JP2002293755A - METHOD FOR PRODUCING beta-ALKYLHALOHYDRIN ETHER - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a β-alkylchlorohydrin ether and an alkylglycidyl ether in high yield at low cost. SOLUTION: The objective method for producing a β-alkylhalohydrin ether comprises reaction between an alcohol and an α-epihalohydrin in theipresence of an acid catalyst, wherein the acid catalyst is characterized by being a mixture of a Lewis acid and a Brϕnsted acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing a β-alkylhalohydrin ether using a mixed catalyst of a Lewis acid and a Bronsted acid. In addition, the present invention relates to a method for producing an alkyl glycidyl ether in which the obtained β-alkylhalohydrin ether is brought into contact with an alkali.

[0002]

2. Description of the Related Art Hitherto, glycidyl ether has been produced roughly by one of the following two methods. (1) A method for producing a corresponding glycidyl ether by reacting an alcohol, α-epihalohydrin and an alkali in a single step in the presence of a phase transfer catalyst such as a quaternary ammonium salt. (2) A method for producing a corresponding glycidyl ether by reacting an alcohol with α-epihalohydrin in the presence of an acid catalyst to obtain a β-alkylhalohydrin ether, followed by a further ring closure reaction with an alkali.

[0003]

However, (1)
In the method (1), it is necessary to use a large excess of α-epihalohydrin in order to suppress a reaction in which alcohols are further added to the produced glycidyl ether. In addition, since alkali and α-epihalohydrin coexist, if water is present in the reaction system, there is a disadvantage that hydrolysis of α-epihalohydrin cannot be avoided. In the method (2), when the acid catalyst is a Bronsted acid such as sulfuric acid, not only the conversion of α-epihalohydrin is low, but also there are many impurities such as dialkyl ethers obtained by dehydrating alcohols, and β-alkylhalohydrides. Phosphorous ether cannot be obtained in high yield.

In the case of Lewis acid catalysts such as boron trifluoride and tin tetrachloride, if water is present in the system, the catalyst is deactivated by hydrolysis, so that the presence of water must be eliminated as much as possible. When water is removed, the conversion of α-epihalohydrin is high, but α-epihalohydrin is α-cleavage-added to the alcohol and α-alkylhalohydrin ether is often produced as a by-product. This α-alkylhalohydrin ether further reacts with α-epihalohydrin to produce a high boiling point addition product. If the reaction mixture contains an α-alkylhalohydrin ether, it will not be converted into an alkyl glycidyl ether during the next ring closure reaction with an alkali, but will remain as an impurity. Alkyl glycidyl ethers are used as epoxy resin diluents, so that those having a large amount of α-alkyl halohydrin ether remaining therefrom have the disadvantage that they are not used for applications such as electronic parts. Under such circumstances, the present applicant has found and applied for a method for producing glycidyl ether using activated clay as a catalyst (Japanese Patent Application No. 5-303266). However, even with this method, impurities such as α-alkylhalohydrin ether were used. Therefore, there has been a demand for a method for producing an alkyl glycidyl ether at a low cost and a high yield.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies in order to solve these problems of the prior art, and as a result, in the reaction between alcohols and α-epihalohydrin, Lewis acid and Bronsted were used. It has been found that if a mixture of an acid and an acid is used as a catalyst, β-alkylhalohydrin ether can be obtained in high yield with little by-products such as α-alkylhalohydrin ether.

[0006] That is, the present invention relates to alcohols and α-
Reacting with epihalohydrin in the presence of an acid catalyst,
The method for producing a β-alkylhalohydrin ether according to the present invention is characterized in that the acid catalyst is a mixture of a Lewis acid and a Bronsted acid. Another object of the present invention is to provide a method for producing an alkyl glycidyl ether in which a β-alkylhalohydrin ether obtained by this reaction is brought into contact with an alkali to cause a ring-closing reaction.

[0007]

BEST MODE FOR CARRYING OUT THE INVENTION Acid Catalyst The acid catalyst used in the present invention must be a mixture of a Lewis acid and a Bronsted acid, and the molar ratio is expressed as Lewis acid / Bronsted acid. 0.1 ~
It is important to be within the range of 20 and preferably within the range of 0.3 to 5. That is, when the molar ratio is 0.1
If it is less than 3, the catalytic activity decreases and impurities increase. Conversely, if it exceeds 20, the catalytic activity decreases, which is not preferable.

The Lewis acid used in the present invention includes zinc chloride, ferric chloride, aluminum chloride, tin tetrachloride, tin dichloride, boron trifluoride, antimony pentachloride and the like. These Lewis acids may be used alone or in combination of several kinds. Among them, preferred are at least one selected from the group consisting of zinc chloride, ferric chloride and aluminum chloride, which have advantages of high catalytic activity and rapid reaction. Ferric chloride and tin tetrachloride may be anhydrous or hydrated. Even if a small amount of water is present in the reaction system of the present invention, selectivity,
Does not affect yield.

The Brönsted acid used in the present invention includes sulfuric acid, phosphoric acid, phosphorous acid, 1-hydroxyethane-1,
1-diphosphonic acid and the like. Further, sulfonic acids such as benzenesulfonic acid, paratoluenesulfonic acid, and phenolsulfonic acid may be used. These Bronsted acids may be used in combination of several kinds. Among them, preferred is at least one selected from the group consisting of sulfuric acid, phosphoric acid, phosphorous acid and 1-hydroxyethane-1,1-diphosphonic acid, which have high catalytic activity and perform the reaction promptly. There are advantages that can be.

Alcohols The alcohols used in the present invention include, for example, the following general formula (1) R ^1- (OR ² ) _P -OH (1) wherein R ¹ is a total of 1 to 36 carbon atoms. Represents a saturated or unsaturated, linear or branched hydrocarbon group, R ² represents an alkylene group having 2 to 4 carbon atoms, and P represents a number of 0 to 100. ] Are represented. Specifically, methanol, ethanol, propanol, butanol, pentanol, hexanol, heptanol, octanol, nonanol, decanol, undecanol,
In addition to aliphatic saturated alcohols such as dodecanol, tridecanol, tetradecanol, pentadecanol, hexadecanol, heptadecanol, octadecanol, nonadecanol, eicosadecanol, 2-ethylhexanol and 3,5-dimethylhexanol And aliphatic unsaturated alcohols such as allyl alcohol, oleyl alcohol, and linole alcohol, and alkylene oxide adducts thereof. As the alkylene oxide adduct, an ethylene oxide adduct (general formula (1)
In formula (1), R ² is ethylene, a propylene oxide adduct (when R ² is a propylene group in the general formula (1)), and a butylene oxide adduct (when R ² is a butylene group in the general formula (1)). Can be As the alcohols, those having no alkylene oxide added thereto (when P = 0 in the general formula (1)) are preferably primary alcohols. Among the alkylene oxide adducts, ethylene oxide adducts are preferable, and the number of moles P of addition is preferably from 1 to 20.

[0011] As the alpha-epihalohydrin used in the present invention alpha-epihalohydrin, alpha-epichlorohydrin, alpha-epibromohydrin, alpha-but epi-iodo epichlorohydrin, and the like, epichlorohydrin is preferred. In the reaction for producing a β-alkylhalohydrin ether from an alcohol and α-epihalohydrin, the alcohol is used in an amount of 0.7 to 5.0 mole times, preferably 1.0 to 3 times, the amount of α-epihalohydrin relative to α-epihalohydrin. .
It is used in an amount of 0 mole times. The Lewis acid is used in an amount of 0.0005 to 0.1 mol times, preferably 0.1 mol, per mol of the alcohol.
It is preferred to use a molar amount of 0.0001 to 0.05 times, and the Brönsted acid is used in an amount of 0.0005 to 0.5 to the alcohol.
It is preferable to use a molar amount of 05 times, preferably 0.001 to 0.03 times. The reaction temperature is 0 to 180 ° C, preferably 50 to 130 ° C, and the reaction time is 0.5 to 5 ° C.
Time is preferred.

Production of Alkyl Glycidyl Ether To produce an alkyl glycidyl ether from the β-alkyl halohydrin ether obtained by the above reaction, the β-alkyl halohydrin ether is removed by contacting the β-alkyl halohydrin ether with an alkali according to a conventional method. The ring may be closed by a hydrogen halide reaction. It is not necessary to remove the acid catalyst from the reaction mixture before adding the alkali. However, unreacted alcohols can be removed at normal pressure or reduced pressure from the viewpoint of reuse and ease of separation (recovery). It is preferable to recover by means such as distillation. Examples of the alkali used here include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkaline earth metal hydroxides such as calcium hydroxide and barium hydroxide. Potassium oxide is preferred. Further, in the dehydrohalogenation reaction of β-alkylhalohydrin ether, 1.0 to 1.0
It is preferable to use 2.0 mole times, particularly 1.1 to 1.5 mole times of alkali. The form of the alkali to be contacted may be a solid or a liquid.
It is preferably added as a 0-48% aqueous solution. Also,
The reaction temperature is preferably 30 to 120 ° C, and the reaction is preferably performed for 2 to 5 hours. When the use amount of the alkali exceeds the above range, or when the dehydrohalogenation reaction is performed at a temperature exceeding 120 ° C., the generated alkyl glycidyl ether is hydrolyzed to alkyl glyceryl ether, which may greatly reduce the yield. is there. On the other hand, when the amount of the alkali used is less than the above range or less than 30 ° C., the progress of the dehydrohalogenation reaction is unfavorably slow. After completion of the reaction, usually, the aqueous layer and the organic layer are separated by standing, and the separated organic layer is distilled to obtain a product glycidyl ether. Depending on the required purity of the product, the product can be obtained without distillation of the separated organic layer.

[0013]

The present invention will be described below with reference to examples. [Example 1] 1 contained in a 300 ml four-necked flask
-Butanol 74.1 g (1.0 mol), zinc chloride 0.39 g (0.0029 mol) and sulfuric acid 0.10 g
(0.001 mol) was heated to 100 ° C. while stirring under a nitrogen atmosphere. Next, 46.3 g (0.5 mol) of epichlorohydrin was added dropwise over 0.5 hour, and the mixture was stirred for 3 hours. During this time, the reaction temperature was 110 ±
Maintained at 5 ° C. Conversion rate of raw material epichlorohydrin 98
%, Generated β-butylchlorohydrin ether is 9%
5.7% by weight, 1.0% by weight of by-product α-butylchlorohydrin ether, and 1.6% by weight of high-boiling by-product. After recovering excess 1-butanol from the reaction mixture under reduced pressure, 110 g of a 20% by weight aqueous sodium hydroxide solution was added, and the mixture was stirred at 70 ° C. for 2 hours. After cooling to room temperature, the aqueous layer was removed and the residue was purified by distillation under reduced pressure to obtain 61.8 g of butyl glycidyl ether (yield 95.0).
%).

Example 2 74.1 g (1.0 mol) of 1-butanol contained in a 300 ml four-necked flask
l), 0.38 g of ferric chloride hexahydrate (0.0014
mol) and sulfuric acid 0.30 g (0.003 mol)
The temperature was raised to 80 ° C. while stirring under a nitrogen atmosphere. Next, 46.3 g of epichlorohydrin (0.5 mol
l) was added dropwise over 0.5 hours and stirred for 3 hours. During this time, the reaction temperature was kept at 90 ± 5 ° C. The conversion of the raw material epichlorohydrin was 97%, the produced β-butylchlorohydrin ether was 94.8% by weight, the by-product α-butylchlorohydrin ether was 1.7% by weight, and the high-boiling by-product was 2%. 0.0% by weight. After recovering excess 1-butanol from the reaction mixture under reduced pressure, 110 g of a 20% by weight aqueous sodium hydroxide solution was added, and the mixture was stirred at 70 ° C. for 2 hours. After cooling to room temperature, the aqueous layer was removed and the residue was purified by distillation under reduced pressure to obtain 61.4 g of butyl glycidyl ether (yield 94.3%).

Example 3 116.2 g (2.0 mol) of allyl alcohol contained in a 300 ml four-necked flask
l), 0.6 g of aluminum chloride (0.0045 mo)
l) and 0.20 g (0.002 mol) of sulfuric acid were heated to 80 ° C. while stirring under a nitrogen atmosphere.
Next, 74.0 g (0.8 mol) of epichlorohydrin
Was added dropwise over 0.5 hour and stirred for 3 hours. During this time,
The reaction temperature was kept at 90 ± 5 ° C. The conversion of the raw material epichlorohydrin was 99%, the generated β-allylchlorohydrin ether was 95.2% by weight, the by-product α-allylchlorohydrin ether was 1.3% by weight, and the high-boiling by-product was 2%. .
It was 3% by weight. After recovering excess allyl alcohol from the reaction mixture under reduced pressure, 176.0 g of a 20% by weight aqueous sodium hydroxide solution was added, and the mixture was heated at 70 ° C. for 2 hours.
Stirred for hours. After cooling to room temperature, the aqueous layer was removed and the residue was purified by distillation under reduced pressure to obtain 85.9 g of allyl glycidyl ether (yield 94.1%).

Example 4 74.2 g (1.0 mol) of 1-butanol contained in a 300 ml four-necked flask
l), 0.39 g (0.003 mol) of anhydrous ferric chloride
And 1-hydroxyethane-1,1-diphosphonic acid 60
0.10 g (0.001 mol) of a 0.1% aqueous solution (trade name: manufactured by Yokkaichi Gosei Co., Ltd .: Ferriox 115) was heated to 100 ° C. while stirring under a nitrogen atmosphere.
Next, 46.3 g (0.5 mol) of epichlorohydrin
Was added dropwise over 0.5 hour and stirred for 3 hours. During this time,
The reaction temperature was kept at 110 ± 5 ° C. The conversion of the raw material epichlorohydrin is 96%, the generated β-butylchlorohydrin ether is 94.9% by weight, the by-product α-butylchlorohydrin ether is 1.0% by weight, and the high-boiling by-product is It was 1.6% by weight. After recovering excess 1-butanol from the reaction mixture under reduced pressure, 110 g of a 20% by weight aqueous sodium hydroxide solution was added, and the mixture was stirred at 70 ° C. for 2 hours. After cooling to room temperature, the aqueous layer was removed and purified by distillation under reduced pressure to obtain 60.5 g of butyl glycidyl ether (yield 93.0%).

Comparative Example 1 74.2 g (1.0 mol) of 1-butanol contained in a 300 ml four-necked flask.
And 0.40 g (0.003 mol) of aluminum chloride
Was heated to 100 ° C. while stirring under a nitrogen atmosphere. Next, 46.3 g of epichlorohydrin (0.
5 mol) was added dropwise over 0.5 hour, and the mixture was stirred for 3 hours. During this time, the reaction temperature was kept at 110 ± 5 ° C. The conversion of the raw material epichlorohydrin was 11%, and the generated β-butylchlorohydrin ether was 6% by weight. The dehydrohalogenation reaction with alkali could not be performed.

Comparative Example 2 116.2 g (2.0 mol) of allyl alcohol contained in a 300 ml four-necked flask
l) and 0.6 g of anhydrous tin tetrachloride (0.0023 mol)
l) was heated to 100 ° C. while stirring under a nitrogen atmosphere. Next, 74.0 g of epichlorohydrin
(0.8 mol) was added dropwise over 0.5 hours, and the mixture was stirred for 3 hours. During this time, the reaction temperature was kept at 100 ± 5 ° C. 100% conversion of raw material epichlorohydrin, β-
Allyl chlorohydrin ether was 84.3% by weight, by-product α-allyl chlorohydrin ether was 3.5% by weight, and high-boiling by-products were 5.2% by weight. After recovering excess allyl alcohol from the reaction mixture under reduced pressure, a 20% by weight aqueous sodium hydroxide solution was added to the reaction mixture.
6.0 g was added, and the mixture was stirred at 70 ° C. for 2 hours. After cooling to room temperature, the aqueous layer was removed and the residue was purified by distillation under reduced pressure to obtain 74.0 g of allyl glycidyl ether (yield: 81.0%).

Comparative Example 3 74.1 g (1.0 mol) of 1-butanol contained in a 300 ml four-necked flask.
And 0.2 g of activated clay was heated to 90 ° C. while stirring under a nitrogen atmosphere. Next, 46.2 g (0.5 mol) of epichlorohydrin was added dropwise over 0.5 hours, and the mixture was stirred for 3 hours. During this time, the reaction temperature is 90 ± 5 ° C
Kept. The conversion of the raw material epichlorohydrin is 98%, the generated β-butyl chlorohydrin ether is 87.8% by weight, the by-product α-butyl chlorohydrin ether is 6.5% by weight, and the high boiling by-product is 5%. 0.4% by weight.
After recovering excess 1-butanol from the reaction mixture under reduced pressure, 110 g of a 20% by weight aqueous sodium hydroxide solution was added, and the mixture was stirred at 70 ° C. for 2 hours. After cooling to room temperature, the aqueous layer was removed and the residue was purified by distillation under reduced pressure to obtain 56.6 g of butyl glycidyl ether (yield: 87.1%).

Comparative Example 4 74.2 g (1.0 mol) of 1-butanol contained in a 300 ml four-necked flask.
And ferric chloride hexahydrate 0.39g (0.003mo
l) was heated to 100 ° C. while stirring under a nitrogen atmosphere. Next, 46.2 g of epichlorohydrin
(0.5 mol) was added dropwise over 0.5 hour, and the mixture was stirred for 3 hours. During this time, the reaction temperature was kept at 110 ± 5 ° C. Conversion of raw material epichlorohydrin 7.4%, generated β-
Butyl chlorohydrin ether was 4.6% by weight.

Comparative Example 5 116.2 g (2.0 mol) of allyl alcohol contained in a 300 ml four-necked flask
l) and 0.6 g (0.006 mol) of sulfuric acid were heated to 90 ° C. while stirring under a nitrogen atmosphere. Next, 46.2 g (0.5 mol) of epichlorohydrin was added dropwise over 0.5 hours, and the mixture was stirred for 3 hours. During this time, the reaction temperature was kept at 100 ± 5 ° C. The conversion of the raw material epichlorohydrin was 49%, the generated β-allylchlorohydrin ether was 20.7% by weight, the by-product α-allylchlorohydrin ether was 1.3% by weight, and the high-boiling by-product was 2% by weight. .
0% by weight and 7.3% by weight of diallyl ether.

Examples 1 to 4 show that a product can be obtained in high yield by using a catalyst in which the Lewis acid and Bronsted acid of the present invention are mixed. From Example 2 and Comparative Example 4, and from Example 3 and Comparative Example 1, it can be seen that when the reaction is carried out using only a Lewis acid as a catalyst (no Bronsted acid is present), the reaction hardly proceeds.
From Comparative Example 5, it can be seen that when only Bronsted acid (sulfuric acid) was used as the catalyst, the desired reaction proceeded slowly and many side reactions occurred. In addition, Comparative Examples 2 and 3 show that only the Lewis acid catalyst having strong catalytic activity generates a large amount of by-products and the yield is low.

[0023]

According to the method of the present invention, β-ephalohydrin is produced from alcohols and α-epihalohydrin in extremely high yield.
An alkyl chlorohydrin ether is obtained, and an alkyl glycidyl ether can be produced at a high yield at a low cost by a dehydrohalogenation reaction with an alkali.

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Claims (5)

[Claims] 1. A process for producing a β-alkylhalohydrin ether in which an alcohol is reacted with α-epihalohydrin in the presence of an acid catalyst, wherein the acid catalyst is a mixture of a Lewis acid and a Bronsted acid. A method for producing a β-alkylhalohydrin ether. 2. The process for producing a β-alkylhalohydrin ether according to claim 1, wherein the molar ratio of the mixture (Lewis acid / Bronsted acid) is 0.1 to 20. 3. The β-alkylhalohydrin ether according to claim 1, wherein the Lewis acid is at least one selected from the group consisting of zinc chloride, ferric chloride and aluminum chloride. Manufacturing method. 4. The method according to claim 1, wherein the Bronsted acid is at least one selected from the group consisting of sulfuric acid, phosphoric acid, phosphorous acid and 1-hydroxyethane-1,1-diphosphonic acid. A method for producing the described β-alkylhalohydrin ether. 5. A β-alkylhalohydrin ether obtained by the method according to any one of claims 1 to 4,
A method for producing an alkyl glycidyl ether, which comprises bringing a ring closure reaction into contact with an alkali.