JP2002114727A - Method for producing glyceryl ether - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method by which an ultrahigh reactional yield is obtained, an excessively large heat quantity of reaction produced during the reaction can readily be controlled and the reactional time can remarkably be shortened. SOLUTION: This method for producing a glyceryl ether represented by general formula (3) comprises carrying out a ring opening reaction of epoxy group while feeding a glycidyl ether represented by general formula (1) (wherein, R1 denotes a 1-32C hydrocarbon group; A1 denotes a 2-4C alkylene group; and p denotes a number of 0-200) into a mixture liquid containing a carboxylic acid, a base and water.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a process for producing glyceryl ether, and more particularly to a process for producing glyceryl ether which can control a remarkable exotherm generated during the reaction in a high yield and can greatly shorten the time required for the reaction.

[0002]

2. Description of the Related Art As a method for producing glyceryl ether,
(1) a method of hydrolyzing glycidyl ether in the presence of an acid or alkali, (2) a method of hydrolyzing glycidyl ether using ethylene glycol monoalkyl ether as a solvent in the presence of a phase transfer catalyst, (3) an alkyl halide or A method of reacting an alkyl sulfonate with an alcoholate of 1,2-O-isopropylidene glycerol and then hydrolyzing it, (4) reacting glycidyl ether with a carbonyl compound to produce a 1,3-dioxolane compound After, a method of hydrolysis, (5) a method of reacting glycidyl ether with a carboxylic acid to form a glycerol monoester, and then a method of hydrolysis, (6) a reaction of glycidyl ether and an acid anhydride under a catalyst to glycerol A method of producing a diester and then hydrolyzing it is known.

[0003]

However, among the above-mentioned production methods, the method (1) has a non-uniform reaction system, so that decomposition of the target substance or polymerization of the raw materials occurs, which leads to a decrease in yield and quality. There is a problem of inviting, a method for improving this is disclosed in JP-A-6-25053, JP-A-5-43500 and the like, but the yield is insufficient and the reaction system is homogenized This requires a large amount of a substance to be used, and increases the production cost.
In the method (2), although the heterogeneity of the reaction system is improved, there is a problem that glycidyl ether reacts with the solvent and the yield decreases. In the method (3), it is difficult to obtain raw materials, and the reaction must be performed in an anhydrous state. (Four)
The method has problems of coloring and odor by by-products. In the method (5), the glycidyl ether is further reacted with the produced target product, so that it is necessary to use a large excess of carboxylic acid. The method (6) requires strict temperature control, and requires a large excess of an acid anhydride. In addition, since excessive heat of reaction is generated at the time of ring opening of glycidyl ether, when a method other than (3) is performed in a batchwise manner, the reaction solution may be heated or pressurized, so that there is not enough room for the reaction apparatus. In many cases, a certain cooling capacity or pressure resistance is required.

An object of the present invention is to provide a process for producing glyceryl ether, which can easily obtain a high reaction yield in one step and can stably control the heat generated during the reaction.

[0005]

Means for Solving the Problems The inventors of the present invention carry out a reaction while supplying glycidyl ether to a mixed solution containing a carboxylic acid, a base and water. It has been found that the reaction yield can be remarkably improved, the amount of reaction heat generated during the reaction can be controlled by controlling the raw material supply rate, and a considerable time reduction effect can be obtained under reaction conditions requiring an excessive amount of time. Was.

[0006] That is, the present invention relates to a mixed solution containing a carboxylic acid, a base and water, which has the general formula (1)

[0007]

Embedded image

Wherein R ¹ represents a hydrocarbon group having ¹ to 32 carbon atoms; A ¹ represents an alkylene group having 2 to 4 carbon atoms;
Represents a number from 0 to 200. A ring-opening reaction of an epoxy group is performed while supplying a glycidyl ether represented by the following formula (hereinafter, referred to as “glycidyl ether (1)”);

[0009]

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[Wherein R ¹ , A ¹ and p have the same meaning as described above. ] (Hereinafter referred to as "glyceryl ether (2)").

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION The hydrocarbon group having ¹ to 32 carbon atoms represented by R ¹ in the general formula (1) is a linear or branched alkyl group having 1 to 32 carbon atoms, Examples thereof include a linear or branched alkenyl group having 32 carbon atoms and an aryl group having 6 to 14 carbon atoms. Examples of the alkylene group having 2 to 4 carbon atoms represented by A ¹ include an ethylene group, a trimethylene group, a propylene group, and a butylene group. p is preferably 0. R
¹ - (OA ¹⁾ _p - Specific examples are methyl group, an ethyl group,
n-propyl group, n-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n-decyl group, n-undecyl group, n-dodecyl group, n-tridecyl group, n-tetradecyl group, n-pentadecyl group, n-hexadecyl group, n-heptadecyl group, n-octadecyl group, n-nonadecyl group, n-eicosyl group, n-heneicosyl group, n-docosyl group, n-tricosyl group, n-tetracosyl group, n-pentacosyl group, n-hexacosyl group, 2-ethylhexyl group,
3,5-dimethylhexyl group, phenyl group, naphthyl group, 9-
Examples include an octadecenyl group, a 9,12-octadecadienyl group, an n-butoxyethoxyethyl group, and an n-octyloxyethyl group.

Examples of the carboxylic acid include a linear or branched, saturated or unsaturated carboxylic acid having 1 to 36 carbon atoms. Examples of such carboxylic acids include saturated fatty acids such as formic acid, acetic acid, octanoic acid, lauric acid, stearic acid, triacontanic acid, 2-ethylhexanoic acid, and 3,5-dimethylhexanoic acid; oleic acid, linoleic acid, and the like. Unsaturated fatty acids; divalent fatty acids such as oxalic acid, succinic acid, glutaric acid and adipic acid; aromatic carboxylic acids such as benzoic acid and phthalic acid; hydroxy such as glycolic acid, lactic acid, citric acid, malic acid and gluconic acid Carboxylic acids; halogenocarboxylic acids such as chloroacetic acid. Among them, a carboxylic acid having 8 to 24 carbon atoms is preferable because coexistence with a base forms a carboxylate to exhibit an emulsifying action and can reduce the nonuniformity of the reaction. The amount of the carboxylic acid to be added is 0.002 to 0.5001 equivalents, particularly 0.02 to the total supply of the glycidyl ether (1).
~ 0.31 equivalents are preferred.

[0013] Examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide. And potassium hydroxide are preferred. The amount of the base added is 0.001 to 0.5 equivalent, particularly 0.01 to 0.5 equivalent to the total supply amount of glycidyl ether (1).
0.3 equivalent is preferred.

The reaction ratio of glyceryl ether (2) can be increased by making the ratio of the carboxylic acid to the base an excess of the carboxy group of the carboxylic acid to the base. Here, the reaction yield refers to the molar ratio of the sum of glyceryl ether (2) and glycerol carboxylic acid monoester to glycidyl ether (1). Glycerol carboxylic acid monoester can be easily converted to glyceryl ether (2) by making the molar ratio of the base to carboxylic acid in the solution after the reaction equal to or more than the equivalent. As the excess of the carboxylic acid, the value obtained by subtracting the number of equivalents of the base from the number of equivalents of the carboxylic acid relative to the total supply amount of glycidyl ether (1) is 0.001 to 0.5 equivalents, particularly 0.1.
It is preferably from 01 to 0.3 equivalent.

The amount of water used is preferably from 1 to 100 molar equivalents, particularly preferably from 1 to 10 molar equivalents, based on the total supply of glycidyl ether (1). If the amount of water used is large, the reaction solution is likely to be non-uniform, and the base concentration will be diluted, resulting in a slow reaction rate.
There is a problem that the productivity of glyceryl ether per unit volume is reduced. Further, an arbitrary amount of water may be additionally supplied in parallel with the supply of glycidyl ether (1) during the reaction for the purpose of promoting uniformity of the reaction solution.

The method of supplying the glycidyl ether (1) includes a method of continuously supplying at a constant supply rate over time, a method of continuously changing the supply rate over time, a method of performing an intermittent supply at a constant supply rate, A method of changing the supply speed is exemplified. The supply position may be any position in the reaction solution, on the gas-liquid interface of the reaction solution, or on the gas-liquid interface of the reaction solution.

The glycidyl ether (1) is preferably supplied at such a rate that the glycidyl ether (1) to be supplied is rapidly consumed in the reaction solution and does not cause concentration accumulation. When such a glycidyl ether (1) is supplied at a speed at which the glycidyl ether (1) is rapidly consumed, the required cooling capacity can be easily estimated because reaction heat proportional to the reaction amount is generated. Conversely, if the supply is performed at a rate higher than the consumption rate, glycidyl ether (1) accumulates in the reaction system, and the conditions for the batch reaction from the beginning are approached, and the effect of the present invention is diminished. As a method for confirming the concentration accumulation of glycidyl ether (1), the degree of turbidity of the reaction solution can be used as an index. When the ratio of glycidyl ether (1) to the generated glyceryl ether in the reaction solution increases, a phenomenon in which the layers are separated and the appearance becomes turbid is observed. By utilizing this, the above object can be achieved by controlling the supply amount of glycidyl ether (1) so as to maintain the transparency of the reaction solution. The method for controlling the transparency is not particularly limited, but a method in which reaction conditions in which turbidity does not occur in a transparent glass container is previously selected, and glycidyl ether is used when turbidity occurs using an absorptiometer.
The method of adjusting the supply amount of (1) can be mentioned.
In this case, a quartz glass cell (10 mm optical path length, 20 mm
C)), when measuring the transmitted light of the reaction solution at a wavelength of 600 nm, as an index of the transparency of the reaction solution, preferably an absorbance of 1 or less when glycidyl ether (1) is blank,
0.3 or less is more preferable.

In the present invention, by adding a surfactant to a mixed solution containing a carboxylic acid, a base and water, the reaction solution to be separated is emulsified or dispersed, and the reaction speed is accelerated. A significant effect of shortening the required reaction time can be obtained. As such a surfactant, any of an anionic surfactant, a cationic surfactant, an amphoteric surfactant and a nonionic surfactant can be used. Examples of anionic surfactants include soap, alkyl sulfate, alkyl polyoxyethylene sulfate, alkylbenzene sulfonate, α-olefin sulfonate, monoalkyl phosphate, N-acyl-N-methyltaurate, and acyl isethione. Acid salts, N-acyl glutamates, N-acyl sarcosinates, alkenyl succinates, and the like.As the cationic surfactant, alkyl trimethyl ammonium salt,
Dialkyldimethylammonium salts, triethanolamine / difatty acid ester quaternary salts, alkylbenzenedimethylammonium salts, alkylammonium salts, alkylpyridinium salts, etc., and the amphoteric surfactants include alkyldimethylamine oxide, alkylcarboxybetaine, alkyl Sulfobetaine, amide amino acid salts and the like, and nonionic surfactants include polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, fatty acid polyoxyethylene ester, fatty acid sorbitan ester, fatty acid polyoxyethylene sorbitan ester, fatty acid Sucrose ester, alkyl polyglucoside, fatty acid diethanolamide, fatty acid monoglyceride, alkyl monoglyceryl ether and the like. That. Among these, alkyl glyceryl ethers, particularly the following general formula (3)

[0019]

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Wherein R ² represents a hydrocarbon group having 1 to 32 carbon atoms, A ² represents an alkylene group having 2 to 4 carbon atoms, and q
Represents a number from 0 to 200. ]

Alkyl glyceryl ether represented by
Is similar to the molecular structure of glycidyl ether (1)
Because of its high ability to equalize the reaction system, glycidyl
Easily obtained by hydrolysis of ether (1)
Very preferred. R in the general formula (3) ^Two, A^TwoAnd q
Is R in the aforementioned general formula (1).¹, A¹Same as p
And the like.

When alkyl glyceryl ether is used as the surfactant, a part of the reaction product may be used at the start of the reaction.

The amount of the surfactant to be added is preferably 0.1 to 50% by weight, particularly preferably 1 to 30% by weight, based on the total amount of the glycidyl ether (1). If the added amount is too small, the reaction liquid is difficult to emulsify or homogenize, and the rate at which glycidyl ether (1) can be supplied is restricted, or the reaction yield is reduced. On the other hand, if the addition amount is too large, the amount of glyceryl ether produced per unit volume decreases, and the production efficiency decreases.

The reaction temperature is preferably from 60 to 300 ° C, particularly preferably from 80 to 200 ° C. If the temperature is too low, a long time is required for the reaction, and if the temperature is too high, the pressure increases due to the steam pressure, and the facility load increases.

The stirring blade used in the present invention is not particularly limited. Flat blades, inclined flat blades, flat blade disk turbines, inclined blade disk turbines, curved blades, propellers, faudler types, bull margin types, anchor types, full zones Mold, a max blend type, a homomixer and the like. Among them, for the reaction in the heterogeneous phase, it is necessary to use a high-shear type stirring blade such as a flat blade, a flat blade with a slope, a flat blade disk turbine, a tilted blade disk turbine, and a homomixer. Is preferred.

[0026]

Example 1 434 g of acetic acid (manufactured by Kishida Chemical Co .; primary grade, purity 99% or more),
Sodium hydroxide (manufactured by Wako Pure Chemical Industries; special grade, purity 95)
%) 286 g and ion-exchanged water 1289 g are put into a 20 L autoclave, and two inclined flat blades (width 3 cm, height 1 cm, inclination angle)
While stirring at 680 rpm at 45 °), the temperature was raised to 200 ° C. by a mantle heater. Then, while maintaining at 200 ° C, n-
6800 g of octyl glycidyl ether (purity: 98%) was continuously dropped into the autoclave at a constant flow rate for 2 hours, kept at a constant temperature for 1 hour for aging, and then cooled to 80 ° C. In the reaction operation for a total of 3 hours, a cooling operation such as air cooling or water cooling for preventing temperature rise was not required. Further, 15 g of sodium hydroxide was added to the reaction product, and the mixture was stirred and maintained for 1 hour. After quantitative analysis of the final reaction product by gas chromatography, the yield of n-octylglyceryl ether was 98%. Met.

Comparative Example 1 The procedure of Example 1 was repeated, except that n-octyl glycidyl ether, acetic acid, sodium hydroxide and ion-exchanged water were charged all at once, kept at 200 ° C. for 3 hours with stirring at 800 rpm, and then cooled. 200 ° C reached 18 ° C
Minutes later, the temperature reached 235 ° C due to heat generation.
After air cooling to 200C, the temperature was maintained at 200C. The yield of n-octyl glyceryl ether was 94%.

Example 2 5.12 g of adipic acid (manufactured by Wako Pure Chemical Industries; special grade, purity of 99.5% or more), 2.58 g of sodium hydroxide and ion-exchanged water
78.90 g was placed in a 300 mL autoclave, and the temperature was raised to 100 ° C. with a mantle heater while stirring at 800 rpm with two inclined flat blades (width 3 cm, height 1 cm, inclination angle 45 °).
Then, while maintaining the temperature at 100 ° C., 120 g of n-butyl glycidyl ether (manufactured by Kishida Chemical Co., Ltd., primary grade, purity of 95% or more) was dropped into the autoclave continuously at a constant flow rate for 18 hours,
After being kept at a constant temperature for one hour for aging, it was cooled to 80 ° C.
Further, 0.37 g of sodium hydroxide was added to the reaction product, and 1
After stirring and maintaining for a period of time, the final reaction product was subjected to quantitative analysis by gas chromatography, and as a result, the yield of n-butylglyceryl ether was 95%.

Comparative Example 2 The procedure of Example 2 was repeated except that n-butyl glycidyl ether, adipic acid, sodium hydroxide and ion-exchanged water were charged all at once, stirred at 100 ° C. for 18 hours, cooled and cooled. As a result, the yield of n-butyl glyceryl ether was 92%.

Example 3 Citric acid (manufactured by Kishida Chemical Co .; special grade, purity 99.5% or more)
300 g of 98 g, 0.30 g of calcium hydroxide (manufactured by Wako Pure Chemical Industries; special grade, purity 96% or more) and 110.46 g of ion-exchanged water
The mixture was placed in an autoclave and heated to 200 ° C. with a mantle heater while stirring at 800 rpm with two inclined flat blades (width 3 cm, height 1 cm, inclination angle 45 °). Then, while maintaining at 200 ° C., 105 g of n-butyl glycidyl ether (manufactured by Kishida Chemical Co .; primary grade, purity of 95% or more) was continuously dropped into the autoclave at a constant flow rate for 3 hours, and kept at a constant temperature for 1.5 hours for aging. Then, it was cooled to 80 ° C. In the reaction operation for a total of 4.5 hours, no cooling operation such as air cooling or water cooling for preventing temperature rise was required. Further, 0.30 g of calcium hydroxide was added to the reaction product, and the mixture was stirred and held for 1 hour. The final reaction product was quantitatively analyzed by gas chromatography. As a result, the yield of n-butyl glyceryl ether was as follows.
93%.

Comparative Example 3 The procedure of Example 3 was repeated except that n-butyl glycidyl ether, citric acid, calcium hydroxide and ion-exchanged water were charged all at once, stirred at 200 ° C. for 1 hour, cooled and cooled. As a result, the yield of n-butyl glyceryl ether was 90%.

Example 4 Lauric acid (trade name: LUNAC L-98, manufactured by Kao Corporation, purity 98%)
86.00 g, potassium hydroxide (Kishida Chemical; 1
Grade, purity 85%) 2L of 17.35g and 75.84g of deionized water
Put in an autoclave, 4 flat curved blades (5 cm wide, height
While stirring at 400 rpm at 1.1 cm), the temperature was increased to 110 ° C. by a mantle heater. Then, while keeping at 110 ° C,
1000 g of n-octyl glycidyl ether (98% purity) and 113.76 g of ion-exchanged water were continuously dropped into the autoclave at a constant flow rate for 6 hours, kept at a constant temperature for aging for 2 hours, and then cooled to 80 ° C. Further, 10.41 g of potassium hydroxide was added to the reaction product, and the mixture was stirred and maintained for 1 hour. After quantitative analysis of the final reaction product by gas chromatography, the yield of n-octylglyceryl ether was 97%. %
Met.

Comparative Example 4 The procedure of Example 4 was repeated except that n-octyl glycidyl ether, lauric acid, potassium hydroxide and ion-exchanged water were charged all at once, stirred at 110 ° C. for 7 hours, cooled and cooled. However, the yield of n-octyl glyceryl ether was 94%.

Example 5 Lauric acid (trade name: LUNAC L-98, manufactured by Kao Corporation, purity 98%)
12.88 g), 2.27 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries; special grade, 95% purity) and 24.33 g of ion-exchanged water
Into a 300mL autoclave, and insert two flat blades (width 3c
m, height 1 cm, inclination angle 45 °), and the temperature was raised to 100 ° C with a mantle heater while stirring at 800 rpm. Then 1
While maintaining the temperature at 00 ° C, 150 g of n-octadecylglycidyl ether (98% purity) was continuously dropped into the autoclave at a constant flow rate for 3 hours, kept at a constant temperature for aging for 4 hours, and then cooled to 80 ° C. Further, 0.38 g of sodium hydroxide was added to the reaction product, and the mixture was stirred and held for 1 hour. After quantitative analysis of the final reaction product by gas chromatography, the yield of n-octadecylglyceryl ether was 81%.
%Met.

Comparative Example 5 The procedure of Example 5 was repeated except that n-octadecylglycidyl ether, lauric acid, sodium hydroxide and ion-exchanged water were charged at once, stirred at 100 ° C. for 7 hours, and then cooled. However, the yield of n-octadecylglyceryl ether was 73%.

Example 6 9.57 g of acetic acid (manufactured by Kishida Chemical Co .; primary grade, purity of 99% or more),
Sodium hydroxide (manufactured by Wako Pure Chemical Industries; special grade, purity 95)
%) 4.98 g, 15 g of sodium lauryl sulfate (trade name: Emar O, manufactured by Kao Corporation) and 28.44 g of ion-exchanged water are placed in a 300 mL autoclave, and two inclined flat blades (width 3 cm, height 1)
The temperature was raised to 110 ° C. with a mantle heater while stirring at 800 rpm at an inclination angle of 45 cm. Then, while maintaining the temperature at 110 ° C, n-octyl glycidyl ether (purity 98%) 15
0 g was continuously dropped into the autoclave at a constant flow rate for 12 hours, kept at a constant temperature for 3 hours for aging, and then cooled to 80 ° C. Further, 1.66 g of sodium hydroxide was added to the reaction product, and the mixture was stirred and maintained for 1 hour. After quantitative analysis of the final reaction product by gas chromatography, the yield of n-octylglyceryl ether was 98%. %Met.

Example 7 9.57 g of acetic acid (manufactured by Kishida Chemical Co .; first grade, purity 99% or more)
Sodium hydroxide (manufactured by Wako Pure Chemical Industries; special grade, purity 95)
%) 4.98 g, polyoxyethylene lauryl ether (trade name Emulgen 123P, manufactured by Kao Corporation) 15 g and ion-exchanged water
28.44 g was put in a 300 mL autoclave, and the temperature was raised to 110 ° C. with a mantle heater while stirring at 800 rpm with two inclined flat blades (width 3 cm, height 1 cm, inclination angle 45 °).
Then, while maintaining at 110 ° C., 150 g of n-octyl glycidyl ether (98% purity) was continuously dropped into the autoclave at a constant flow rate for 12 hours, kept at a constant temperature for 3 hours for aging, and then cooled to 80 ° C. Further, 1.66 g of sodium hydroxide was added to the reaction product, and the mixture was stirred and maintained for 1 hour. After quantitative analysis of the final reaction product by gas chromatography, the yield of n-octylglyceryl ether was 98%.
%Met.

Example 8 9.57 g of acetic acid (manufactured by Kishida Chemical Co .; primary grade, purity 99% or more),
Sodium hydroxide (manufactured by Wako Pure Chemical Industries; special grade, purity 95)
%) 4.98 g, n-octyl glyceryl ether (purity 99
%) And 28.44 g of ion-exchanged water are placed in a 300 mL autoclave, and two inclined flat blades (width 3 cm, height 1 cm, inclination angle)
The temperature was raised to 110 ° C. by a mantle heater while stirring at 800 rpm at 45 °). Then, while maintaining the temperature at 110 ° C, n-
150 g of octyl glycidyl ether (purity: 98%) was continuously dropped into the autoclave at a constant flow rate for 12 hours, kept at a constant temperature for aging for 3 hours, and then cooled to 80 ° C. Further, 1.66 g of sodium hydroxide was added to the reaction product, and the mixture was stirred and maintained for 1 hour. After quantitative analysis of the final reaction product by gas chromatography, the yield of n-octylglyceryl ether was 98%. %Met.

Example 9 9.57 g of acetic acid (manufactured by Kishida Chemical Co .; primary grade, purity 99% or more),
2-ethylhexyl glyceryl ether (99% purity) 30
g, 2.00 g of ion-exchanged water and 6.61 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries; special grade, 95% purity) in a 300 mL round bottom flask, each having a crescent blade (width 4 cm, height 1.6). The temperature was raised to 110 ° C. while stirring at 300 rpm in (cm). At this time, the generated steam was condensed in the cooler and returned to the round bottom flask again. Then, while keeping the temperature at 110 ° C., each flask was charged with 150 g of 2-ethylhexyl glycidyl ether (manufactured by Shell Japan, 99% purity).
g and ion-exchanged water at a constant flow rate in one hour,
On the other hand, while continuously monitoring the turbidity of the reaction solution visually, the solution was dropped at a constant flow rate for a total of 6 hours only when the reaction solution was clarified. The reaction was terminated when the conversion was 99% by quantitative analysis by gas chromatography, and the reaction product was obtained after cooling to 80 ° C. Further, 0.04 g of sodium hydroxide was added to the reaction product, and the mixture was stirred and maintained for 1 hour. As a result of quantitative analysis of the final reaction product by gas chromatography, the yield of 2-ethylhexyl glyceryl ether was 89% when supplied for 1 hour, and 93% when turbidity was monitored. %Met.

Comparative Example 6 In Example 9, 2-ethylhexyl glycidyl ether was added without adding 2-ethylhexyl glyceryl ether.
Acetic acid, ion-exchanged water and sodium hydroxide were charged all at once, stirred and maintained at 110 ° C, and cooled to a conversion of 99%. The same operation was performed except that the yield was 2-ethylhexyl glyceryl ether. Was 87%.

Example 10 Lauric acid (trade name: LUNAC L-98, manufactured by Kao Corporation, purity 98%)
28.35 g of potassium hydroxide (available from Kishida Chemical; first grade, purity 85%) for 88.90 g and 391.90 g of ion-exchanged water.
g, 25.11 g, and 14.35 g each in a 2 L autoclave, and four curved flat blades (5 cm in width, 1.1 c in height)
While stirring at 400 rpm in m), the temperature was raised to 160 ° C. with a mantle heater. Then, while maintaining the temperature at 160 ° C., add n-amyl glycidyl ether (purity) to each autoclave.
(98%) 800 g was continuously dropped into the flask at a constant flow rate for 1 hour, kept at a constant temperature for 1 hour for aging, and then cooled to 80 ° C. In the reaction operation for a total of 2 hours, no cooling operation such as air cooling or water cooling for preventing temperature rise was required.
Further, the cumulative addition amount of potassium hydroxide to the reaction product is 28.70.
g, and the mixture was stirred and maintained for 1 hour. The final reaction product was quantitatively analyzed by gas chromatography. As a result, the yield of n-amyl glyceryl ether was 28.35. g was 89%, 25.11 g was 93%, and 14.35 g was 97%.

Comparative Example 7 The procedure of Example 10 was repeated, except that n-amylglycidyl ether, lauric acid, ion-exchanged water and potassium hydroxide were charged at once, stirred at 160 ° C. for 2 hours, cooled and cooled. When the temperature was raised to 171 to 179 ° C. during the reaction, a cooling operation by air cooling was performed. The yield of n-amyl glyceryl ether was 28.3% for potassium hydroxide.
It was 78% for 5 g, 86% for 25.11 g, and 93% for 14.35 g.

Example 11 Acetic acid (manufactured by Kishida Chemical Co .; first grade, purity 99% or more) 63.82
g, 100 g of n-octyl glyceryl ether (99% purity)
And 189.60 g of ion-exchanged water and 44.08 g of sodium hydroxide (manufactured by Wako Pure Chemical Industries; special grade, 95% purity), 42.08
g, 22.14 g in each 2L autoclave, 400 sheets with 4 curved flat blades (5cm width, 1.1cm height)
While stirring at rpm, the temperature was raised to 110 ° C. by a mantle heater. Then, while keeping at 110 ° C., each autoclave was charged with n-octyl glycidyl ether (98% purity).
00 g was continuously dropped into the flask at a constant flow rate for 12 hours, kept at a constant temperature for 3 hours for aging, and then cooled to 80 ° C. In the reaction operation for a total of 15 hours, a cooling operation such as air cooling or water cooling for preventing temperature rise was not particularly required.
Further, when the total amount of sodium hydroxide added to the reaction product is 4
4.29 g was added and stirred for 1 hour. After the final reaction product was analyzed quantitatively by gas chromatography, the yield of n-octylglyceryl ether was 93% for 44.08g, 42.08
g was 97% and 22.14 g was 99%.

Comparative Example 8 In Example 11, n-octyl glycidyl ether, acetic acid, ion-exchanged water and sodium hydroxide were added all at once without adding n-octyl glyceryl ether, and 110 ° C.
The operation was carried out in the same manner except that the mixture was cooled after stirring for 100 hours, and a cooling operation by air cooling was performed because a sudden rise in temperature to 112 to 115 ° C. was observed during ripening. The yield of n-octyl glyceryl ether is 87% when the amount of sodium hydroxide is 44.08 g, 94% when 42.08 g, and 97% when 22.14 g.
%Met.

Example 12 9.57 g of acetic acid (manufactured by Kishida Chemical Co .; first grade, purity: 99% or more)
Sodium hydroxide (manufactured by Wako Pure Chemical Industries; special grade, purity 95)
%) 4.98 g and ion-exchanged water 28.44 g were placed in a 300 mL autoclave, and stirred at 800 rpm with two inclined flat blades (width 3 cm, height 1 cm, inclination angle 45 °), and heated to 110 ° C with a mantle heater. The temperature rose. Then, while maintaining 110 ° C,
30 g of n-octyl glycidyl ether (98% purity) are intermittently dropped into the autoclave in 40 hours, and then 120 g.
Was continuously dropped into the autoclave in 10 hours, and the reaction product was obtained after cooling to 80 ° C. at the 52th hour when the conversion to glyceryl ether was 99% by quantitative analysis by gas chromatography. . In addition, sodium hydroxide is added to the reaction product.
After adding 1.66 g and keeping stirring for 1 hour, the final reaction product was subjected to quantitative analysis by gas chromatography. As a result, the yield of n-octylglyceryl ether was 98%.

Comparative Example 9 n-octyl glycidyl ether, acetic acid, sodium hydroxide and ion-exchanged water were charged all at once, stirred and maintained at 110 ° C., and the conversion to glyceryl ether was determined by quantitative analysis by gas chromatography. The same operation was performed except that the mixture was cooled at the 85th hour when it became 99%, and the yield of n-octylglyceryl ether was 96%.

[0047]

According to the process for producing glyceryl ether of the present invention, an extremely high reaction yield can be obtained, an excessive amount of heat generated during the reaction can be easily controlled, and the reaction time can be greatly reduced.

 ──────────────────────────────────────────────────続 き Continued on the front page (72) Inventor Hiroshi Oka 1334 Minato, Wakayama City, Wakayama Prefecture, Kao Corporation Research Laboratory (72) Inventor Mitsugu Morishita, 1334 Minato, Wakayama City, Wakayama Prefecture, Kao Research Center F-term (reference) 4H006 AA02 AC41 BA02 BA06 BA29 BA49 GP01 GP10 4H039 CA60 CF90 4J005 AA03 BD01 BD03

Claims (6)

[Claims] 1. A mixed solution containing a carboxylic acid, a base and water is added with a compound of the general formula (1) [Wherein, R ¹ represents a hydrocarbon group having ¹ to 32 carbon atoms, A ¹ represents an alkylene group having 2 to 4 carbon atoms, and p represents a number of 0 to 200. A ring-opening reaction of an epoxy group is carried out while supplying the glycidyl ether represented by the general formula (2). [Wherein, R ¹ , A ¹ and p have the same meanings as described above. Glyceryl ether represented by the formula: 2. The method according to claim 1, wherein the carboxylic acid has 8 to 24 carbon atoms. 3. The method according to claim 1, wherein the liquid mixture contains a surfactant. 4. The surfactant is represented by the general formula (3): [In the formula, R ² represents a hydrocarbon group having 1 to 32 carbon atoms, A ² represents an alkylene group having 2 to 4 carbon atoms, and q represents a number of 0 to 200. 4. The method according to claim 3, wherein the glyceryl ether is represented by the formula: 5. The process according to claim 1, wherein the feed rate of the glycidyl ether represented by the general formula (1) is controlled so that the reaction solution has transparency. 6. The process according to claim 1, wherein the equivalent of the carboxylic acid in the mixture is in excess of the equivalent of the base.