JP2933450B2 - Method for producing epoxide - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a method for producing epoxides.

[0002]

2. Description of the Related Art Epoxides represented by propylene oxide (hereinafter abbreviated as PO) and epichlorohydrin are useful compounds as basic raw materials for resins and adhesives. As the production method, a method of reacting a base with an aqueous solution of chlorhydrin obtained by reacting olefin with chlorine water is mainly used. In the reaction (hereinafter, abbreviated as "saponification reaction") for reacting a base with an aqueous solution of chlorhydrin in the above-mentioned production method, epoxide, which is a target substance, reacts with water to produce diol as a by-product. For example, if epoxide is PO
In the case of, propylene glycol (hereinafter abbreviated as PG)
Is by-produced by several percent.

[0003] These diols not only reduce the yield of epoxide, which is the target product in the saponification reaction, but also require considerable labor for disposal of the diol itself. That is, since the diol has high water solubility, it has to be dissolved in the aqueous solvent of the saponification reaction, and it is necessary to detoxify the diol by a method such as activated sludge treatment when disposing the aqueous solvent.

[0004]

Therefore, development of a method for suppressing diol by-products in the saponification reaction has been desired.

[0005]

Means for Solving the Problems The inventor of the present invention has intensively studied to solve the above problems. as a result,
By reacting chlorohydrin with calcium oxide and / or calcium hydroxide in the presence of an organic solvent capable of dissolving the co-produced calcium chloride, it has been found that epoxide can be produced by suppressing the by-product of diol, The present invention has been proposed.

That is, the present invention provides a method for producing epoxide by reacting chlorohydrin with calcium oxide and / or calcium hydroxide in a solvent.
As a solvent, water- containing that can dissolve the co-produced calcium chloride
An epoxide production method characterized by using an organic solvent in an amount of 40% by weight or less .

In the present invention, known compounds can be used without any limitation as long as chlorohydrin has a chlorine atom on one of two adjacent carbon atoms in the molecule and a hydroxyl group on the other. Specific examples of chlorohydrin that can be suitably used in the present invention include, for example, ethylene chlorohydrin, propylene chlorohydrin, butylene chlorohydrin, 2-phenyl-2-chloroethanol and the like.

[0008] Chlorhydrin as a raw material in the present invention may be produced by any method. For example, a method of distilling from an aqueous solution of chlorhydrin obtained by reacting an olefin with chlorine water is preferably used.

In the present invention, it is necessary to use an organic solvent capable of dissolving calcium chloride produced together with the epoxide. Chlorhydrin and calcium oxide and / or
Alternatively, in the reaction with calcium hydroxide, calcium chloride is produced together with the desired epoxide. When an organic solvent having a low solubility of calcium chloride is used, in a saponification reaction that proceeds on the solid surface of calcium oxide and / or calcium hydroxide, the generated calcium chloride does not dissolve in the organic solvent and the calcium oxide and / or water does not dissolve. Covers the surface of calcium oxide. As a result, the saponification reaction is substantially stopped. Therefore, in the present invention, it is necessary to use an organic solvent that can dissolve calcium chloride. Although the solubility of calcium chloride depends on the concentration of the reaction substrate in the organic solvent, it is preferably at least 1 g / 100 g at room temperature, particularly preferably at least 5 g / 100 g in order to perform the saponification reaction smoothly. More preferred.

Specific examples of the organic solvent that can be suitably used in the present invention include monohydric alcohols such as methanol and ethanol; and dihydric alcohols such as ethylene glycol and propylene glycol.

The amount of the above-mentioned organic solvent is not particularly limited, but in order for the reaction of the present invention to proceed satisfactorily, the calcium chloride concentration in the organic solvent should be within the range of the saturation solubility at the reaction temperature or lower. Is preferred. Usually, the concentration of chlorhydrin and calcium oxide and / or calcium hydroxide in an organic solvent is 1 to 60 g.
/ 100 g is preferably used.

In the present invention, the organic solvent is
About water. Vice Namaryo of Jio <br/> le by the inclusion of water increases, but conversion of chlorohydrin is directed
Up . Therefore, within the allowable range of the by-product diol amount, it is possible to improve the conversion of chlorohydrin by Rukoto the organic solvent in the presence of water. Tolerance
The content of water to be obtained may be determined in consideration of the conversion rate of chlorohydrin and the amount of diol by-products .
0 to 40% by weight.

As the reaction conditions, the same conditions as in the conventional reaction using water as a solvent can be employed. Specifically, the reaction ratio of chlorhydrin to calcium oxide and / or calcium hydroxide is such that calcium oxide and / or calcium hydroxide is 0.1 mol per mol of chlorhydrin.
It is preferable to use it in the range of 10 to 10 mol. The reaction temperature is preferably in the range from room temperature to 200 ° C. The reaction pressure may be any of pressurization, normal pressure, and reduced pressure, but normal pressure or slight pressure is preferable from the viewpoint of facility of the equipment. The reaction may be carried out in any of a flow system, a batch system, and a semi-batch system without any limitation. It is preferable to stir during the reaction.

[0014]

According to the present invention, epoxide is produced by reacting chlorhydrin with calcium oxide and / or calcium hydroxide in an organic solvent capable of dissolving calcium chloride, thereby suppressing diol by-products. be able to.

[0015]

EXAMPLES In order to explain the present invention more specifically,
Hereinafter, the present invention will be described with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples.

Example 1 A mixture of 20 mmol of propylene chlorohydrin, 100 mmol of calcium oxide, and 5 g of methanol (23 g / 100 g of calcium chloride solubility at room temperature) was reacted at 90 ° C. for 30 minutes with stirring. After cooling to room temperature,
As a result of analyzing the reaction solution, PO was produced in a yield of 59%. The amount of PG produced was only 0.00011 by weight relative to the produced PO.

Example 2 A mixture of 20 mmol of propylene chlorohydrin, 100 mmol of calcium oxide, and 5 g of ethanol (solubility of calcium chloride at room temperature: 20 g / 100 g) was reacted at 90 ° C. for 30 minutes with stirring. After cooling to room temperature,
As a result of analyzing the reaction solution, PO was produced in a yield of 40%. The amount of PG produced was only 0.00009 by weight relative to the produced PO.

EXAMPLE 3 A mixture of 20 mmol of propylene chlorohydrin, 10 mmol of calcium oxide and 5 g of ethylene glycol (solubility of calcium chloride at room temperature 21 g / 100 g)
Heat at 90 ° C. for 30 minutes with stirring. After cooling to room temperature, the reaction solution was analyzed, and as a result, PO was produced in a yield of 40%. The amount of PG produced was only 0.00010 by weight relative to the produced PO.

Examples 4 to 6 20 mmol of propylene chlorohydrin, 10 mmol of calcium oxide, 5 g of methanol and the amount of water shown in Table 1 (in the first column of Table 1, methanol contained in a mixed solvent of methanol and water) The mixture was heated at 75 ° C. with stirring for 30 minutes. Table 1 shows the yield of produced PO and the weight ratio of PG to PO by-product. Examples using only water as a solvent are also shown in Table 1 as comparative examples.

[0020]

[Table 1]

Claims (1)

(57) [Claims] (1) Chlorhydrin and calcium oxide and / or
Alternatively, in a method of producing epoxide by reacting with calcium hydroxide in a solvent, an organic solvent having a water content of 40% by weight or less capable of dissolving co-produced calcium chloride is used as a solvent. Characteristic epoxide manufacturing method.