JP2001240594A - Production method of glycidyl ether compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a production method of a glycidyl ether compound which obtains the objective products at a high yield without deterioration of product quality and can reduce the COD of the drainage. SOLUTION: A halohydrin ether shown with formula (1) which is dissolved in a hydrophilic organic solvent is reacted with an alkali solution, subsequently, after the solid phase of an alkali halide is separated from the reaction product. The production method of a glycidyl ether is characterized by recovering the glycidyl ether from the liquid phase. [In the formula (1), R shows a polyhydric alcohol group, X shows a halogen atom and n is one or more integer].

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a glycidyl ether compound. In particular, drainage C
The present invention relates to an improvement in a manufacturing method with a reduced OD load.

[0002]

2. Description of the Related Art Various methods have been proposed for producing glycidyl ether compounds. For example,
In the method described in British Patent No. 827450, epihalohydrin is added to alcohol using a Lewis acid catalyst such as boron trifluoride etherate, and an alkali aqueous solution is added to the obtained halohydrin ether compound to effect ring closure. A glycidyl ether compound. At that time, in order to remove by-product alkali halide, water is added to the ring-closure reaction product to dissolve it, and the organic layer and the aqueous layer are separated. However, in this method, the glycidyl ether compound of the product dissolves in the aqueous layer to lower the yield, and the COD concentration is too high to discard the separated aqueous layer as it is. It was necessary to recover the glycidyl ether compound.

Further, in the method described in British Patent No. 1256026, when an aqueous alkali solution is added to a halohydrin ether compound to effect ring closure, a hydrophobic solvent such as ethylene dichloride or toluene is present, and water is added. A ring closure reaction is advanced while azeotropically distilling off, and the by-product alkali halide is separated by filtration. The glycidyl ether compound present in the filtered alkali halide is extremely difficult to remove by washing, and the product yield is reduced. In order to increase the yield of the product, cleaning using an extremely large amount of solvent is required.

Further, in the method described in JP-B-59-24149, a water-soluble solvent or an aqueous solution thereof is used for washing the alkali halide by performing the above-mentioned ring closing reaction while distilling off water under reduced pressure. are doing. In addition, this method has an advantage that it has a high yield and does not generate wastewater. However, due to the heat history at the time of distilling off water, it is inevitable that the quality deteriorates, such as a decrease in product purity. And may be mixed into the product again.

[0005]

In view of the state of the prior art as described above, the desired product can be obtained in high yield without lowering the product quality, and the COD concentration in the wastewater can be reduced. The present inventors have conducted intensive studies to provide a method for producing a glycidyl ether compound, and have reached the present invention.

[0006]

That is, the gist of the present invention resides in the following general formula (1):

Embedded image [In the above general formula, R is a polyhydric alcohol residue, X is a halogen atom, and n is an integer of 1 or more. Is reacted with an aqueous alkali solution in a state of being dissolved in a hydrophilic organic solvent, and then the solid phase alkali halide is separated from the reaction product, and then the glycidyl ether compound is separated from the liquid phase. And recovering the glycidyl ether compound.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION The halohydrin ether compound as a raw material of the present invention is usually obtained by subjecting a polyhydric alcohol to an epihalohydrin addition reaction, but is not limited thereto. Also, the addition reaction product is
In addition to the halohydrin ether compound represented by the general formula (1), the following general formula (2)

[0008]

Embedded image

[In the above formula, R, X and n have the same meaning as in formula (1), and m is an integer of 0 or more.
At least one of the n m is an integer of 1 or more. ] -Halohydrin ether compound represented by the formula: The halogen atom in this compound has different properties depending on the position. The halogen atom at the terminal position is dehydrochlorinated with an aqueous alkali solution to close the ring, and oxirane oxygen is formed. Is not dehydrochlorinated. That is, the term "saponifiable halogen" refers only to the former.

In the present invention, the polyhydric alcohol is not particularly limited as long as it has at least two alcoholic hydroxyl groups in the molecule. Specifically, ethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,4-butanediol, 2,3-butanediol, diethylene glycol, 1,5-pentane Diol, 2,2-dimethyl-
1,3-propanediol, trimethylolethane,
1,6-hexanediol, 2,4,6-hexanetriol, triethylene glycol, 2-ethyl-2-butyl-1,2-propanediol, 1,12-octadecanol, glycerol, erythritol, pentaerythritol, Sorbitol, mannitol, inositol, 1,1,1-trimethylolpropane, 1,4-dimethylolbenzene, 4,4-dimethyloldiphenyl, dimethylolxylene, dimethylolnaphthalene, and the like. Further, the polyhydric alcohol may be polyethylene glycol, polypropylene glycol, diglycerol, triglycerol, or other polyglycerol, which is a polycondensate of the above compounds, and bis (2,3-dihydroxypropyl ether) And ether alcohols such as dihydroxyethyl ether such as dipentaerythritol, dimethylolanisole, bisphenol and resorcinol, and ethylene oxide adducts and propylene oxide adducts of the above compounds. Of course, a mixture of these compounds may be used. The epihalohydrin is selected from epichlorohydrin, epibromohydrin and the like.

In the halohydrin ether compound, the number n for substituting the hydroxyl group of the polyhydric alcohol differs depending on the amount of epihalohydrin used, and monohalohydrin ether,
It is selected from dihalohydrin ether and the like.

As the hydrophilic organic solvent used in the method of the present invention, those which can be freely mixed with water are preferable.
And a compound containing 10% by weight or more of water, or a mixture containing the compound. Specific examples of the hydrophilic organic solvent (the number in parentheses after the compound name, unless otherwise specified,
Shows the solubility of water at 25 ° C. Those without a number indicate that they are freely mixed. ) Are methanol, ethanol, n-propanol, isopropanol, n-butanol (20.3), isobutanol (1
8), 2-butanol (33.6), tert-butanol, n-amyl alcohol (10.5), tert-
Alcohols such as amyl alcohol (23), furfuryl alcohol, tetrahydrofurfuryl alcohol,
Ethers such as 1,4-dioxane, tetrahydrofuran, tetrahydropyran, acetone, methyl ethyl ketone (12.5, 20 ° C.), ketones such as acetonitrile acetone, diacetone alcohol, and ethyl formate (1
7), propyl formate (17), esters such as methyl lactate and ethyl lactate, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol diethyl ether (1
8), glycols such as ethylene glycol monobutyl ether, diethylene glycol, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and propylene glycol, or glycol ethers. When selecting, it is necessary to consider that the compound is inert to alkalis and other reactants under the actual reaction conditions.

In the present invention, the starting halohydrin ether compound needs to be reacted with an alkali in a state of being dissolved in a hydrophilic organic solvent, but actually, it depends on the type of the halohydrin ether compound. An appropriate one is selected from the hydrophilic organic solvents exemplified above. In order to carry out the reaction in a homogeneous liquid phase, it is preferable to use a hydrophilic organic solvent in an amount that completely dissolves the water present in the reaction system.However, if the amount is too large, the energy required for solvent recovery is increased, The possibility of side reactions such as polymerization, solvation, and hydration increases due to the heat history. Usually, 10 of halohydrin ether compounds
An amount of up to 5 times by weight, preferably up to 5 times by weight, of the hydrophilic organic solvent is used. Even if the amount of the hydrophilic organic solvent used is reduced, it is necessary to use an amount of the hydrophilic organic solvent that dissolves 30% or more of the water present in the reaction system. That is, the properties of the by-product alkali halide are determined by the amount of water that does not dissolve in the hydrophilic organic solvent. If the amount of water is large, the filterability is poor and the viscosity is high.

The type of alkali used in the reaction is not particularly limited, and is selected from conventional ones. Specific examples include sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, potassium carbonate and the like. These alkalis can be added in the form of an aqueous solution or a solid. The concentration of the aqueous alkali solution is usually 10% by weight or more, preferably 20 to 60% by weight.
Is selected. That is, if the concentration is too low, the productivity decreases due to an increase in the amount of the hydrophilic solvent used, and not only does the energy required for solvent recovery increase, but also the heat history causes polymerization, solvation, hydration, etc. Problems such as an increase in the possibility of occurrence of a reaction occur, which is not preferable.

The reaction between the halohydrin ether compound and the aqueous alkali solution is carried out at a temperature of 0 to 100 ° C. and 5 to 60 ° C.
It is performed under the condition of 0 minutes. That is, the reaction is carried out under such conditions that the halohydrin ether compound as the raw material, the hydrophilic organic solvent and water, and the glycidyl ether compound as the product maintain a liquid phase, preferably a uniform liquid phase. In addition, a reaction at a high temperature for a long period of time results in an increase in undesired side reaction products.
The reaction is preferably completed at 60 ° C. for 5 to 300 minutes.

The product of the ring closure reaction is composed of a liquid phase containing a glycidyl ether compound and a solid phase alkali halide precipitated therein, and the two can be separated by conventional means such as filtration and centrifugation.

The solid-phase alkali halide by-produced by the ring closure reaction in the method of the present invention has good properties, is extremely easy to separate, and has a greatly reduced amount of the product glycidyl ether compound attached thereto. It can be dissolved in water and discarded without the need for special wastewater treatment.

On the other hand, since the liquid phase from which the solid phase has been separated contains a hydrophilic organic solvent and water in addition to the product glycidyl ether compound, these are removed by conventional means such as distillation.
If necessary, the product glycidyl ether compound can be recovered by further removing a side reaction product.

[0019]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail with reference to embodiments.

Example 1 Preparation of Chlorhydrin Ether Sorbitol 4 was placed in a four-necked flask having an inner volume of 0.5 L.
5.5 g and 0.21 of boron trifluoride etherate catalyst
g of epichlorohydrin and 31.8 g of epichlorohydrin.
The reaction was performed while maintaining the temperature of 70 to 80 ° C. while maintaining the temperature at 70 to 80 ° C., and the same temperature was maintained and aged for 2 hours after the completion of the dropwise addition. 147 g).

Production of Glycidyl Ether The S obtained above was placed in a four-necked flask having an inner volume of 0.5 L.
Add 50 g of or-CHE and 100 g of n-butanol and stir well to prepare a homogeneous solution. To this, 30.7 g of a 50% by weight aqueous NaOH solution was added dropwise over 5 minutes, and after the addition, the mixture was reacted for 60 minutes while maintaining the temperature at 40 to 50 ° C. n-Butanol is 91.8 of water present in the reaction system.
% Was dissolved. The obtained reaction product is a fine solid by-product N
Since it contained aCl, it was filtered off using filter paper (5A). The NaCl was dissolved in water and removed as wastewater in the form of a saturated solution. The COD concentration of the wastewater is 20,000
It was 0 ppm. On the other hand, the filtrate was distilled to remove n-butanol and water, and then the insoluble matter was removed from the residue in the kettle by filtration through celite. The product glycidyl ether of WPE (weight per epoxy group) 175 was 33.9 g. (95.0% yield).

Example 2 Production of Glycidyl Ether In a four-necked flask having an inner volume of 0.5 L, 50 g of Sor-CHE obtained in Example 1 and 33 g of n-butanol were added, and the mixture was sufficiently stirred to prepare a homogeneous solution. To this, 30.7 g of a 50% by weight aqueous NaOH solution was added dropwise over 5 minutes, and after the addition, the mixture was reacted for 60 minutes while maintaining the temperature at 40 to 50 ° C. n-Butanol is used for 30.000% of water present in the reaction system.
3% was dissolved. The obtained reaction product contained fine solid by-product NaCl, which was separated by filtration using filter paper (5A). The NaCl was dissolved in water and removed as wastewater in the form of a saturated solution. The COD concentration of the wastewater is 19,0
It was 00 ppm. On the other hand, the filtrate was distilled to remove n-butanol and water, and then the insoluble matter was removed from the residue in the kettle by filtration through celite to obtain 34.3 g (yield 96.1%) of a product glycidyl ether of WPE178. Was.

Example 3 Preparation of chlorhydrin ether Into a 0.5 L four-necked flask, 60 g of glycerin was added.
And 0.28 g of boron trifluoride etherate catalyst, 211 g of epichlorohydrin was added dropwise over 30 minutes, and the reaction was carried out while maintaining the temperature at 70 to 80 ° C.
After completion of the dropwise addition, the mixture is maintained at the same temperature for 2 hours and aged, and glycerin polychlorohydrin ether (hereinafter referred to as G
271 g).

Preparation of Glycidyl Ether The above obtained G was placed in a four-necked flask having an inner volume of 0.5 L.
100 g of L-CHE and 300 g of isobutanol are added and sufficiently stirred to prepare a homogeneous solution. To this, 50.9 g of a 50% by weight aqueous NaOH solution was added dropwise over 5 minutes, and after the addition, the mixture was reacted for 60 minutes while maintaining a temperature of 40 to 50 ° C. Isobutanol is 100% water present in the reaction system
Was dissolved and the reaction was performed in a homogeneous liquid phase. Since the obtained reaction product contains NaCl by-product in the form of fine solid, filter paper (5
This was filtered off using A). The NaCl was dissolved in water and removed as wastewater in the form of a saturated solution. The COD concentration of the wastewater was 15,000 ppm. On the other hand, the filtrate was distilled to remove isobutanol and water,
Insoluble matter is removed from the residue in the kettle by filtration through Celite,
73.3 g of glycidyl ether of product 142 (yield 10
0%).

Example 4 Production of Glycidyl Ether In a four-necked flask having an inner volume of 0.5 L, 100 g of GL-CHE obtained in Example 3 and 100 g of isobutanol are put, and sufficiently stirred to prepare a homogeneous solution. In addition, 50
50.9 g of a weight% NaOH aqueous solution was added dropwise over 5 minutes,
After the dropwise addition, the reaction was carried out for 60 minutes while maintaining the temperature at 40 to 50 ° C. Isobutanol is used for the water 4 present in the reaction system.
4.4% were dissolved. The obtained reaction product contained fine solid by-product NaCl, which was separated by filtration using filter paper (5A). The NaCl was dissolved in water and removed as wastewater in the form of a saturated solution. The COD concentration of the wastewater is 1
It was 6,000 ppm. On the other hand, the filtrate was distilled to remove isobutanol and water, and then insolubles were removed from the residue in the kettle by filtration through celite to obtain 73.4 g (yield 100%) of a product glycidyl ether of WPE141.

Example 5 Preparation of Chlorhydrin Ether 50 g of glycerin was placed in a 0.5 L four-necked flask.
And 0.22 g of boron trifluoride etherate catalyst were added thereto, and 175.8 g of epichlorohydrin was added dropwise over 30 minutes, and the reaction was carried out while maintaining the temperature at 70 to 80 ° C. The temperature was maintained and aged to obtain 225.8 g of GL-CHE.

Preparation of Glycidyl Ether The above obtained G was placed in a four-necked flask having an inner volume of 0.5 L.
100 g of L-CHE and 100 g of n-propanol are added and sufficiently stirred to prepare a homogeneous solution. To this, 50.96 g of a 48% by weight aqueous NaOH solution was added dropwise over 5 minutes,
After the dropwise addition, the reaction was carried out for 60 minutes while maintaining the temperature at 40 to 50 ° C. n-Propanol is one of the water present in the reaction system.
00% was dissolved and the reaction was performed in a homogeneous liquid phase. The obtained reaction product contained fine solid by-product NaCl, which was separated by filtration using filter paper (5A). The NaCl was dissolved in water and removed as wastewater in the form of a saturated solution. In addition, the COD concentration of the wastewater was 13,000 ppm. On the other hand, the filtrate was distilled to remove n-propanol and water, and then the insoluble matter was removed from the residue in the kettle by filtration through celite, and 73.3 g of a glycidyl ether product of WPE141 was obtained.
(99.6% yield).

Example 6 Preparation of Chlorhydrin Ether Sorbitol 35 was placed in a four-necked flask having an inner volume of 0.5 L.
g, glycerin 35 g and boron trifluoride etherate catalyst 0.06 g, and epichlorohydrin 17
6.0 g was added dropwise over 30 minutes, and the reaction was carried out while maintaining the temperature at 70 to 80 ° C. After the completion of the dropwise addition, the mixture was kept at the same temperature for 2 hours and aged. Mixture of phosphorus ethers (hereinafter abbreviated as Sor / GL-CHE)
246.0 g were obtained.

Production of Glycidyl Ether The S obtained above was placed in a four-necked flask having an inner volume of 0.5 L.
or / GL-CHE 50 g and 2-butanol 150 g
And stir well to prepare a homogeneous solution. In addition, 5
26.0 g of a 0 wt% NaOH aqueous solution was added dropwise over 5 minutes, and after the addition, the mixture was reacted for 60 minutes while maintaining the temperature at 40 to 50 ° C. 2-Butanol dissolved 100% of the water present in the reaction system, and the reaction was performed in a homogeneous liquid phase. The obtained reaction product contained fine solid by-product NaCl, which was separated by filtration using filter paper (5A). This NaCl is
Dissolved in water and removed as wastewater in the form of a saturated solution. In addition,
The COD concentration of the wastewater was 20,000 ppm. On the other hand, the filtrate was distilled to distill off 2-butanol and water.
34.0 g (yield 95.3%) of a product glycidyl ether of WPE148 was obtained.

Comparative Example 1 Production of Glycidyl Ether In a four-necked flask having an inner volume of 0.5 L, 50 g of the Sor-CHE obtained in Example 1 and 50 g of n-butanol were added, and the mixture was sufficiently stirred to prepare a homogeneous solution. To this, 70.9 g of a 20 wt% NaOH aqueous solution was added dropwise over 5 minutes, and after the addition, the mixture was reacted for 60 minutes while maintaining the temperature at 40 to 50 ° C. n-Butanol is used for the water present in the reaction system.
1% was dissolved. Since the obtained reaction product contains NaCl as a by-product in the form of fine solid, 10.8 g of water was added to dissolve the solution, and then the solution was transferred to a separating funnel and allowed to stand for 30 minutes.
112.2 g of a saturated aqueous solution was collected and removed as wastewater. The COD concentration of the wastewater is 230,000 ppm
Met. On the other hand, the liquid in the upper layer was distilled to remove n-butanol and water, and then the insoluble matter was removed from the bottom liquid by filtration with a filter paper (5A) to obtain 20.5 g of glycidyl ether (a product of WPE176, yield 57. 3%).

Comparative Example 2 Production of Glycidyl Ether A GL-CHE (50 g) obtained in Example 2 and n-butanol (50 g) were placed in a four-necked flask having an inner volume of 0.5 L, and sufficiently stirred to prepare a homogeneous solution. To this, 76.0 g of a 20 wt% NaOH aqueous solution was added dropwise over 5 minutes, and after the addition, the mixture was reacted for 60 minutes while maintaining the temperature at 40 to 50 ° C. n-Butanol is 14.9 of water present in the reaction system.
% Was dissolved. The obtained reaction product is a fine solid by-product N
Since it contains aCl, 20.0 g of water was added to dissolve it, then it was transferred to a separating funnel and allowed to stand for 30 minutes, and the lower NaCl
111.4 g of a saturated aqueous solution was collected and removed as wastewater. The COD concentration of the wastewater was 50,000 ppm. On the other hand, the liquid in the upper layer was distilled to remove n-butanol and water, and then the insoluble matter was removed from the bottom liquid by filtration with a filter paper (5A), and 36.9 g of a glycidyl ether product of WPE143 (yield 94. 5%).

Comparative Example 3 Production of Glycidyl Ether In a four-necked flask having an inner volume of 0.5 L, 50 g of Sor / GL-CHE obtained in Example 4 and 50 g of n-butanol were added.
g and stir well to prepare a homogeneous solution. to this,
59.5 g of a 20 wt% NaOH aqueous solution was added dropwise over 5 minutes, and after the addition, the mixture was reacted for 60 minutes while maintaining the temperature at 40 to 50 ° C. n-Butanol dissolved 18.7% of the water present in the reaction system. Since the obtained reaction product contains NaCl as a by-product in the form of fine solid, 10.0 g of water was added to dissolve the solution, and then the solution was transferred to a separating funnel and allowed to stand for 30 minutes.
90.8 g of aCl saturated aqueous solution was separated and removed as waste water. The COD concentration of the wastewater is 100,000 pp
m. On the other hand, the filtrate was distilled to remove n-butanol and water, and then insoluble matter was removed from the residue in the kettle by filtration with celite to obtain 33.2 g (yield 95.0%) of a product glycidyl ether of WPE149. Was.

[0033]

According to the present invention, the desired product can be obtained in a high yield without deteriorating the product quality.
A method for producing a glycidyl ether compound capable of reducing the D concentration is achieved.

 ────────────────────────────────────────────────── ─── Continuing on the front page (72) Inventor Koji Mase 710, Rokomi, Yokkaichi-shi, Mie F-term (reference) 4C048 BB09 CC01 CC02 CC03 XX02

Claims (5)

[Claims] (1) The following general formula (1): [In the above general formula, R is a polyhydric alcohol residue, X is a halogen atom, and n is an integer of 1 or more. Is reacted with an alkali in a state of being dissolved in a hydrophilic organic solvent, and then a solid-phase alkali halide is separated from the reaction product.
A method for producing a glycidyl ether compound, comprising recovering a glycidyl ether compound from a liquid phase. 2. The method for producing a glycidyl ether compound according to claim 1, wherein the hydrophilic organic solvent is a compound that dissolves at least 10% by weight of water at 25 ° C. or a mixture containing the compound. 3. An alkali having a concentration of 10% by weight.
The method for producing a glycidyl ether compound according to claim 1 or 2, wherein the glycidyl ether compound is added in the form of the above aqueous solution or solid. 4. The process for producing a glycidyl ether compound according to claim 1, wherein the reaction is carried out in a homogeneous liquid phase. 5. The process for producing a glycidyl ether compound according to claim 1, wherein a hydrophilic organic solvent is used in an amount that dissolves at least 30% of water present in the reaction system.