   The manufacturing method of the alkyl glycoside in any one of Claims 1-10 whose acid catalyst is a Bronsted acid.   The method for producing an alkyl glycoside according to any one of claims 1 to 11, wherein the higher alcohol is a linear saturated alcohol having 8 to 14 carbon atoms.