JPH10212280A - Production of high purity epoxy compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce an epoxy compound having a molecular structure having whole active hydrogen atoms substituted with epoxypropyl groups, as a high purity industrial product from a compound having carboxyl group or amide group in the molecule. SOLUTION: A 2,3-epoxypropyl derivative or a 2-methyl-2,3-epoxypropyl derivative is obtained as a highly pure product by (step A) carrying out an additional reaction of an epihalohydrin or a 2-methylepihalohydrin with a compound having 2-4 carboxyl groups or 1-3 amide groups in the molecule in the presence of a catalyst such as a tertiary amine, etc., (step B) adding an alkali metal hydroxide to the obtained reaction product to prepare a slurry containing an epoxy derivative, (step C) washing the obtained slurry with an aqueous solution containing a purification auxiliary such as sulfonic acid to prepare a purified liquid material containing the epoxy derivative, and (step D) removing the epihalohydrin or 2-methylepihalohydrin by distillation from the obtained purified liquid material.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to an improvement in a method for producing an epoxy compound having a 2,3-epoxypropyl group or a 2-methyl-2,3-epoxypropyl group as a high-purity product. From the compound having 2 to 4 carboxyl groups or the compound having 1 to 3 amide groups in the molecule, all the active hydrogen atoms of the carboxyl group or amide group are 2,3-epoxypropyl group or 2-
2,3-epoxypropyl derivative having a molecular structure substituted with a methyl-2,3-epoxypropyl group or 2-
The present invention relates to a method for efficiently producing a methyl-2,3-epoxypropyl derivative as a high-purity product capable of obtaining a transparent and stable melt when melted.

[0002]

2. Description of the Related Art US Pat. No. 3,859,314 discloses that a polycarboxylic acid and two or more moles of epichlorohydrin per mole of a carboxyl group of the polycarboxylic acid are reacted with a tertiary amine, a tertiary amine salt or a tertiary amine. A quaternary ammonium compound is used as a catalyst to react at a temperature of 150-200 ° F. until the acid value becomes zero, and the resulting chlorohydrin ester is formed at a temperature of 90-130 ° F. and at the reaction temperature. Disclosed is a method for producing a glycidyl ester of a polycarboxylic acid by causing a dehydrohalogenation reaction by gradually adding an alkali metal hydroxide under a reduced pressure sufficient to remove distilled water.

[0003] The specification discloses that a product obtained by subjecting a chlorohydrin ester of isophthalic acid to a dehydrohalogenation reaction is washed with water, and then epichlorohydrin is distilled from the washed product under reduced pressure by distillation. An example is shown in which a diglycidyl isophthalate having an epoxy equivalent of 152 and a total chlorine content of 0.8% was produced by removal. This epoxy equivalent is 1.0 with respect to the theoretical value of 139.
9 times.

[0004] JP-B-44-20323 discloses that a compound having an amide group is reacted in the presence of a phosphonium halide, and then the reaction product is treated with an alkaline compound to obtain an N-form of the compound having an amide group.
A method for producing a glycidyl derivative is disclosed. Examples in the specification describe that the triglycidyl isocyanurate-containing product obtained by the above method is washed with water, an aqueous solution of monosodium phosphate and distilled water, and then the volatiles are removed from the washed material at 110 ° C. under reduced pressure. To give a product of triglycidyl isocyanurate in 89% yield, and the final product obtained by crystallization from a 50% by weight methanol solution of this product is 100% of its The epoxide equivalent is 0.92, contains 1.0% by weight of chlorine, and
This illustrates that the reduction rate of the epoxide equivalent in 100 g when heated for 15 hours was 10%.

Japanese Patent Publication No. 45-22751 discloses that cyanuric acid and epichlorohydrin at a molar ratio of 6 to 30 times the amount of cyanuric acid can be reacted with a tertiary amine, a quaternary ammonium base or a quaternary ammonium salt in the presence of a catalyst. After the reaction at １６165 ° C., a stoichiometric excess of a concentrated aqueous solution of alkali hydroxide of 5-40% is added, and the resulting reaction product is added to water, sodium dihydrogen phosphate. A method is disclosed in which triglycidyl isocyanurate is produced as a product by adding an aqueous solution, a dilute aqueous solution of sodium hydroxide, and the like, washing the mixture by stirring, and finally distilling epichlorohydrin with a rotary evaporator. And the examples show that the product contains 9.49-9.8 moles of oxirane oxygen per kg and contains 0.5-1.1% chlorine.

US Pat. No. 3,198,241 discloses that
A fluid containing volatile and non-volatile substances is caused to flow by gravity on a vertically arranged heat transfer surface, whereby a thin film of the fluid is formed on the heat transfer surface, and the heat exchange fluid A method is disclosed in which volatile substances are repeatedly evaporated from the fluid film by heat transfer to separate and recover non-volatile substances from volatile substances.

[0007] US Pat. No. 4,395,542 includes:
Heating triglycidyl isocyanurate containing 2000 ppm or more of epichlorohydrin and related volatiles to a temperature sufficient to easily flow it but insufficient to cause thermal decomposition, for example, 143-159 ° C;
By passing the heated product under a pressure of 1 to 500 mmHg through a column filled with a fine wire gauze or the like or a multi-stage evaporating stripper under gravity by one or more times, the product is subjected to multi-stage stripping and 10p
A method for producing triglycidyl isocyanurate containing sub-pm amounts of epichlorohydrin and related volatiles is disclosed.

[0008]

The above-mentioned products of the epoxy compound according to the conventional method can be used for ordinary applications such as raw materials for polyester-based paints, but gradually or depending on the application, these epoxy compounds can be used. It is desired to provide compounds as high-purity industrial products. In particular, since these epoxy compounds have been used for encapsulants for semiconductor devices, conductive adhesives, solder resists, etc., polyvalent carboxylic acids or 1-carboxylic acids useful for these applications have been used.
It is desired to provide a 2,3-epoxypropyl derivative or a 2-methyl-2,3-epoxypropyl derivative of a compound having two or more amide groups as an industrial product having high purity. By combining the conventional production method as described above with a known purification method, it is possible to produce a product that satisfies the demand for high purification to some extent. For example, the intermediate product 2,3
An epichlorohydrin solution of an epoxypropyl derivative,
Or 2-methyl-2,3-epoxypropyl derivative 2
Increasing the number of repetitions of water washing of the methyl epichlorohydrin solution or repeating recrystallization of the product 2,3-epoxypropyl derivative or 2-methyl-2,3-epoxypropyl derivative from an alcohol solution such as methanol; Thereby, the purity of the product can be increased.

However, these glycidyl esters, N-glycidyl compounds and the like are generally dissolved in water in a non-negligible amount at the time of washing with water, so that repeated washing of the product as described above results in a decrease in product yield. In addition, the purification method by recrystallization as described above cannot be applied to non-crystalline epoxy compound products. Since it is difficult to remove fine insoluble impurities, it is ultimately difficult to achieve a fundamental purification to obtain a transparent melt by melting.

In the production method described in Japanese Patent Publication No. 45-22751, the last removal of epichlorohydrin is carried out by a rotary evaporator with low efficiency, and the product yield is considerably low. Is disadvantageous for industrial production. Also in the method described in JP-B-44-20323, the last removal of epichlorohydrin is carried out by volatilization under reduced pressure, but the publication does not disclose an evaporation method for increasing the purity of the product. .

The above-mentioned falling film according to the method disclosed in US Pat. No. 3,198,241 is a film formed by flowing down a fluid under its own weight, such as triglycidyl isocyanurate containing epichlorohydrin at a low concentration. With a fluid having a high viscosity, it is difficult to form a thin film in a short time. In the method disclosed in this US patent, it is necessary to increase the number of times a falling film is formed at a high temperature, and it takes not only long time to remove epichlorohydrin but also the product during the long time at this high temperature. Is likely to decrease in purity.

In the above-mentioned method disclosed in US Pat. No. 4,395,542, the fluid flows down by its own weight. Therefore, in the case of a high-viscosity fluid such as triglycidyl isocyanurate containing a low concentration of epichlorohydrin, a thin film is formed under the flow. Is not formed. In the evaporation method by multi-stage stripping, US Pat.
The removal of epichlorohydrin can be completed in a shorter time as compared with the method of evaporating with a falling film described in Japanese Patent No. 41, but when a large-scale apparatus is used, a high molecular weight substance adheres to the inner wall of the stripper. As a result, this may hinder smooth heat transfer or may be mixed as insoluble foreign matter into the product after stripping. In particular, when a product containing such an insoluble foreign matter is used to produce a transparent resin molded product, the transparency of the molded product is reduced, or when a coating film is formed as a coating, the surface of the coating film is reduced. This causes problems such as a decrease in smoothness of the film.

The present invention relates to a compound having 2 to 4 carboxyl groups or 1 to 3 amide groups in a molecule, wherein all the active hydrogen atoms of the carboxyl group or amide group are 2,2.
2,3- having a molecular structure substituted with a 3-epoxypropyl group or a 2-methyl-2,3-epoxypropyl group
An epoxypropyl derivative or a 2-methyl-2,3-epoxypropyl derivative is prepared such that it has a high oxirane oxygen content, a high thermal stability and a low ionic halogen content, and that a transparent melt is obtained by melting. It is intended to provide a method for efficiently producing an industrial product.

[0014]

SUMMARY OF THE INVENTION A 2,3-epoxypropyl derivative of a compound having 2 to 4 carboxyl groups or 1 to 3 amide groups in the molecule of the present invention or 2-methyl-
A method for producing a 2,3-epoxypropyl derivative as a high-purity product includes a compound having 2 to 4 carboxyl groups or 1 to 3 amide groups in the molecule, and active hydrogen of the carboxyl group or amide group of the compound. Epihalohydrin or 2-methyl epihalohydrin in an amount of 1.2 to 60 mol per mol of atom, and tertiary amine, quaternary ammonium base, quaternary ammonium salt, trisubstituted phosphine or quaternary phosphonium salt as a catalyst By reacting the compound with epihalohydrin or 2-methylepihalohydrin in a reaction mixture containing
Or a step (A) of forming a reaction product containing a 2-hydroxy-2-methyl-3-halopropyl derivative, and the reaction product obtained in the step (A) in the reaction product before the above-mentioned reaction. The dehydrohalogenation reaction is performed on the derivative by gradually adding an alkali metal hydroxide in an amount of 1 to 2 mol per 1 mol of the active hydrogen atom of the carboxyl group or amide group of the compound contained. And forming a slurry containing the precipitated alkali metal halide and stirring the slurry until the dehydrohalogenation reaction is complete, thereby obtaining a 2,3-epoxypropyl derivative or 2-methyl −
Step (B) of preparing a slurry containing the 2,3-epoxypropyl derivative and the alkali metal halide produced by this reaction, by removing the alkali metal halide from the slurry prepared in the step (B) or this slurry. The obtained liquid is purified with a sulfonic acid having a solubility of 1% by weight or more in water at 30 ° C. as a purification aid, a sulfonate, a carboxylate having 7 or more carbon atoms in the molecule,
(C) preparing a purified liquid containing the above derivative by washing with an aqueous solution containing an effective amount of an alcohol sulfate ester having 4 or more carbon atoms in the molecule or a mixture thereof; And removing the epihalohydrin or 2-methylepihalohydrin therein from the purified liquid prepared in the step (C) by evaporation to obtain a 2,3-epoxypropyl derivative of the above compound or 2-methyl-2,3 (D) producing an epoxypropyl derivative as a high-purity product.

In the present invention, the epoxy equivalent of a product of an epoxy compound is defined as the number of grams of a product containing 1 mol of oxirane oxygen atoms. The ionic halogen content of the product is obtained by dissolving the product in a mixed solution of 100 parts by weight of acetonitrile and 25 parts by weight of pure water, or obtained by extracting the product with the above mixed solution. This is a value obtained by measuring the product solution obtained as an analyte by ion chromatography analysis and represents the content of ionic halogen present in the form of a salt in the product.

The thermal stability of the product is determined by the difference between the epoxy equivalent of the product before heating and the epoxy equivalent of the product after heating the product in a closed container at 150 ° C. for 24 hours. Expressed as a percentage of the epoxy equivalent, the smaller the percentage of increased epoxy equivalent, the higher the thermal stability of the product. The turbidity at the time of melting of the product is represented by the kaolin turbidity of the melt obtained by defoaming after melting the product. This kaolin turbidity is obtained by diluting a mixture of 1 g of kaolin as a special grade reagent and 10 ml of 37% by weight formalin with pure water. 2, when the kaolin concentration is 30 ppm, kaolin turbidity 3 is defined, and when the kaolin concentration is 50 ppm, kaolin turbidity 4 is defined.
The turbidity of the melt of the above-mentioned product, which corresponds to the kaolin turbidity, indicates the kaolin turbidity of the above-mentioned product at the time of melting. The lower the turbidity of the product melt, the higher the purity of the product. Kaolin turbidity of 1 or less is substantially transparent.

The product obtained by the above step (D) of the present invention has an epoxy equivalent of 1.0 to 1.1 times the theoretical epoxy equivalent of the compound, a thermal stability of an epoxy equivalent increase rate of 3% or less, 10% or less. It is a high-purity product having an ionic halogen content of not more than ppm by weight and a kaolin turbidity of not more than 1 when melted.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION The compound having 2 to 4 carboxyl groups in the molecule used as a raw material in the step (A) may be a compound which has been conventionally used as a raw material for producing an epoxy compound. Examples include maleic acid,
Aliphatic dicarboxylic acids such as succinic acid, itaconic acid, fumaric acid, adipic acid, pimelic acid, suberic acid, sebacic acid or unsaturated fatty acid such as dimer acid or trimer acid; phthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid , Hymic acid, tetrachlorophthalic acid,
Aromatic dicarboxylic acids such as hexahydrophthalic acid, phenylenediacetic acid or naphthalic acid; aromatic tricarboxylic acids such as trimellitic acid or trimesic acid; and aromatic tetracarboxylic acids such as pyromellitic acid. 1
Carboxyl groups have one active hydrogen atom, so the molecule contains two dicarboxylic acids and three tricarboxylic acids.
And four tetracarboxylic acids each have four active hydrogen atoms. Acid anhydrides of these compounds having a carboxyl group can also be used as long as they react in the step (A) as a compound having a carboxyl group. The number of active hydrogen atoms in the molecule of these acid anhydrides is represented by the number of all carboxyl groups contained in the molecule when the acid anhydride is hydrolyzed. Preferred examples of the compound having 2 to 4 carboxyl groups include phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, trimesic acid, pyromellitic acid and the like.

The compound having 1 to 3 amide groups in the molecule may be any of those conventionally used as raw materials for producing epoxy compounds. For example, N, N'-
Examples thereof include dimethyl urea, N, N'-diphenyl urea, ethylene urea, hydantoin, and isocyanuric acid. Of these, hydantoin and isocyanuric acid are preferable. Ethylene urea, N, N'-dimethylurea and N,
N'-diphenylurea has one amide group but 2
Has two active hydrogen atoms, hydantoin has two amide groups and has two active hydrogen atoms. Isocyanuric acid has three amide groups and three active hydrogen atoms.

Examples of the epihalohydrin include epichlorohydrin, epibromohydrin, epiiodohydrin and the like. Of these, epichlorohydrin, which is easily available, is preferable. Examples of 2-methylepihalohydrin include 2-methylepichlorohydrin, 2-methylepibromohydrin, 2-methylepiiodhydrin, and the like, and 2-methylepichlorohydrin is easily available and is preferred.

As the catalyst, amines, quaternary ammonium compounds, substituted phosphines, quaternary ammonium compounds and the like can be used. For example, primary amines such as butylamine and secondary amines such as dibutylamine Although tertiary amines, quaternary ammonium bases, quaternary ammonium salts, trisubstituted phosphines, quaternary phosphonium salts and the like can be used as preferred catalysts.

Examples of preferred catalysts include triethylamine, tri-n-propylamine, tributylamine,
Tertiary amines such as benzyldimethylamine or triethanolamine; quaternary ammonium hydroxides such as tetramethylammonium hydroxide or benzyltrimethylammonium hydroxide; benzyltrimethylammonium chloride, benzyltrimethylammonium acetate, methyl Quaternary ammonium salts such as triethylammonium chloride, tetramethylammonium chloride or tetraethylammonium chloride; trisubstituted phosphines such as triphenylphosphine, tolylphosphine or tributylphosphine; methyltriphenylphosphonium bromide, methyltriphenylphosphonium chloride Product, ethyltriphenyl chloride, methyltriphenylphosphonium iodide, benzyltriphenylphosphonium bromide or Quaternary phosphonium salts, and the like such as Le triphenylphosphonium bromide, tetramethyl ammonium chloride Among these, tetraethylammonium bromide, ethyl triphenyl phosphonium bromide is preferable. When terephthalic acid is used as a raw material, an alkali metal halide such as sodium bromide can be used as a catalyst.

Examples of the alkali metal hydroxide include hydroxides of sodium, potassium, lithium and the like. Of these, sodium hydroxide, potassium hydroxide and the like are preferable. It is preferred to use a concentrated aqueous solution, for example, an aqueous solution of 20 to 70% by weight, preferably 40 to 60% by weight.

In the step (A), four kinds of raw materials can be employed. The first raw material is composed of the compound having a carboxyl group and epihalohydrin, and the second raw material is
The third raw material is composed of the compound having an amide group and epihalohydrin, and the fourth raw material is composed of the compound having an amide group and 2-methyl epihalohydrin. Become. When any of the raw materials is employed, epihalohydrin or 2-methylepihalohydrin is used in an amount of 1.2 to 60 mol per mol of active hydrogen atoms of the compound having a carboxyl group or the compound having an amide group.
Moles, preferably 2 to 20 moles, and most preferably 5 to 10 moles.

In the step (A), the compound having a carboxyl group or an amide group is added to epihalohydrin or 2-halide.
By subjecting methyl epihalohydrin to an addition reaction,
2- of the compound having a carboxyl group or an amide group
A hydroxy-3-halopropyl derivative or a 2-hydroxy-2-methyl-3-halopropyl derivative is formed.
Therefore, the bis (2-hydroxy-3-halopropyl) ester or bis (2-hydroxy-2-methyl-3-halopropyl) ester is derived from the dicarboxylic acid,
From the tricarboxylic acid, its tris (2-hydroxy-3-halopropyl) ester or tris (2-hydroxy-2-methyl-3-halopropyl) ester, and from the tetracarboxylic acid, its tetrakis (2-
(Hydroxy-3-halopropyl) ester or tetrakis (2-hydroxy-2-methyl-3-halopropyl)
Esters are formed respectively. The N, N'-bis (2-hydroxy-3-halopropyl) derivative or bis (2-hydroxy-2-methyl-
3-Halopropyl) derivative is converted from hydantoin to its N, N'-bis (2-hydroxy-3-halopropyl)
Derivatives or bis (2-hydroxy-2-methyl-3-halopropyl) derivatives, and from isocyanuric acid, its tris (2-hydroxy-3-halopropyl) ester or tris (2-hydroxy-2-methyl-3) ester. -Halopropyl) esters are each formed.

The addition reaction in step (A) can be carried out in the absence of a catalyst, but is preferably promoted by using a substance which promotes the reaction. As the substance for accelerating the reaction, a wide range of substances having a relatively weak action, for example, from an alkali metal hydroxide such as sodium hydroxide to the above-mentioned catalyst having a relatively strong action can be used. However, it is preferable to promote the reaction using the above-mentioned preferred catalyst. Therefore, this addition reaction is preferably carried out in a reaction mixture consisting of the above-mentioned raw material and a tertiary amine, a quaternary ammonium base, a quaternary ammonium salt, a trisubstituted phosphine or a quaternary phosphonium salt of the catalyst, preferably from 60 to 130. It is performed by heating at a temperature of ° C. The amount of the catalyst is 0.001 to 0.1 mol, particularly 0.01 to 0.1 mol of the above-mentioned catalyst compound per 1 mol of the compound having a carboxyl group or the compound having an amide group.
A ratio of 05 mol is preferred. The above molar ratio is also preferable for the alkali metal halide catalyst used when reacting terephthalic acid as a raw material. The reaction mixture may contain, at its initial stage, 0.1 to 2% by weight of water, based on the epihalohydrin or 2-methyl epihalohydrin therein, in order to accelerate the reaction.

The heating of the reaction mixture is preferably continued until 90% or more, particularly preferably all, of the active hydrogen atoms of the carboxyl group or the amide group of the compound in the reaction mixture have disappeared. The detection of this active hydrogen atom in the reaction mixture can be performed, for example, by liquid chromatography analysis. In this manner, usually, by the above-mentioned heating for 2 to 10 hours, a reaction product containing epihalohydrin and the above 2-hydroxy-3-halopropyl derivative, or 2-methyl epihalohydrin and the above 2-hydroxy-2-methyl-3 A reaction product containing the halopropyl derivative is formed.

In the step (B), from the 2-hydroxy-3-halopropyl derivative and the by-product 2-hydroxy-1,3-dihalopropane contained in the reaction product formed in the step (A), or 2-hydroxy-2-methyl-3
-Halopropyl derivative and by-product 2-hydroxy-2
These compounds are converted into epoxy compounds by causing a so-called dehydrohalogenation reaction for releasing hydrogen halide from -methyl-1,3-dihalopropane.

Thus, by this reaction, epihalohydrin is produced from the by-product 2-hydroxy-1,3-dihalopropane and 2-hydroxy-2-methyl-by-product.
1,3-Dihalopropane produces 2-methylepihalohydrin, respectively. Further, from the bis (2-hydroxy-3-halopropyl) ester of the dicarboxylic acid generated in the step (A), the bis (2,3-
The bis (2-hydroxy-2-methyl-3-halopropyl) ester of the dicarboxylic acid produces the bis (2-methyl-2,3-epoxypropyl) ester of the carboxylic acid. .

Similarly, from the tris (2-hydroxy-3-halopropyl) ester of tricarboxylic acid, the tris (2,3-epoxypropyl) ester of tricarboxylic acid and the tris (2-hydroxy-2-halopropyl) ester of tricarboxylic acid can be obtained. The tris (2-methyl-2,3-epoxypropyl) ester of this tricarboxylic acid is formed from the methyl-3-halopropyl) ester.

From the tetrakis (2-hydroxy-3-halopropyl) ester of tetracarboxylic acid, the tetrakis (2,3-epoxypropyl)
Esters and the tetracarboxylic acid tetrakis (2
-Hydroxy-2-methyl-3-halopropyl) ester forms tetrakis (2-methyl-2,3-epoxypropyl) ester of this tetracarboxylic acid.

From the N, N'-bis (2-hydroxy-3-halopropyl) derivative of the urea derivative, the N, N'-bis (2,3-epoxypropyl) derivative of the urea derivative and the urea derivative From the N, N'-bis (2-hydroxy-2-methyl-3-halopropyl) derivative, the N, N'-bis (2-methyl-2,3-epoxypropyl) derivative of the urea derivative is formed, respectively. .

From the N, N'-bis (2-hydroxy-3-halopropyl) derivative of hydantoin, the N, N'-bis (2,3-epoxypropyl) derivative of hydantoin and the N, N 'of hydantoin are obtained. The N, N'-bis (2-methyl-2,3-epoxypropyl) derivative of hydantoin is generated from the -bis (2-hydroxy-2-methyl-3-halopropyl) derivative.

From the tris (2-hydroxy-3-halopropyl) ester of isocyanuric acid, the tris (2,3-epoxypropyl) ester of isocyanuric acid and the tris (2-hydroxy-2-methyl-3) ester of isocyanuric acid are used. (Halopropyl) ester produces tris (2-methyl-2,3-epoxypropyl) ester of isocyanuric acid, respectively.

In the step (B), the reaction product formed in the step (A) is added to the reaction product under reflux of the epihalohydrin or 2-methylepihalohydrin before the addition reaction. 1-2 mol per 1 mol of active hydrogen atom of the carboxyl group or amide group of the compound,
Preferably the alkali metal hydroxide in an amount of preferably from 1 to 1.2 mol is gradually dissolved, preferably as a 20 to 70% by weight aqueous solution, particularly preferably as a 40 to 60% by weight aqueous solution.
Preferably, it is added little by little as droplets. This addition causes the dehydrohalogenation reaction to produce an alkali metal halide and water in the reaction mixture. Then, the alkali metal halide precipitates to form a slurry containing the precipitated alkali metal halide. The dehydrohalogenation reaction is carried out in the presence of an aprotic and polar solvent such as dimethylformamide or methyl isobutyl ketone in an amount of 5 to 30% by weight with respect to the epihalohydrin in the slurry. The rate of the dehydrohalogenation reaction can be increased, and the content of hydrolyzable halogen in the product obtained by the step (D) described below can be reduced.
As a method of carrying out this reaction in the co-presence of the above amount of aprotic and polar solvent, a method of adding this solvent to the reaction mixture in step (A) may be used, but the method is carried out at a relatively low temperature. In the step (B), a method is preferred in which the solvent is added to the slurry to allow the reaction to proceed.

By forming a slurry in this manner and maintaining the slurry at a temperature as low as possible, for example, 10 to 80 ° C., preferably 20 to 70 ° C. under reduced pressure, epihalohydrin or The water added and the water formed, together with the 2-methyl epihalohydrin, are continuously evaporated, the vapor is condensed in a condenser, the condensed water is discharged out of the reaction mixture and the condensed epihalohydrin or 2- Methyl epihalohydrin is refluxed into the slurry. Furthermore, with this addition,
It is preferable to maintain the degree of decompression near 100 mmHg in the initial stage, gradually increase the degree of decompression as the addition proceeds, and increase the degree of decompression to around 60 mmHg in the latter half of this addition. The reaction of this step (B) can be usually completed in 1 to 10 hours.

The reaction in the step (B) is preferably carried out while stirring the slurry. For a reaction performed on a small scale, ordinary stirring with, for example, paddle blades, turbine blades or the like is sufficient, but the reaction of step (B) is performed on a large scale.
For example, when performed in a slurry having a volume of 20 liters or more, ordinary stirring is not sufficient. If the stirring is insufficient, the precipitated alkali metal halide, water and alkali metal hydroxide are unevenly distributed on the bottom or the wall of the reactor where the flow of the liquid is likely to be insufficient, or the state is bulky. Occurs and prevents smooth evaporation of water. If the dispersion of the precipitated alkali metal halide, water and alkali metal hydroxide is insufficient, side reactions are likely to occur in the unevenly distributed portions as described above, and the subsequent steps (C) and (C) By reducing the yield and purity of the product obtained by D), by maintaining the slurry under sufficient agitation such that such an uneven distribution of the precipitated alkali metal halide, water and alkali metal hydroxide does not occur. It has been found that the product yield and purity can be maintained at a high level.

To stir the slurry so as not to cause the uneven distribution of the precipitated alkali metal halide, water and alkali metal hydroxide by simply increasing the rotation speed of a stirrer having paddle blades or turbine blades, Particularly, it is not efficient for a slurry having a large volume of 100 liters or more. When the concentration of the precipitated alkali metal halide in the slurry increases as the reaction proceeds, a large resistance is caused to the high-speed rotation of the stirrer. In some cases, even if the rotation speed of the stirrer is increased in such a manner, the precipitated alkali metal halide, water, and alkali metal hydroxide may be pressed against the vessel wall. In a larger volume slurry, the water contained in the slurry is more likely to evaporate closer to the upper liquid level, but the water contained in the slurry at the bottom of the reactor often does not boil. Therefore, when the precipitated alkali metal halide, water and alkali metal hydroxide collectively stagnate at the bottom of the reactor, side reactions are likely to occur in the slurry in contact therewith as described above.

Providing a high flow rate to the slurry is not very important, and stirring to provide a partial swirl to the slurry is not very effective. Rather, agitation such that a uniform dispersion is maintained throughout the slurry is preferred. Examples of such preferred agitation include a circulating flow in which the liquid layer rises from the bottom of the reactor along the reactor side wall to the upper liquid level of the slurry, And a stirrer that causes uniform mixing due to the entrained flow reversed near the side wall toward the lower center and the entrained flow subdivided by lateral shearing of the entrained flow. The circulating stream, the entrained stream and the stirrer which causes the subdivision of the entrained stream are already known and are also commercially available. Further preferable stirring can be performed by providing a baffle to the reactor together with the stirrer for causing the preferable stirring.

Therefore, in the step (B) in which a large volume slurry of 100 liters or more is handled, the reaction product obtained in the step (A) is added to the reaction product obtained in the step (A) in a reactor under reflux of epihalohydrin therein. An aqueous solution of 20 to 70% by weight of an alkali metal hydroxide in an amount of 1 to 2 mol, preferably 1 to 1.2 mol, per 1 mol of active hydrogen atoms of the compound contained before the addition reaction , Preferably 40 to
By gradually adding as a 60% by weight aqueous solution,
A slurry containing the precipitated alkali metal halide is formed, and the added and formed water is removed by evaporation from the slurry, preferably a slurry maintained at 20-60 ° C under reduced pressure, and the dehalogenation is carried out. Until the hydrogen reaction is completed, the slurry is subjected to a circulating flow rising from the bottom of the reactor containing the slurry to the liquid level along the side wall thereof and the rising circulating flow is reversed around the side wall of the liquid surface to form a reactor. By a method (B ′) of maintaining the stirring under uniform stirring of the slurry by the entrainment flow toward the lower center and the subdivision of the entrainment flow by transverse shearing of the entrainment flow, containing the precipitated alkali metal halide, 2,3-epoxypropyl derivative of a compound having a carboxyl group or an amide group and epihalohydrin or 2-methyl Slurry containing 2,3-epoxypropyl derivative and 2-methyl-epihalohydrin is preferably prepared. Since this method (B ') can significantly reduce the amount of by-produced impurities in the reaction product, tris (2,3-epoxypropyl) ester of isocyanuric acid or tris (2-methyl-2,3 -Epoxypropyl) ester, bis (2,3) terephthalic acid
-Epoxypropyl) ester or bis (2-methyl-
In the case of producing products of crystalline derivatives such as 2,3-epoxypropyl) ester, the purity can be significantly increased by the subsequent production step (E), which is advantageous for the production of these products.

As the purification aid used in the step (C), a water-soluble organic group-containing compound having a solubility of 1% by weight or more in water at 30 ° C. is used. When an organic group-containing compound having a solubility of less than 1% by weight in water at 30 ° C. is used as a purification aid, the compound having such a low solubility is transferred from the aqueous solution to the organic layer in contact with the aqueous solution. However, it remains even in the product collected in a later step and deteriorates the quality of the product. As a trend, as the number of carbon atoms contained in the organic group in the compound increases,
Although the solubility of the organic group-containing compound in water decreases, a compound containing an organic group and having a solubility of 1% by weight or more in water at 30 ° C. as described above is preferable. As a purification aid, a compound that generates an acidic or alkaline aqueous solution when dissolved in water can also be used as long as it allows a reduction in efficiency such as a reduction in product yield or an additional washing step. However, as a compound which does not cause such a decrease in efficiency, a compound which can obtain a neutral aqueous solution when dissolved in water is preferable.

Examples of the compound used as a purification aid include sulfonic acid, sulfonate, carboxylate, alcohol sulfate, and mixtures thereof. These compounds may contain a hydrocarbon group, an amide group, an ester group, a hydroxy group, an ether group, an acetoxy group, a hydrocarbon group substituted with these groups, and the like. And as the salt, a salt of a monoacid base which gives the salt a higher water solubility than a salt of a polyacid base such as a magnesium, calcium or aluminum salt, for example, an alkali metal such as sodium, potassium or lithium Salts, amine salts such as monoethanolamine, diethanolamine or triethanolamine, or ammonium salts are preferred.

Preferred examples of the sulfonic acid include alkyl-substituted benzenesulfonic acid having 1 to 3 carbon atoms, such as benzenesulfonic acid, toluenesulfonic acid and xylenesulfonic acid, and naphthalenemonosulfonic acid. Examples of preferred sulfonic acid salts include alkali metal salts such as sodium salt of benzenesulfonic acid, amine salts such as ammonium salt or triethanolamine salt, having 1 to 3 carbon atoms such as toluenesulfonic acid. Alkali metal salts such as sodium salts of alkyl-substituted benzenesulfonic acids, amine salts such as ammonium salts or triethanolamine salts, formaldehyde condensates of these alkyl-substituted benzenesulfonic acid salts, p-
Alkali metal salts such as sodium salt of hydroxybenzenesulfonic acid, amine salts such as ammonium salt or triethanolamine salt, alkali metal salts such as sodium salt of p-nonylbenzenesulfonic acid, ammonium salt or triethanolamine salt Amine salts such as sodium salts of naphthalenesulfonic acid, amine salts such as ammonium salts or triethanolamine salts, or alkali salts of aromatic sulfonic acids such as formaldehyde condensates of these naphthalenesulfonic acid salts. Metal salts, ammonium salts or amine salts; alkali metal salts such as sodium salt of methanesulfonic acid; amine salts such as ammonium salt or triethanolamine salt; alkali metal salts such as sodium salt of ethanesulfonic acid; Salts or amine salts such as triethanolamine salt, alkali metal salts such as sodium salt of vinylsulfonic acid, amine salts such as ammonium salt or triethanolamine salt, polymers of these vinylsulfonic acid salts, 2-aminoethane Alkali metal salts such as sodium salt of sulfonic acid; amine salts such as ammonium salt or triethanolamine salt; alkali metal salts such as sodium salt of octyl sulfoacetate; amine salts such as ammonium salt or triethanolamine salt. ,
Alkali metal salts such as sodium salt of butanesulfonic acid, amine salts such as ammonium salt or triethanolamine salt, alkali metal salts such as sodium salt of hexanesulfonic acid, amine such as ammonium salt or triethanolamine salt. Salts, alkali metal salts such as octanesulfonic acid sodium salt, amine salts such as ammonium salt or triethanolamine salt, or alkali metal salts such as decanesulfonic acid sodium salt, ammonium salt or triethanolamine salt. Examples of such an amine salt include alkali metal salts, ammonium salts, and amine salts of alkanesulfonic acids having up to 10 carbon atoms.

Examples of preferred carboxylate salts include alkali metal salts such as the sodium salt of heptanoic acid, alkali metal salts such as the sodium salt of octanoic acid, or alkali metal salts such as the sodium salt of decanoic acid. 1
Alkali metal salts of monovalent alkanoic acids having up to one carbon atom; alkali metal salts of aromatic monovalent carboxylic acids such as sodium benzoate, monosodium salt of salicylic acid or sodium salt of cinnamic acid; phthalic acid A dialkali metal salt of an aromatic divalent carboxylic acid such as a disodium salt of; a dialkali metal salt of an alicyclic hydrocarbon dicarboxylic acid such as a disodium salt of hexahydrophthalic acid; a sodium salt of o-hydroxybenzoic acid; Examples thereof include alkali metal salts of hydroxybenzenecarboxylic acid such as sodium salt of p-hydroxybenzoic acid.

Examples of preferred alcohol sulfates include alkali metal salts such as the sodium salt of butyl sulfate, amine salts such as ammonium or triethanolamine salts, and alkali metal salts such as the sodium salt of heptyl sulfate. Salts, amine salts such as ammonium salts or triethanolamine salts, alkali metal salts such as octyl sulfate sodium salts, amine salts such as ammonium salts or triethanolamine salts, sodium salts of decyl sulfate esters. Amine salts such as alkali metal salts, ammonium salts or triethanolamine salts, alkali metal salts such as sodium salts of lauryl sulfate, amine salts such as ammonium salts or triethanolamine salts, sodium salts of myristyl sulfate Alkali metal salts such as salts, amine salts such as ammonium salts or triethanolamine salts, alkali metal salts such as sodium salt of lauryl diethylene glycol ether sulfate, amine salts such as ammonium salts or triethanolamine salts, nonylphenol Examples thereof include alkali metal salts such as sodium salt of polyethylene glycol ether sulfate, ammonium salts and amine salts such as triethanolamine salt. Alkali metal salts of alcohol sulfates having 10 to 28 carbon atoms can also be used, such as alkali metal salts such as the sodium salt of sulfate of lauryl polyethylene glycol ether.

Particularly preferred compounds include sodium, potassium, lithium, ammonium or triethanolamine salts of benzenesulfonic acid, and sodium, potassium, lithium, ammonium or triethanolamine salts of toluenesulfonic acid. , Sodium, potassium, lithium, ammonium or triethanolamine salts of vinylsulfonic acid, or polymers of these vinylsulfonic acid salts, sodium, potassium, lithium, ammonium or triethanolamine lauryl sulfate Salts, sodium, potassium, lithium, ammonium or triethanolamine salts of water-soluble formaldehyde condensates of naphthalenesulfonic acid, sodium, potassium or lithium salts of cinnamic acid, salici Sodium salt of the acid, potassium salt or lithium salt, disodium salt of tetrahydrophthalic acid,
Examples include dipotassium salts or dilithium salts, disodium salts of phthalic acid, dipotassium salts or dilithium salts, toluenesulfonic acid, benzenesulfonic acid and the like. When these compounds are used as refining aids, the heat stability and the transparency of the product recovered in the subsequent step can be significantly improved. Furthermore, the most preferable aromatic sulfonic acid, its alkali metal salt, and the like do not remain in the product recovered in the subsequent step, and hardly cause deterioration in the quality of the product due to the purification aid.

By washing the slurry in the step (C), the alkali metal halide, the remaining catalyst, the remaining alkali metal hydroxide, and other impurities contained in the slurry are removed from the slurry by the water in contact with the slurry. Transfer to a layer and a purified liquid is prepared. The aqueous layer dissolves a small amount of epihalohydrin and 2,3-epoxypropyl derivative or 2-methylepihalohydrin and 2-methyl-2,3-epoxypropyl derivative contained in the slurry in addition to these transfer components. contains. Therefore, in this purification, it is advantageous to increase the product yield by using as little water as possible, and to enhance the production efficiency by completing the washing in as short a time as possible.

When the slurry is washed with an aqueous solution of the compound as a purification aid, the purification aid in the aqueous layer hardly migrates to the organic layer, and can be sufficiently prepared in a short time with a relatively small amount of water. It was found that a purified liquid was obtained, and in particular, the product recovered in the subsequent step (D) was purified so as to show a kaolin turbidity of 1 or less upon melting.

The washing of the slurry is two to three times
It is preferable to repeat the process three times. The more the amount of the refining aid is used, the more effective it is. However, even if the amount is increased to 5% by weight or more, the effect is not improved. In the method of washing repeatedly as described above, in the first and second times, 0.01 to 5 parts by weight, preferably 0.05 to 2 parts by weight, most preferably 100 parts by weight of the derivative in the slurry. 0.1-1 part by weight of the above-mentioned purification aid is used as its aqueous solution, and the third time the amount of the purification aid is reduced so that no contamination of the purification aid occurs in the product, 0.001 to 5 parts by weight, preferably 0.001 to 2 parts by weight, most preferably 0.001 part by weight with respect to parts by weight
It is preferred to use 精製 1 part by weight of the purification aid as an aqueous solution thereof. The amount of water used to wash the slurry depends on the amount of water contained in the slurry at each of these times.
It is preferably about 0.5 to 50 times, especially about 1 to 5 times the weight of the -epoxypropyl derivative or the 2-methyl-2,3-epoxypropyl derivative. When washing with an aqueous solution of a purification aid having relatively low water solubility, it is preferable to further wash with a small amount of pure water thereafter. A weakly acidic neutralizing agent such as sodium dihydrogen phosphate may coexist in the aqueous solution used for this washing. The temperature of the aqueous solution used for washing is about 10 to 40 ° C, particularly 20 to 30 ° C.
Is preferred.

This washing is carried out by sufficiently contacting the slurry layer with the above aqueous solution for washing, and using any of various conventionally known apparatuses, either a batch type or a continuous type. It can also be done by a method.
For example, the slurry, the above-described amount of the purification aid and water are separately or together supplied as an aqueous solution into a vessel equipped with a stirrer, and the slurry is stirred so that the slurry layer and the washing water layer are in sufficient contact. Can be performed. The stirring time varies depending on the stirring intensity, but can be completed in a short time of about 5 to 10 minutes by ordinary stirring. After the stirring is stopped, the liquid in the container is allowed to stand still. The time required for this standing still varies depending on the intensity of stirring as described above, but according to ordinary stirring, it may be about 5 to 60 minutes, preferably about 10 to 30 minutes. However, when the slurry layer is washed with the aqueous solution by the method of stirring in the vessel in this manner, the organic layer still remains after this washing, as is sometimes the case when using an aqueous solution with insufficient concentration of the purification aid. May show turbidity. The fine liquid particles of the organic layer formed to bring the slurry layer and the aqueous solution layer for washing into sufficient contact are relatively easily united to form an organic layer again, whereas the fine liquid particles of the organic layer are formed again. It has been found that the droplets of the aqueous solution do not easily coalesce, and as a result, the droplets of the fine aqueous solution disperse in the re-formed organic layer over a long period of time, causing the turbidity. Was. The re-formed aqueous layer hardly contains the fine liquid particles of the organic layer. However, the organic layer is recovered while the fine liquid particles of the aqueous solution are dispersed as described above, and this liquid is recovered in a later step (D). It has been found that evaporation of the epihalohydrin from the organic layer produces a less pure product. It is considered that the stable dispersion of the liquid droplets of the fine aqueous solution in the organic layer is maintained by the impurities that migrate from the organic layer and exist around the liquid particles of the aqueous solution.

As a preferable washing method of the slurry, the above aqueous solution is introduced into a slurry column as liquid particles having an average diameter of 0.1 to 10 mm, and the slurry is mixed with the slurry by raising the slurry in the slurry column. And then coalescing the droplets to form an aqueous layer, or coalescing the droplets into an already formed aqueous layer and separating the droplets from the slurry column, It has been found that products can be manufactured efficiently and with high purity. The washing method using the liquid particles is performed in an amount sufficient to dissolve the precipitated alkali metal halide in the slurry containing the precipitated alkali metal halide prepared in the step (B).
Preferably, by removing the precipitated alkali metal halide by a method of adding water or the above aqueous solution by 2 to 3 times by weight and stirring gently, or by filtering a slurry containing the precipitated alkali metal halide. It is preferably applied to the obtained liquid. Preferred washing with such liquid droplets is as follows: the aqueous solution layer formed by combining the liquid droplets in the column of liquid material as described above is again put into the column of the upper liquid material by 0.1%.
By repeatedly introducing, raising and coalescing as liquid particles having an average diameter of 10 to 10 mm, it is possible to carry out more efficiently and to obtain a purified liquid material that does not exhibit turbidity.

Therefore, in the step (C), an aqueous solution containing the above-mentioned purification aid is added to a column of the liquid obtained by removing the above-mentioned precipitated alkali metal halide in an amount of 0.1%.
Liquid particles having an average diameter of 10 to 10 mm, preferably 0.3 to 10 mm, the liquid particles are raised in a liquid column, and the liquid particles are combined to form a layer of the aqueous solution. After that, the aqueous solution layer is applied to the upper liquid material column again by 0.1 to 10 mm, preferably 0.3 to 10 m.
m as a liquid particle having an average diameter of m, the liquid particle is raised, and the coalescence is repeated.
The purified liquid can be preferably prepared by the method (C ′) in which the supply of the aqueous solution of the purification aid is continued until about 5 parts by weight of the purification aid is supplied. In this method (C '), the amount of water supplied with the purification aid is:
The amount is preferably about 50 to 5000 parts by weight based on 100 parts by weight of the derivative, and this method (C ′) can be applied repeatedly.

Since this method (C ') has a very high purification effect, it can be advantageously used to purify a liquid material having a large amount of impurities obtained without using the preferable method (B') in the step (B). Can be achieved. Furthermore, according to this method (C ′), even if the amount of the purification aid used is reduced, the aqueous solution does not remain in the organic layer, so that it can be effectively purified, and its extreme By way of example, this water (C ′) is obtained using
Even when performing the washing operation, compared with the method of recovering the organic layer by stirring the organic layer and water in the container and then allowing it to stand for a long time,
In addition, improved purification can be achieved in a short time.
In particular, tris (2,3-epoxypropyl) ester or tris (2-methyl-2,3-epoxypropyl) ester of isocyanuric acid and bis (2,3
-Epoxypropyl) ester or bis (2-methyl-
In the case of producing a product of a crystalline derivative such as (2,3-epoxypropyl) ester, the purity can be further increased by the subsequent purification step (E), so that water containing no purification aid is used. The method of carrying out the washing operation of (C ′), that is, the column of the liquid obtained by removing the precipitated alkali metal halide is charged with water containing no purification aid in an amount of 0.1 to 10 mm, preferably 0.1 to 10 mm. 0.3 ~
Liquid particles having an average diameter of 10 mm are introduced, the liquid particles are raised in a column of liquid material, and the liquid particles are combined to form a water layer. 0.1-10 mm, preferably 0.3-
Introducing the liquid particles having an average diameter of 10 mm, raising the liquid particles, and repeating the coalescence,
5 parts per 100 parts by weight of the above derivative in the liquid
The process (C ") which is continued until 0 to 5000 parts by weight of water is supplied is suitable for the production of products of these crystalline derivatives, and this process (C") can be applied repeatedly.

As described above, in the liquid material column, 0.1%
The method of repeatedly introducing and raising the liquid particles of the aqueous solution having an average diameter of 10 to 10 mm and forming a layer of the aqueous solution by coalescence can be performed by using an apparatus made for such a method. By way of example, this device has a cylindrical portion, a cylindrical liquid storage portion provided continuously above the cylindrical portion and installed above the cylindrical portion, and a cylindrical shape provided continuously below the cylindrical portion and provided below. The liquid storage unit includes a liquid storage unit, a lid that covers the upper liquid storage unit, and a rotating shaft that penetrates the center of the lid and is inserted to the lower end of the cylindrical unit. The upper liquid storage portion has substantially the same inner diameter as the cylindrical portion and a height sufficient to store the liquid, and a liquid discharge port is provided at an upper portion thereof. The lid is provided with a liquid supply conduit extending therethrough and extending to near the lower end of the upper liquid reservoir. The lower liquid storage part has substantially the same inner diameter as the cylindrical part and a depth sufficient to store liquid, a liquid outlet is provided at the bottom thereof, and a lower liquid storage part has a middle part. A liquid supply conduit extending through the side wall and extending to near the lower end of the rotating shaft is provided. On the rotating shaft, a plurality of perforated disks are attached at equal intervals from the lower end to a height near the upper end of the cylindrical portion, and a plurality of donut-shaped baffles are provided on the inner wall of the cylindrical portion at positions sandwiched between the perforated disks. Installed. A band ring is attached to the lower side of the outer periphery of each perforated disk, and the holes of the perforated disk
The board is provided so as to penetrate from the upper surface to the lower surface of the board so as to generate droplets having an average diameter of 0.1 to 10 mm. The rotation shaft reciprocates at a certain rotation angle by the operation of a driving device connected to the upper end.

An organic liquid which is immiscible with water and has a specific gravity larger than that of water is supplied from the liquid supply conduit of the lid to the above-mentioned washing device up to the middle of the upper part of the liquid storage part. While reciprocating rotation, and then supplying the aqueous solution for washing from the liquid supply conduit of the lower liquid storage section,
The aqueous solution is discharged from the outlet of the conduit into the organic liquid, is captured in the ring of the lowermost perforated plate, becomes liquid droplets of the aqueous solution through the through-holes, and is formed above the perforated plate in the organic liquid column. And is dispersed while moving upward in the column of organic liquid. The dispersion particles are trapped in the ring of the second-stage perforated plate from the bottom while being moved toward the center of the cylinder by the baffle plate provided on the inner wall of the cylindrical portion, and coalesce there, and then the through-holes are formed again. Through the column of organic liquid above the perforated plate as liquid droplets, and are dispersed while moving upward in the column of organic liquid. In this way, the aqueous solution supplied from the middle of the lower liquid storage section rises while repeatedly dispersing and merging the liquid particles in the column of the organic liquid, and finally the organic liquid in the upper liquid storage section. It reaches the top of the column and forms a layer of aqueous solution on top of the column and is stored. As the supply of the aqueous solution from the middle of the lower liquid reservoir is further continued, the amount of the aqueous layer on the organic liquid column gradually increases, and the aqueous solution that reaches the liquid outlet of the upper liquid reservoir is discharged from the outlet. It overflows and is discharged from. By performing the supply of the organic liquid and the supply of the aqueous solution continuously, the organic liquid and the aqueous solution can be brought into continuous and countercurrent contact. The supply speed of the organic liquid and the supply speed of the aqueous solution can be adjusted, and the size of the liquid particles of the aqueous solution can be adjusted by adjusting the rotation speed of the rotating shaft. Such a washing device can be obtained as a commercial product.

By continuously supplying the liquid and the aqueous solution to the washing device, the liquid and the aqueous solution can be brought into continuous contact inside the washing device as described above. The purified liquid can be continuously collected from the bottom of the apparatus. Even with such a water washing method, until 0.01 to 5 parts by weight of the above-mentioned purification aid is supplied to 100 parts by weight of the derivative in the organic layer,
It is preferable to continue introducing the aqueous solution into the organic layer. The water washing apparatus as described above can also be applied to the method (C ″) using water containing no purification aid.

In this way, a purified liquid containing epihalohydrin is usually prepared by the step (C) at a concentration such as 70 to 90% by weight of epichlorohydrin. In the step (D), epihalohydrin or 2-methylepihalohydrin usually contained therein and other volatile components contained in a small amount are removed from the liquid material thus purified by evaporation, and these volatile components are contained. No products are manufactured. The vapor is led to a condenser and recovered as a liquid.

To concentrate the liquid by evaporating epihalohydrin or 2-methylepihalohydrin from the purified liquid material, for example, use a conventional evaporator, rotary evaporator, flash evaporator, falling film evaporator or the like. Although the method can be easily carried out by the method, when the concentration of epihalohydrin or 2-methylepihalohydrin in the concentrated liquid reaches about 10% by weight, the liquid shows high viscosity. In particular, when the concentration of epihalohydrin or 2-methylepihalohydrin in the liquid reaches 1% by weight or less, the evaporation rate of these evaporation components is rapidly reduced, and it is difficult to efficiently remove these evaporation components. When the concentration of these components is 10% by weight or less, particularly 1% by weight or less, if the purification in the step (C) is insufficient, 100 to 16%
It has been found that at high temperatures, such as 5 ° C., the oxirane oxygen content tends to decrease. It is considered that this decrease in the oxirane oxygen content is caused by a trace amount of impurities remaining due to insufficient washing in the step (C). However, when using an aqueous solution deficient in purification aid, it is difficult to completely remove impurities even if the number of washings in step (C) is increased, and increasing this number of washings is It is not preferable because the yield of the product obtained in the step (D) decreases. Therefore, step (C)
In the purification in the above, an aqueous solution of a purification aid having a high washing effect is used to prepare a liquid substance containing impurities in an acceptable trace amount, and in step (D), the liquid substance or its concentrated liquid It is preferable to remove these evaporated components in a short time to produce a product substantially free of these evaporated components.

On a substrate heated to a temperature of 100 to 165 ° C., apply this liquid or a concentrate thereof having a thickness of less than 500 microns, preferably a concentrate having an epihalohydrin or 2-methyl epihalohydrin concentration of 1 to 60% by weight. It has been found that when a film is formed, the above-mentioned evaporating component evaporates quickly from the film, and a liquid film having a reduced evaporating component concentration is formed. However, forming a film of this liquid or its concentrate less than 30 microns is
It is not efficient because the area of the coating formed from this liquid or its concentrate per unit weight is correspondingly increased. According to a preferred embodiment of the present invention, the coating film of the liquid material or the concentrated liquid to be formed is applied with an applicator to obtain 1
30 to 5 minutes on the surface of the substrate heated to a temperature of 00 to 165 ° C.
It is formed with a thickness of 00 microns, preferably 100-450 microns. Then, under reduced pressure, preferably 5 mmHg
By evaporating the above-mentioned evaporation component from the coating film under the pressure of the following evaporation component, the concentration of the evaporation component in the coating film can be reduced in a short time.

In the case of a liquid film substantially containing no evaporating component having a concentration of the evaporating component of 100 ppm by weight or less, especially 10 ppm by weight or less, the formed coating film is heated as it is to remove the evaporating component. Although it can be obtained by a method of evaporating, it can be obtained by a more efficient method. According to a preferred embodiment of the present invention, the substrate surface, preferably a vertical surface, has a sufficient spread in the vertical and horizontal directions, 30 to 500 microns, preferably 100 to 450 microns.
Forming a coating film of the liquid material or the concentrate thereof with a thickness of micron so that the concentration of the evaporating component gradually decreases from one end thereof to the opposite end thereof, preferably from the upper end to the lower end; Under a reduced pressure of 5 mmHg or less, for example, under a pressure of an evaporation component of 0.1 to 5 mmHg, 100 to 165
C., preferably at a temperature of 120 to 160.degree. C., and evaporating the evaporating component at a temperature of from 120 to 160.degree. While supplying and gradually moving the liquid under evaporation and film thickness maintenance from the coating film toward the opposite end, a liquid material having a reduced concentration of the evaporated component from the opposite end is preferably collected continuously. According to the method (D ′), the liquid component or its concentrated solution can be efficiently removed from the evaporated component.

According to this method (D '), epihalohydrin, 2-methylepihalohydrin and other volatile substances contained in the liquid obtained in the step (C) can be removed in a short time and substantially by using these volatile components. Can be removed to a level that does not contain, so that the generation of insoluble contaminants that occurs while the temperature is maintained at a high temperature to evaporate these evaporation components can be significantly suppressed. Therefore, as described above, it is obtained when none of the preferred method (B ') in the step (B), the preferred method (C') in the step (C), and the method using no purification aid (C ") are used. This method (D ') can provide a product containing no insoluble foreign matter even from a liquid material having a large amount of impurities.
In particular, tris (2,3-epoxypropyl) ester or tris (2-methyl-2,3-epoxypropyl) ester of isocyanuric acid and bis (2,3
-Epoxypropyl) ester or bis (2-methyl-
In the case of producing products of crystalline derivatives such as (2,3-epoxypropyl) ester, if these products contain the insoluble foreign substances as described above, they are also removed by the subsequent purification step (E). However, if the above-mentioned insoluble foreign substances are not contained, the purity can be further increased by the purification step (E). It is suitable.

[0062] The preferred method of removing the evaporated components can be carried out smoothly by using an evaporator made for such a method. For example, the evaporator has a cylindrical portion, a lid portion having a liquid supply port and a vapor discharge port at an upper portion of the cylindrical portion, and a bottom portion having a liquid discharge port at a lower portion of the cylindrical portion. A jacket for circulating a heating medium for heating is provided outside the cylindrical portion, and a steam outlet is connected to a pressure reducing device having a condenser. Inside the cylindrical portion, there are a rotating shaft inserted from the lid portion, a disk attached to the upper portion of the rotating shaft, and a support member positioned below the disk and fixed to the rotating shaft. An applicator which is previously attached via a spring or fitted with a clearance in the holder is provided. The applicator uses the adjusted force of this spring
Or it is pressed against the inner surface of the cylindrical part by the centrifugal force at the time of rotation,
And it is installed so that the inner surface of this cylindrical part can slide by rotation of a rotating shaft. The applicator has the shape of an elongated rectangular parallelepiped, and its cylindrical side has a vertically elongated flat surface. In this plane, a plurality of grooves are cut at regular intervals from the top to the bottom of the plane so as to traverse the plane at a fixed inclination angle with respect to the horizontal line.

By adjusting the strength of the spring for pressing the applicator of the evaporator, the supply speed of the liquid or its concentrate, the temperature of the coating in the evaporator, etc., the coating formed on the inner surface of the cylinder is adjusted. The thickness is adjusted. When the liquid substance or its concentrated liquid is supplied from the liquid supply port of the lid while rotating the rotating shaft, the liquid reaches the disk inside the cylinder, and then the liquid on the disk moves on the disk by centrifugal force. It flows toward the outer circumference and leaves the outer circumference of the disk to reach the top of the inner surface of the cylinder. The liquid that has reached the upper portion of the inner surface of the cylinder is applied to the inner surface of the cylinder by the flat portion of the rotating applicator, and a coating film is formed on the inner surface of the cylinder. Then, the liquid material or the concentrated liquid supplied subsequently is brought into contact with the corner of the plane on the cylindrical side of the applicator to cause mixing with the lower coating film,
It is moved downward on the inner surface of the cylinder through a groove that crosses at an angle of inclination. When the supply of the liquid material or the concentrate thereof is continued while rotating the rotating shaft in this manner, a coating film can be formed on the entire inner surface of the cylinder.

When the rotary shaft is rotated and the supply of the liquid or the concentrated liquid is continued while causing the evaporation component to evaporate from the formed film of the liquid or the concentrated liquid, the applicator passes. While the coating is renewed periodically, the coating with the highest concentration of evaporating component at the top of the inner surface of the cylinder, the concentration of the evaporating component gradually decreases downward, and the coating with the lowest concentration of evaporating component at the bottom It can be formed on the inner surface. If the supply of the liquid substance or its concentrated liquid is further continued while rotating the rotating shaft, the liquid having the lowest concentration of the evaporating component accumulates at the bottom of the evaporator. This accumulated liquid can be recovered from the outlet at the bottom of the evaporator. Evaporators for causing such evaporation are already known,
And it can also be obtained as a commercial product.

As a method of removing these evaporated components from the liquid substance or the concentrated liquid thereof using the above-described evaporator, the concentration of the evaporated components is reduced to 100 ppm or less, preferably 50 ppm or less at one time, rather than in multiple steps. For example, a method in which a liquid is first reduced to a concentration of about 2000 to 4000 ppm of an evaporating component, and a liquid having a concentration substantially equal to that containing substantially no evaporating component is reached from the liquid having the second concentration as described above. It is preferable to carry out. When the product is purified by the recrystallization method as described later, it is not necessary to remove the evaporated components by evaporation to such an extent that they do not substantially contain the evaporated components. For example, the epihalohydrin or 2-methylepihalohydrin content of about 1000 ppm is required. Products.

By this step (D), bis (2,3-epoxypropyl) ester or bis (2-methyl-2,3-epoxypropyl) ester of phthalic acid, isophthalic acid or terephthalic acid; trimellitic acid or trimesic acid Tris (2,3-epoxypropyl) ester or tris (2-methyl-2,3-epoxypropyl) ester; N, N'-bis (2,3-epoxypropyl) derivative of hydantoin or N, N'-bis ( 2-methyl-2,3-epoxypropyl) derivatives; preferred derivatives such as tris (2,3-epoxypropyl) ester or tris (2-methyl-2,3-epoxypropyl) ester of isocyanuric acid are obtained as high-purity products. Can be

As described above, in each of the steps (A) to (D), a preferred method can be adopted, and by combining such preferred steps (A) to (D), the present invention can be carried out. A high-purity epoxy compound can be produced by a preferable method. Such a preferred method is a method comprising step (A), step (B) employing method (B '), step (C) employing step (C') and step (D); step (A) , A step (B), a step (C) employing the method (B '), and a step (D) employing the method (D'); a step (A), a step (B), and a method (C '). ) And step (D) employing method (D '), and the most preferred method is step (A), step (B) employing method (B'). ), A step (C) employing the method (C ′) and a step (D) employing the method (D ′). These preferred or most preferred methods are suitable for industrial production performed on a large scale.
Especially terephthalic acid bis (2,3-epoxypropyl)
Ester or bis (2-methyl-2,3-epoxypropyl) ester, or tris (2,2-isocyanuric acid)
In the case of producing a crystalline derivative such as 3-epoxypropyl) ester or tris (2-methyl-2,3-epoxypropyl) ester, a purification method is not used as described above, but the preferred method (C ″) is used. Alternatively, by adopting a method combining these, it is possible to obtain these products with high purity, for example, after the step (A), in the step (B), in the step (B) and the method (B ′). In the method (D), the method (D ′) is used in combination, and in the step (B), the method (B ′) is used in combination with the method (C ″) using water containing no purification aid in the step (C). Method and process (C) to be adopted
And (D ′) in step (D), and most preferably, method (B ′) and step (B) in step (B). The method (C ″) using water containing no purification aid in (C) and the method (D ′) in step (D) are used in combination.

As the derivatives obtained in the step (D), bis (2,3-epoxypropyl) ester of terephthalic acid, bis (2-methyl-2,3-epoxypropyl) ester of terephthalic acid and tris (isocyanuric acid) 2,
Since compounds such as 3-epoxypropyl) ester and tris (2-methyl-2,3-epoxypropyl) ester of isocyanuric acid are crystalline, these compounds are:
The step (E) added to the step (D) allows for further purification by a recrystallization method. In the step (E), the step (D)
As a solvent for dissolving the product recovered in the above, methanol, ethanol, propanol, methyl ethyl ketone, ethyl acetate, benzene, toluene or a mixture thereof can be used, and methanol is particularly preferable. In the recrystallization method, the above product is dissolved in 1 to 10 times by weight, preferably 2 to 6 times by weight of the solvent at a temperature near its boiling point, and then gradually, preferably 2 to 30 ° C /
It is preferable to precipitate crystals by cooling at a temperature lowering rate over time. The precipitated crystals can be easily separated from the solution by a conventional method, for example, filtration, and then the separated crystals are washed with the above-mentioned solvent, if desired, and then dried by a conventional method to obtain a final product. Is collected. The final product has a lower epoxy equivalent and higher thermal stability than the product before purification by the recrystallization method. This step (E) can also be used in industrial production carried out on a large scale, in particular to produce end products of high purity, and as described above, methods (B '), (C'), Method (C "), Method (D ')
In the method employing any one of the above, the method is carried out in a mode of adding the compound after the step (D).

[0069]

【Example】

Example 1 Step (A): In a 2 liter glass reaction flask equipped with a stirrer having paddle blades, 20 g of water was added.
5.5 g of tetraethylammonium bromide, 925
g (10 moles) of epichlorohydrin and 166 g (1
Mol) of terephthalic acid to form a reaction mixture. Next, the reaction mixture in the flask was heated with stirring to raise the temperature. When the temperature of the reaction mixture reached 89 ° C., the reaction mixture began to boil under atmospheric pressure but continued to heat. The generated vapor was cooled in a condenser, and the liquefied epichlorohydrin was continuously refluxed into the total volume flask, and the liquefied water was discharged out of the flask for 3 hours to raise the temperature of the reaction mixture to 121 ° C. Was reached. At this point, the heating was stopped and the reaction mixture was cooled to obtain a reaction product having a temperature of 45 ° C. Liquid chromatography analysis confirmed that this reaction product did not contain a compound having a carboxyl group of the starting terephthalic acid.

Step (B): Then, while maintaining the total amount of the reaction product in the flask at 45 ° C., 176 g of a 50% by weight aqueous solution of sodium hydroxide (N
(a mol of aOH) is 100 mm.
The reaction mixture was formed by starting under reduced pressure of Hg, while at the same time water and epichlorohydrin were evaporated from the reaction mixture under vigorous stirring. While gradually increasing the degree of decompression,
The vapor is cooled in a condenser, the liquefied epichlorohydrin is continuously refluxed into the volumetric flask, and the liquefied water is continuously discharged out of the flask, and the degree of vacuum is reduced to 60 m.
Upon reaching mHg, the dropping was completed to prepare a slurry containing precipitated sodium chloride. It took 6 hours from the start of the dropping to the completion.
During this time, the reaction mixture under stirring became cloudy with precipitated sodium chloride, but was kept uniform throughout. According to liquid chromatography analysis, 1% of the compound having a 2-hydroxy-3-chloropropyl group was obtained in the obtained slurry.
It was below.

Step (C): The total amount of the slurry obtained in the step (B), 600 g of distilled water and 2 g of sodium toluenesulfonate were stirred for 5 minutes in a glass vessel, and then allowed to stand. At the elapse of 10 minutes from the start of the placement, the first epichlorohydrin layer was completely recovered, and the aqueous layer was transferred to another container. Next, the whole amount of the recovered epichlorohydrin layer,
600 g of a 5% by weight aqueous solution of sodium dihydrogen phosphate in distilled water
And 2 g of sodium toluenesulfonate were stirred in a glass container for 5 minutes and then allowed to stand.
After the elapse of minutes, the entire epichlorohydrin layer was recovered for the second time, and the aqueous layer was transferred to another container.

Next, the total amount of the epichlorohydrin layer collected for the second time and 800 g of distilled water were stirred in a glass container for 5 minutes and allowed to stand, and 10 minutes after the start of the standing, the final epichlorohydrin layer was removed. By recovering the entire amount, a purified liquid was prepared. Step (D): The entire amount of the final epichlorohydrin layer obtained in step (C) is supplied to a rotary evaporator, and the epichlorohydrin is distilled off by heating under reduced pressure. Heated. After cooling to room temperature, the contents were taken out of the evaporator to obtain 257 g of a product. This product amount was calculated to be 92% yield based on the starting terephthalic acid used in step (A).

This product contains no detectable ionic chlorine and has an epoxy equivalent of 146, a kaolin turbidity of 1 or less when melted at 140 ° C., and a turbidity of 24 at 150 ° C. in a closed vessel.
An epoxy equivalent of 148 when heated for an hour. The rate of change of the epoxy equivalent by this heating was calculated to be 1.4%. Step (E): After melting the product obtained in step (D), 100 g of the melt is gradually added to 400 g of methanol in a flask with stirring to form a methanol solution of the product. Was heated to the reflux temperature of methanol, and the methanol solution was cooled to 5 ° C. over 12 hours to precipitate white crystals in the solution. The white crystals were separated by filtration and dried to obtain 75 g of a final product.

This final product has an epoxy equivalent of 140,
It shows a kaolin turbidity of 1 or less when melted at 140 ° C. and an epoxy equivalent of 141 when heated at 150 ° C. for 24 hours in a closed vessel.
It was calculated to be 7%. Comparative Example 1 The slurry obtained in the step (B) in the same manner as in the example 1 was stirred and allowed to stand still in the same manner as the step (C) in the example 1 except that sodium toluenesulfonate was not used. The epichlorohydrin layer 10 minutes after the standing was strongly turbid. After further standing for 12 hours, the epichlorohydrin layer was collected as the first epichlorohydrin layer. The second washing was performed in the same manner without using sodium toluenesulfonate. However, the epichlorohydrin layer at 10 minutes after the standing was strongly turbid. The epichlorohydrin layer after further standing for 12 hours was collected as a second epichlorohydrin layer. The final washing was carried out in the same manner without using sodium toluenesulfonate. However, the epichlorohydrin layer at 10 minutes after standing was strongly turbid. After leaving still for 12 hours, it was collected as a final epichlorohydrin layer.

The final epichlorohydrin layer was treated in the same manner as in step (D) of Example 1 to obtain 251 g of product from the evaporator, which product had an epoxy equivalent of 151 and an ion equivalent of 5 ppm by weight. Indicates the chlorine content,
Kaolin turbidity 2 when melted at 140 ° C and 24 at 150 ° C
When heated for an hour, the epoxy equivalent was 158, and the change rate of this epoxy equivalent was calculated to be 4.6%.

This product was treated in the same manner as in the step (E) of Example 1 to obtain a dried final product of 70 g.
Was obtained as white crystals. The final product has an epoxy equivalent of 142, a kaolin turbidity of 2 at 140 ° C. when melted, and an epoxy equivalent of 145 when heated at 150 ° C. for 24 hours in a closed container. The rate of change of this epoxy equivalent is calculated as 2%. Was done.

Example 2 Steps (A) and (B): A slurry containing precipitated sodium chloride was obtained in the same manner as in Steps (A) and (B) of Example 1. Step (C): A final epichlorohydrin layer was recovered in the same manner as in step (C) of Example 1, except that 2 g of sodium vinyl sulfonate was used instead of 2 g of sodium toluene sulfonate.

Step (D): From the final epichlorohydrin layer obtained in step (C), the step (D) of Example 1 was used.
257 g of product from the evaporator were obtained. This product contains no ionic chlorine to be detected,
An epoxy equivalent of 146, a kaolin turbidity of 1 or less when melted at 140 ° C., and an epoxy equivalent of 148 when heated at 150 ° C. for 24 hours in a closed vessel.

Example 3 Steps (A) and (B): A slurry containing precipitated sodium chloride was obtained in the same manner as in Steps (A) and (B) of Example 1. Step (C): A final epichlorohydrin layer was recovered in the same manner as in step (C) of Example 1 except that 2 g of sodium octanesulfonate was used instead of 2 g of sodium toluenesulfonate.

Step (D): The step (D) of Example 1 was determined from the total amount of the final epichlorohydrin layer obtained in the step (C).
257 g of product from the evaporator were obtained. This product contains no detectable ionic chlorine and its epoxy equivalent, kaolin turbidity when melted at 140 ° C., and epoxy equivalent when heated at 150 ° C. in a closed container for 24 hours are the products of Example 1. Were identical to those values.

Example 4 Steps (A) and (B): A slurry containing precipitated sodium chloride was obtained in the same manner as in Steps (A) and (B) of Example 1. Step (C): The final epichlorohydrin layer was recovered in the same manner as in step (C) of Example 1 except that 2 g of ammonium toluenesulfonate was used instead of 2 g of sodium toluenesulfonate.

Step (D): The step (D) of Example 1 was obtained from the total amount of the final epichlorohydrin layer obtained in the step (C).
In a similar manner, 256 g of product from the evaporator were obtained. This product contains no detectable ionic chlorine and
An epoxy equivalent of 47, a kaolin turbidity of 1 or less when melted at 140 ° C., and an epoxy equivalent of 150 when heated at 150 ° C. in a closed container for 24 hours were calculated, and the change rate of this epoxy equivalent was calculated to be 2%.

Example 5 Steps (A) and (B): The same procedure as in step (A) of Example 1 was repeated except that 1065 g of 2-methylepichlorohydrin was used instead of 925 g of epichlorohydrin. The reflux of -methyl epichlorohydrin was started and the temperature of the reaction mixture was allowed to reach 120 ° C over 8 hours. Then, 176 g of a 50% by weight aqueous sodium hydroxide solution was added over 6 hours to the reaction mixture kept at 45 ° C. in the same manner as in the step (B) of Example 1 to obtain a slurry containing precipitated sodium chloride. I got

Step (C): 2 parts of sodium toluenesulfonate were added to the total amount of the slurry obtained in step (B).
The final 2-methylepichlorohydrin layer was recovered in the same manner as in step (C) of Example 1 except that 2 g of potassium benzenesulfonate was used instead of g. Step (D): In the same manner as in Step (D) of Example 1, 284 g of a product from the evaporator was obtained from the entire amount of the final 2-methylepichlorohydrin layer obtained in Step (C).
This product contains no detectable ionic chlorine and contains 163
Epoxy equivalent of 1 or less kaolin turbidity when melted at 140 ° C, and 1 when heated at 150 ° C for 24 hours in a closed container
An epoxy equivalent of 65 was obtained, and the rate of change of the epoxy equivalent was calculated to be 1.2%.

Example 6 Step (A): 30 g of water and 5.5 g were placed in a 2 liter reaction flask equipped with a stirrer having paddle blades.
And 1388 g of tetramethylammonium chloride
(15 mol) of epichlorohydrin and 129 g (1 mol) of cyanuric acid were charged to form a reaction mixture. Next, the reaction mixture in the flask was heated with stirring to raise the temperature. When the temperature of the reaction mixture reached 89 ° C., the reaction mixture began to boil under atmospheric pressure but continued to heat. The generated steam is cooled in a condenser, and the liquefied epichlorohydrin is continuously refluxed into the entire volume flask,
The liquefied water was allowed to drain out of the flask for 5 hours, allowing the temperature of the reaction mixture to reach 120 ° C. At this point, the heating was stopped and the reaction mixture was cooled to obtain a reaction product having a temperature of 45 ° C. Unreacted cyanuric acid was not detected in this product.

Step (B): Then, while maintaining the total amount of the reaction product in the flask at 50 ° C., the reaction product was added with 256 g of a 50% by weight aqueous solution of sodium hydroxide (N
(3.2 mol as aOH)
A reaction mixture was formed by starting under reduced pressure of Hg. At the same time, water and epichlorohydrin were evaporated from the reaction mixture under vigorous stirring. While gradually increasing the degree of vacuum, the steam is cooled in a condenser, the liquefied epichlorohydrin is continuously refluxed into the entire volume flask, and the liquefied water is continuously discharged out of the flask, and the degree of vacuum is reduced to 60 m.
When the mHg was reached, the dropping was completed to obtain a slurry containing precipitated sodium chloride. It took 6 hours from the start of the dropping to the completion thereof. During this time, the reaction mixture under stirring was clouded with precipitated sodium chloride, but was kept uniform throughout. According to the liquid chromatography analysis, 2-
The content of the compound having a hydroxy-3-chloropropyl group was 1% or less.

Step (C): The total amount of the slurry obtained in the step (B), 600 g of distilled water and 2 g of sodium toluenesulfonate were stirred in a glass vessel for 5 minutes, and then allowed to stand. At the elapse of 10 minutes from the start of the placement, the first epichlorohydrin layer was completely recovered, and the aqueous layer was transferred to another container. Next, the whole amount of the recovered epichlorohydrin layer,
600 g of a 5% by weight aqueous solution of sodium dihydrogen phosphate and 2 g of sodium toluenesulfonate were stirred for 5 minutes in a glass container and allowed to stand. After 10 minutes from the start of the standing, the second epichlorohydrin layer was removed. The entire amount was collected, and the aqueous layer was transferred to another container.

Next, the total amount of the epichlorohydrin layer collected for the second time and 800 g of distilled water were stirred in a glass container for 5 minutes and allowed to stand, and 10 minutes after the start of the standing, the final epichlorohydrin layer was removed. The entire amount was recovered. Step (D): The entire amount of the final epichlorohydrin layer obtained in step (C) is supplied to a rotary evaporator, and the epichlorohydrin is distilled off by heating under reduced pressure. Heated. After cooling to room temperature, the content was taken out of the evaporator to obtain 267 g of a product. This product amount was calculated to be 90% yield based on the starting material cyanuric acid used in step (A).

This product contains no detectable ionic chlorine and has an epoxy equivalent of 103, a kaolin turbidity of 1 or less when melted at 140 ° C., and an epoxy equivalent of 104 when heated in a closed vessel at 150 ° C. for 24 hours. And the rate of change of the epoxy equivalent by this heating was calculated to be 1%. Step (E): After melting the product obtained in step (D), 100 g of the melt is gradually added to 400 g of methanol in a flask with stirring to form a methanol solution of the product. After heating the solution to the reflux temperature of methanol and cooling the methanol solution to 5 ° C. over 12 hours, white crystals were precipitated in the solution. The white crystals were separated by filtration and dried to obtain 82 g of a final product.

The final product has an epoxy equivalent of 99, 1
It showed a kaolin turbidity of 1 or less when melted at 40 ° C. and an epoxy equivalent of 99 when heated at 150 ° C. for 24 hours in a closed container. The rate of change of the epoxy equivalent by this heating was calculated as 0%. Comparative Example 2 The slurry obtained in the step (B) in the same manner as in Example 6 was stirred and allowed to stand as in Step (C) in Example 6, except that sodium toluenesulfonate was not used. The epichlorohydrin layer 10 minutes after the standing was strongly turbid. After further standing for 12 hours, the epichlorohydrin layer was collected as the first epichlorohydrin layer. The second washing was performed in the same manner without using sodium toluenesulfonate. However, the epichlorohydrin layer at 10 minutes after the standing was strongly turbid. The epichlorohydrin layer after further standing for 12 hours was collected as a second epichlorohydrin layer. In the final case, the same procedure was carried out without using sodium toluenesulfonate. However, the epichlorohydrin layer at 10 minutes after standing was strongly turbid. After leaving still for 12 hours, it was collected as a final epichlorohydrin layer.

The final epichlorohydrin layer was treated in the same manner as in step (D) of Example 6 to obtain 258 g of a product from the evaporator.
Epoxy equivalent, ionic chlorine content of 4 ppm by weight, and a kaolin turbidity of 3 when melted at 140 ° C. The product exhibited an epoxy equivalent of 113 when heated at 150 ° C. for 24 hours, and the rate of change of the epoxy equivalent was 4.
It was calculated to be 6%.

This product was treated in the same manner as in the step (E) of Example 6 to obtain 80 g of a dried final product.
Was obtained as white crystals. The final product has an epoxy equivalent of 100, a kaolin turbidity of 2 when melted at 140 ° C., and an epoxy equivalent of 101 when heated at 150 ° C. for 24 hours in a closed vessel, with a change in epoxy equivalent of 1%. Was calculated.

Example 7 Steps (A) and (B): Except that 5.5 g of ethyltriphenylphosphonium bromide was used instead of 5.5 g of tetramethylammonium chloride, (A) and (B) of Example 6 were used. In the same manner as in (1), a slurry containing precipitated sodium chloride was obtained.

Step (C): The final epichlorohydrin layer was recovered in the same manner as in Step (C) of Example 6. Step (D): From the final epichlorohydrin layer obtained in step (C), 265 g of a product was obtained from the evaporator in the same manner as in step (D) of Example 6. This product contains no detectable ionic chlorine and exhibits an epoxy equivalent of 104, a kaolin turbidity of 1 or less when melted at 140 ° C, and an epoxy equivalent of 105 when heated in a closed vessel at 150 ° C for 24 hours; The change rate of this epoxy equivalent was calculated to be 1%.

Example 8 Steps (A) and (B): A slurry containing precipitated sodium chloride was obtained in the same manner as in Steps (A) and (B) of Example 1. Step (C): A final epichlorohydrin layer was recovered in the same manner as in step (C) of Example 1, except that 2 g of toluenesulfonic acid was used instead of 2 g of sodium toluenesulfonic acid.

Step (D): From the final epichlorohydrin layer obtained in step (C), the step (D) of Example 1 was used.
In the same manner as in the above, 255 g of a product was obtained from the evaporator.
This product contains no detectable ionic chlorine and 146
Epoxy equivalent of 1 or less kaolin turbidity when melted at 140 ° C, and 1 when heated at 150 ° C for 24 hours in a closed container
An epoxy equivalent of 48 was obtained, and the rate of change of the epoxy equivalent was calculated to be 1.4%.

Example 9 Steps (A) and (B): A slurry containing precipitated sodium chloride was obtained in the same manner as in Steps (A) and (B) of Example 1. Step (C): A final epichlorohydrin layer was recovered in the same manner as in step (C) of Example 1 except that 2 g of sodium benzoate was used instead of 2 g of sodium toluenesulfonate.

Step (D): The step (D) of Example 1 was obtained from the total amount of the final epichlorohydrin layer obtained in the step (C).
258 g of product from the evaporator were obtained. This product contains no detectable ionic chlorine and
An epoxy equivalent of 47, a kaolin turbidity of 1 or less when melted at 140 ° C., and an epoxy equivalent of 150 when heated at 150 ° C. in a closed container for 24 hours were calculated, and the change rate of this epoxy equivalent was calculated to be 2%.

Example 10 Steps (A) and (B): A slurry containing precipitated sodium chloride was obtained in the same manner as in Steps (A) and (B) of Example 1. Step (C): A final epichlorohydrin layer was recovered in the same manner as in step (C) of Example 1, except that 2 g of triethanolamine salt of toluenesulfonic acid was used instead of 2 g of sodium toluenesulfonic acid.

Step (D): From the total amount of the final epichlorohydrin layer obtained in step (C), the step (D) of Example 1 was used.
In the same manner as described above, 256 g of a product was obtained from the evaporator.
This product contains no detectable ionic chlorine and 147
Epoxy equivalent of 1 or less kaolin turbidity when melted at 140 ° C, and 1 when heated at 150 ° C for 24 hours in a closed container
An epoxy equivalent of 49 was obtained, and the rate of change of the epoxy equivalent was calculated to be 1.4%.

Example 11 In this example, an internal volume 2 equipped with a stirrer having paddle blades was used.
Using a 0 liter glass reactor, Example 1
Performed on a scale of 0x. Step (A) could be performed smoothly as in Example 1. Step (B) was also performed in the same manner as in Example 1, but a part of the precipitated sodium chloride started to stagnate around the lower side wall of the reactor during the addition of the aqueous sodium hydroxide solution. When the addition of the aqueous sodium hydroxide solution was continued as it was, the stagnation amount of the precipitated sodium chloride gradually increased and adhered to the side wall of the reactor. The rotation speed of the stirrer was increased to continue adding sodium hydroxide.
Until the addition was complete, the deposited sodium chloride did not disperse in the reaction mixture. The content of the compound having a 2-hydroxy-3-chloropropyl group contained in the obtained slurry was 1% or less. The step (C) was also performed smoothly as in Example 1.

Step (D) was carried out on the same scale as in Example 1 and could be smoothly carried out in the same manner, but the yield was slightly reduced to 9
It was 0%. And the product has 151 epoxy equivalents,
It exhibited a kaolin turbidity of 1 or less when melted at 140 ° C. and an epoxy equivalent of 155 when heated at 150 ° C. for 24 hours in a closed container. The rate of change of the epoxide equivalent by this heating is 2.
It was calculated to be 6%.

Step (E) was carried out in the same manner as in Example 1, but the yield of the final product obtained was slightly reduced to 72
%Met. This final product has 140 epoxy equivalents,
When heated at 150 ° C. for 24 hours in a closed container, it showed an epoxy equivalent of 141. Example 12 In this example, Example 11 was repeated replacing the reactor with two baffles having a length of 15 cm, a width of 2 cm and a thickness of 2 mm.

Step (A) could be performed smoothly as in Example 11. Also in the step (B), the stagnation of the precipitated sodium chloride and the adhesion to the side wall as in Example 11 did not occur, and uniform stirring of the reaction mixture could be maintained. Through steps (C) and (D) in the same manner as in Example 11, a product was obtained with a yield of 93%. The product exhibited an epoxy equivalent of 146, a kaolin turbidity of 1 or less when melted at 140 ° C., and an epoxy equivalent of 148 when heated at 150 ° C. for 24 hours in a closed vessel. The rate of change of the epoxide equivalent due to this heating was calculated to be 1.4%. Step (E) was also performed in the same manner as in Example 11, and a product was obtained with a yield of 75%.

Example 13 In this example, Example 6 was performed on a 100-fold scale. The reactor used was made of stainless steel, 20
It has an inner volume of 0 liters and 60c inside 2 places
It has a baffle with a length of m, a width of 4 cm and a thickness of 4 mm. The used stirrer consists of a rotating shaft and two flat plates attached to the rotating shaft, and these two flat plates are arranged in one plane including the rotating shaft so as to have a structure symmetrical to the left and right of the rotating shaft. It has a lattice portion in the upper 2/3 thereof and a paddle portion in the lower 1/3 thereof. This stirrer has a blade width of 0.53 times the inner diameter of the reactor.

When the stirrer is immersed in the liquid in the reactor and rotated, the lower paddle portion causes the liquid at the lower part of the reactor to flow toward the side wall at the lower part of the reactor, and the liquid is supplied to the reactor. The liquid rises up to the top of the liquid, circulating in a laminar flow along the side walls, where it is subdivided by shear at the grid of a rotating stirrer, inverting and engulfing towards the lower center of the reactor. You. Therefore, when the rotation of this stirrer is continued, the liquid flows upward along the side wall from the lower part of the reactor to the upper liquid level, and the entrainment flow of the liquid, which is reversed from the vicinity of the upper part wall of the liquid and heads toward the lower part of the center of the reactor, The entangled stream is kept uniform while being mixed by the subdivision.

Step (A) could be carried out smoothly as in Example 6. Also in the step (B), the stagnation of the precipitated sodium chloride and the adhesion to the side wall of the reactor as in Example 11 did not occur, and the reaction mixture could be maintained uniform. The step (C) was also performed smoothly as in the case of Example 6. Through the process (D) in the same manner as in Example 6, a product was obtained in a yield of 90%. This product exhibited an epoxy equivalent of 102, a kaolin turbidity of 1 or less when melted at 140 ° C., and an epoxy equivalent of 103 when heated at 150 ° C. for 24 hours in a closed vessel. The rate of change of the epoxide equivalent due to this heating was calculated to be 1%. Step (E) can be carried out in the same manner as in Example 6, and a product can be obtained with a yield of 82%. This product exhibited an epoxy equivalent of 99 and the same epoxy equivalent when heated in a closed vessel at 150 ° C. for 24 hours.

Example 14 Step (A): A glass reactor having an inner volume of 20 liters equipped with a stirrer having paddle blades was charged with 300 g of water, 5
12. 5 g of tetramethylammonium chloride;
A reaction mixture was formed by charging and stirring 88 kg of epichlorohydrin and 1.29 kg of cyanuric acid. Then, the reaction mixture was heated with stirring to raise the temperature.

When the temperature of the reaction mixture reached 89 ° C., the reaction mixture began to boil under atmospheric pressure, but continued to be heated. The generated vapor is cooled in a condenser, and all of the liquefied epichlorohydrin is continuously refluxed into the reactor, and the liquefied water is discharged out of the reactor for 5 hours, thereby lowering the temperature of the reaction mixture. 120 ° C. was reached. At this point, the heating was stopped and the reaction mixture was cooled to obtain a reaction product having a temperature of 45 ° C. Unreacted cyanuric acid was not detected in this reaction product.

Step (B): While keeping the total amount of the above reaction product at 50 ° C. under vigorous stirring, 2.56 kg of a 50% by weight aqueous solution of sodium hydroxide was added dropwise to the reaction product under reduced pressure of 100 mmHg. To form a reaction mixture. At the same time as the start of the dropwise addition, water and epichlorohydrin were evaporated from the reaction mixture.

While gradually increasing the degree of pressure reduction, the steam was cooled in a condenser, all the liquefied epichlorohydrin was continuously refluxed into the reactor, and the liquefied water was continuously discharged out of the reactor. When the degree of pressure reduction reached 60 mmHg, the dropping was completed to obtain a slurry containing precipitated sodium chloride. It took 6 hours from the start of the dropping to the completion. After continuing the above reflux for another 5 minutes, the reduced pressure in the reactor was released and stirring was stopped.

According to the liquid chromatography analysis, the content of the compound having a 2-hydroxy-3-chloropropyl group contained in the obtained liquid product was 1% or less. The whole amount of the slurry obtained by repeating the above steps (A) and (B) four times was prepared for step (C). Step (C): To the above slurry in a vessel, 24 liters of distilled water and 80 g of sodium toluenesulfonate are added and gently stirred to dissolve the precipitated sodium chloride in the slurry in the added water. After allowing the liquid inside to stand, the entire amount of the organic layer was recovered to obtain a transparent liquid.

A water washing apparatus for washing the above liquid material with liquid particles was prepared. The water washing device has a glass cylindrical portion having a height of 300 mm and an inner diameter of 50 mm, a cylindrical liquid storage portion provided continuously above the upper end of the cylindrical portion, and a lower portion provided continuously with the lower end of the cylindrical portion. It has a cylindrical liquid storage portion installed on the lower side, a lid portion covering the upper liquid storage portion, and a rotating shaft inserted through the center of the lid portion and inserted to the lower end of the cylindrical portion. The upper liquid storage portion has substantially the same inner diameter as the cylindrical portion and a height of 160 mm, and a liquid outlet is provided at an upper portion thereof. The lid is provided with a liquid supply conduit extending therethrough and extending to near the lower end of the upper liquid reservoir. The lower liquid storage part has substantially the same inner diameter as the cylindrical part and a depth of 160 mm, a liquid outlet is provided at the bottom thereof, and the lower liquid storage part penetrates the side wall at the middle of the lower liquid storage part. And a liquid supply conduit extending near the lower end of the rotating shaft. Six-stage perforated disks are attached to the rotating shaft at equal intervals from the lower end to the height near the upper end of the cylindrical portion, and the inner wall of the cylindrical portion has a height of 15 m between the perforated disks.
A donut-shaped baffle with a width of m is attached. Each perforated disk has a diameter of 40 mm, on the lower side of the outer circumference of which a band-like ring is installed, and the holes of the perforated disk have a diameter of 2 mm.
It is provided with a diameter of mm and penetrating from the upper surface to the lower surface of the board. The rotating shaft reciprocates by the operation of a driving device connected to its upper end.

After the liquid was supplied to the middle of the liquid storage section on the upper side of the washing device, the rotating shaft was rotated at 110 reciprocations per minute. 0.33 from the liquid supply conduit in the lower liquid reservoir
An aqueous solution containing 3% by weight of sodium toluenesulfonate and 3% by weight of sodium dihydrogen phosphate is supplied at a rate of 0.078 liters per minute, and is contacted with the liquid material from the liquid outlet of the upper liquid storage section. After the discharge of the aqueous solution has started, while discharging the liquid material from the bottom of the lower liquid storage section,
The supply of unpurified liquid was started at a rate of 0.51 liter per minute from the liquid supply conduit at the top of the washing device. Since the liquid obtained at the beginning of this discharge was not purified, it was returned to the liquid storage tank. The supplied aqueous solution is 0.3 to 7
It was observed that the particles were dispersed in the epichlorohydrin layer as liquid particles having a size of about mm. After the discharge of the purified transparent liquid started, 20 liters of the discharged liquid was collected as the purified liquid.

The purified liquid material was added to 0.03
The mixture was washed with a weight% aqueous solution of sodium toluene sulfonate. A second transparent liquid was obtained by continuously supplying the liquid at 0.45 liter per minute and supplying the aqueous solution at 0.19 liter per minute while rotating the rotating shaft at 110 reciprocations per minute. . The epichlorohydrin layer obtained in the second washing was recovered as a liquid purified in the step (C). The purified liquid contained 83% by weight epichlorohydrin.

Step (D): 2 liters collected from the liquid collected in step (C) are put into a rotary evaporator having an internal volume of 10 liters, and distillation of epichlorohydrin is started at a temperature of 60 ° C. under reduced pressure. Then, the temperature was raised while the degree of reduced pressure was gradually reduced, and the distillation of epichlorohydrin was continued to reach a liquid at a temperature of 140 ° C. under a reduced pressure of 2 mmHg. The cooled product then showed an epoxy equivalent of 102.

Example 15 Steps (A) to (C) of Example 6 were performed on a 10-fold scale. Step (D): The liquid recovered in step (C) is treated with a flash evaporator to obtain 70% by weight.
A concentrated solution having an epichlorohydrin concentration of A product of triglycidyl isocyanurate having a reduced epichlorohydrin concentration was obtained by using an evaporator for forming a coating film from this liquid and evaporating epichlorohydrin.

The evaporator used was a cylindrical part having an inner diameter of 315 mm and a height of 735 mm, a lid part having a liquid supply port and a vapor discharge port at the upper part of this cylindrical part, and a liquid part at the lower part of this cylindrical part. It has a bottom with an outlet. A jacket for circulating a heating medium for heating is provided outside the cylindrical portion,
The steam outlet is connected to a pressure reducing device having a condenser. Inside the cylindrical portion, there is a rotary shaft inserted from the lid portion, and an upper portion of the rotary shaft attached to the rotary shaft.
A disc having a diameter of 5 mm and an applicator positioned below the disc and fitted with clearance in a holder fixed to a rotating shaft are arranged. The applicator is installed so as to be pressed against the inner surface of the cylindrical portion by centrifugal force, and to slide on the inner surface of the cylindrical portion by rotation of the rotating shaft. The applicator has the shape of an elongated rectangular parallelepiped having a length of 600 mm, and its cylindrical side has an elongated flat surface with a width of 20 mm in the vertical direction. In this plane, a plurality of grooves are cut from the upper part to the lower part of the plane at an interval of 12 mm and crossing the plane at an inclination angle of 45 degrees with respect to the horizontal line. This groove has a depth of 8 mm and a width of 12 mm.

Heated steam was passed through the jacket of the evaporator, the rotating shaft was rotated at a speed of 200 revolutions per minute, and the pressure reducing device was operated to maintain a reduced pressure of 10 mmHg. The above-mentioned liquid concentrate having an epichlorohydrin concentration of 70% by weight was supplied to the evaporator at a rate of 22.4 kg / hr. A product having an evaporator bottom outlet liquid temperature of 103, an epoxy equivalent of 103, and a contained epichlorohydrin concentration of 2500 ppm was recovered from the outlet at the bottom of the evaporator.

The product thus recovered was a transparent liquid containing no insoluble foreign matter. Next, the recovered liquid product was treated again with the evaporator to obtain a product having a lower epihalohydrin concentration. This time, heating steam was passed through the jacket, the rotating shaft was rotated at a speed of 200 revolutions per minute, and the decompression device was operated for 0.2 mm.
A reduced pressure of mmHg was maintained. The above liquid having an epichlorohydrin concentration of 2500 ppm was fed at a rate of 14.0 kg / h. After a film thickness of 170 microns and an average liquid residence time of 18 seconds, the evaporator bottom outlet liquid temperature of 155 ° C., 103 A product having an epoxy equivalent and a contained epichlorohydrin concentration of 54 ppm was recovered from the outlet at the bottom of the evaporator. The recovered product was a transparent liquid containing no insoluble foreign matter. The yield of triglycidyl isocyanurate was 90% based on the starting cyanuric acid.

Step (E): 54 obtained in step (D)
A methanol solution of the product is formed by gradually adding 100 g of a melt of the product having an epichlorohydrin concentration of ppm to 400 g of methanol in a flask with stirring to form a methanol solution of the product. After that, the methanol solution was cooled to 5 ° C. over 12 hours to precipitate white crystals in the solution. The white crystals were filtered off and dried to give a final product having an epoxy equivalent of 99 in a yield of 82 g.

Example 16 In the same manner as in Steps (A) and (B) of Example 13,
A slurry containing precipitated sodium chloride was prepared. The entire amount of this slurry is then used, as in step (C) of Example 14, but with an increased throughput, a liquid is first prepared by dissolving out precipitated sodium chloride from the slurry by dissolution and washing with water Using the apparatus, a purified liquid was prepared by purifying first with an aqueous solution of sodium toluenesulfonate and sodium dihydrogen phosphate, and then secondly with an aqueous solution of sodium toluenesulfonate.

From this purified liquid, a concentrated solution was prepared by a flash evaporator in the same manner as in step (D) of Example 15, and epichlorohydrin was removed by using an evaporator for evaporating the coating film. , 10
27.0 kg of product having an epoxy equivalent of 1 and an epichlorohydrin concentration of 80 ppm were obtained. Example 17 Steps (A) and (B): A slurry containing precipitated sodium chloride was obtained in the same manner as in Steps (A) and (B) of Example 1.

Step (C): The first time was carried out in the same manner as in Example 1 except that washing was carried out with distilled water without using a purification aid. The second washing was performed in the same manner as in Example 1 except that 2 g of sodium cinnamate was used instead of 2 g of sodium toluenesulfonate. The final washing was performed in the same manner as in Example 1 except that an aqueous solution obtained by adding 0.1 g of sodium cinnamate to 800 g of distilled water was used to prepare a purified liquid.

Step (D): From the total amount of the final epichlorohydrin layer obtained in step (C), 257 g of a product was obtained from the evaporator in the same manner as in Example 1. This product contains no detectable ionic chlorine and its epoxy equivalent, 14
The kaolin turbidity when melted at 0 ° C. and the epoxy equivalent when heated at 150 ° C. in a closed vessel for 24 hours were identical to those of the product obtained in Example 1.

Example 18 Steps (A) and (B): A slurry containing precipitated sodium chloride was obtained in the same manner as in Steps (A) and (B) of Example 1. Step (C): The first time was carried out in the same manner as in Example 1 except that washing with distilled water was performed without using a purification aid.

The second washing was carried out in the same manner as in Example 1, except that 2 g of sodium naphthalenesulfonate, a formaldehyde condensate known as a water-soluble water reducing agent, was used instead of 2 g of sodium toluenesulfonate. The final washing was performed in the same manner as in Example 1 except that an aqueous solution obtained by adding 0.1 g of the above-mentioned formaldehyde condensate of sodium naphthalenesulfonate to 800 g of distilled water was used to prepare a purified liquid.

Step (D): From the total amount of the final epichlorohydrin layer obtained in step (C), 257 g of a product was obtained from the evaporator in the same manner as in Example 1. This product contains no detectable ionic chlorine and its epoxy equivalent, 14
The kaolin turbidity when molten at 0 ° C. and the epoxy equivalent when heated in a sealed container at 150 ° C. for 24 hours were identical to those of the product obtained in Example 1.

Example 19 Steps (A) and (B): A slurry containing precipitated sodium chloride was obtained in the same manner as in Steps (A) and (B) of Example 1. Step (C): The first was carried out in the same manner as in Example 1 except that 0.1 g of disodium phthalate was used instead of 2 g of sodium toluenesulfonate.

In the second washing, instead of 2 g of sodium toluenesulfonate, 0.5 g of disodium phthalate was used.
Was carried out in the same manner as in Example 1 except that The final wash is disodium phthalate 0.1g in 800g distilled water
A purified liquid was prepared in the same manner as in Example 1 except that an aqueous solution to which was added. Step (D): 257 g of a product was obtained from the evaporator in the same manner as in Example 1 from the total amount of the final epichlorohydrin layer obtained in step (C). This product contains no detectable ionic chlorine and its epoxy equivalent, kaolin turbidity when melted at 140 ° C, and epoxy equivalent when heated in a sealed container at 150 ° C for 24 hours are obtained in Example 1. Values were the same for those products.

Example 20 Steps (A) and (B): A slurry containing precipitated sodium chloride was obtained in the same manner as in Steps (A) and (B) of Example 1. Step (C): The first was carried out in the same manner as in Example 1, except that 0.2 g of sodium salicylate was used instead of 2 g of sodium toluenesulfonate.

In the second washing, instead of 2 g of sodium toluenesulfonate, 0.5 g of sodium salicylate was used.
Was carried out in the same manner as in Example 1 except that The final washing was performed in the same manner as in Example 1 to prepare a purified liquid. Step (D): 257 g of a product was obtained from the evaporator in the same manner as in Example 1 from the total amount of the final epichlorohydrin layer obtained in step (C). This product contains no detectable ionic chlorine and its epoxy equivalent, kaolin turbidity when melted at 140 ° C, and epoxy equivalent when heated in a sealed container at 150 ° C for 24 hours are obtained in Example 1. Values were the same for those products.

Example 21 Steps (A) and (B): A slurry containing precipitated sodium chloride was obtained in the same manner as in Steps (A) and (B) of Example 1. Step (C): The first time was carried out in the same manner as in Example 1 except that washing with distilled water was performed without using a purification aid.

The second washing was carried out in the same manner as in Example 1 except that 2 g of sodium lauryl sulfate was used instead of 2 g of sodium toluenesulfonate. The final washing was performed in the same manner as in Example 1 except that an aqueous solution obtained by adding 0.2 g of sodium salt of lauryl sulfate to 800 g of distilled water was used to prepare a purified liquid.

Step (D): From the total amount of the final epichlorohydrin layer obtained in step (C), 257 g of a product was obtained from the evaporator in the same manner as in Example 1. This product contains no detectable ionic chlorine and its epoxy equivalent, 14
The kaolin turbidity when melted at 0 ° C. and the epoxy equivalent when heated at 150 ° C. in a closed vessel for 24 hours were identical to those of the product obtained in Example 1.

Embodiment 22 In this embodiment, in the steps (A) and (B), the first embodiment
Using the reactor used in Example 3, the washing apparatus used in Example 14 in Step (C), and the evaporator from the coating film used in Example 15 in Step (D), Example 11 using terephthalic acid as a raw material
Made on a double scale.

Step (A) could be carried out smoothly as in Example 11. Also in the step (B), the stagnation of the precipitated sodium chloride and the adhesion to the side wall of the reactor as in Example 11 did not occur, and the reaction mixture was kept uniform throughout, and the final reaction mixture was obtained as a slurry. . Step (C)
No purification aid was used. By adding 60 kg of distilled water to the whole amount of the slurry in the vessel and stirring gently, the precipitated sodium chloride in the slurry is dissolved in the added water, and then, after standing for 12 hours, the entire amount of the organic layer is recovered. As a result, a transparent liquid was obtained. Then, by operating in the same manner as in Example 14, the first time, the purified liquid material was recovered by supplying distilled water for washing while supplying the transparent liquid material to the water washing device. . A second time, the collected liquid was washed with distilled water and collected to obtain the liquid purified by the step (C).

In the step (D), a concentrated liquid having an epichlorohydrin concentration of 70% by weight was prepared by first treating the purified liquid with a flash evaporator in the same manner as in Example 15; This concentrated liquid was supplied to the evaporator, and the first time, after maintaining the reduced pressure at an average of 10 mmHg, the average liquid residence time of 15 seconds at a film thickness of 220 microns, the liquid temperature at the outlet at the bottom of the evaporator at 120 ° C was 260 ° C.
A product having an epichlorohydrin content of 0 ppm
Then, for the second time, a reduced pressure of 0.2 mmHg was maintained on average for 1
After an average liquid residence time of 18 seconds at a film thickness of 80 microns, 1
At the outlet liquid temperature at the bottom of the evaporator at 55 ° C., 25.8 kg of a product having an epichlorohydrin content of 60 ppm were recovered.

The recovered product had an epoxy equivalent of 146 and was a clear liquid containing no insoluble contaminants. Example 23 In this example, the process (A) and the process (B)
3 and the evaporator from the coating used in Example 15 in step (D), respectively.

Step (A): A reaction mixture was formed from 1000 g of water, 250 g of sodium bromide as catalyst, 92.5 kg of epichlorohydrin and 8.3 kg of terephthalic acid. The reaction mixture under atmospheric pressure began to boil when its temperature reached 90 ° C., while epichlorohydrin liquefied and refluxed, and water was liquefied and discharged from the reactor while heating was continued for 12 hours. The temperature of the mixture reached 120 ° C. At this point, heating was stopped, and a reaction product at 45 ° C. was obtained by cooling.

Step (B): The dropwise addition of 8.8 kg of a 50% by weight aqueous solution of sodium hydroxide to the whole reaction product at 45 ° C. while maintaining this temperature was started under reduced pressure of 100 mmHg, and the reaction was carried out with stirring. The water and epichlorohydrin were evaporated from the mixture and the epichlorohydrin was refluxed while the pressure was gradually increased, and the water was discharged out of the reactor for 6 hours to complete the dropping.
During this time, the reaction mixture under stirring became cloudy with precipitated sodium chloride, but was kept uniform all the time, and without stagnation of deposited sodium chloride and adhesion to the side wall of the reactor,
The final slurry was reached.

Step (C): The total amount of the slurry in the vessel was 3
kg of distilled water, gently stirred, and allowed to stand for 12 hours.
Then, by collecting the organic layer, a transparent liquid from which precipitated sodium chloride was removed was obtained. Next, 3 kg of a 5% by weight aqueous solution of sodium dihydrogen phosphate was added to the total amount of the transparent liquid, stirred, and allowed to stand for 6 hours, and the organic layer was recovered to recover a purified transparent liquid. Again, 3 kg of distilled water was added to the total amount of the transparent liquid, stirred, allowed to stand for 6 hours, and then the organic layer was recovered.
The purified clear liquid was collected. The fact that an organic layer without turbidity was obtained in the above-mentioned water washing without using a purification aid is considered to be caused by the catalyst used in the step (A).

Step (D): In the same manner as in Example 15, the purified liquid was first treated with a flash evaporator to prepare a concentrated liquid having an epichlorohydrin concentration of 70% by weight. The concentrated solution was supplied to the evaporator, and the first time, after maintaining a reduced pressure of 10 mmHg on average and a liquid residence time of 16 seconds at a film thickness of 225 μm, the liquid temperature at the outlet of the evaporator bottom at 120 ° C. was 2400
ppm epichlorohydrin content and a second time maintaining a vacuum of 0.2 mmHg on average.
After an average liquid residence time of 20 seconds at a film thickness of 5 microns, 15
At the outlet liquid temperature at the bottom of the evaporator at 5 ° C., 11.4 kg of a product having an epichlorohydrin content of 50 ppm were recovered.

The recovered product had an epoxy equivalent of 153 and was a clear liquid containing no insoluble contaminants. Example 24 Step (A): The same reactor with a stirrer as used in Example 13 was prepared. In the reactor, 3 kg of water, 550 g of tetramethylammonium chloride, 138.8 kg of epichlorohydrin, 12.9
kg of cyanuric acid and charged and stirred to form a reaction mixture. Then, the reaction mixture was heated with stirring to raise the temperature.

When the temperature of the reaction mixture reached 89 ° C., the reaction mixture began to boil under atmospheric pressure, but continued to be heated. The generated vapor is cooled in a condenser, and all of the liquefied epichlorohydrin is continuously refluxed into the reactor, and the liquefied water is discharged out of the reactor for 5 hours, thereby lowering the temperature of the reaction mixture. 120 ° C. was reached. At this point, the heating was stopped and the reaction mixture was cooled to obtain a reaction product having a temperature of 45 ° C. Unreacted cyanuric acid was not detected in this product.

Step (B): While maintaining the total amount of the above reaction product at 50 ° C. with stirring, 25.6 kg of a 50% by weight aqueous solution of sodium hydroxide was added dropwise to the reaction product under reduced pressure of 100 mmHg. Upon initiation a reaction mixture was formed. At the same time, water and epichlorohydrin were evaporated from the reaction mixture. While gradually increasing the degree of vacuum, the steam is cooled in a condenser, all of the liquefied epichlorohydrin is continuously refluxed into the reactor, and the liquefied water is continuously discharged out of the reactor. 6
By completing the dropping at the time when the pressure reached 0 mmHg, a liquid product containing precipitated sodium chloride was obtained. It took 6 hours from the start of the dropping to the completion. During this time, the reaction mixture under stirring was clouded with precipitated sodium chloride, but was kept uniform throughout. After continuing the above reflux for another 5 minutes, the reduced pressure in the reactor was released to stop stirring.

According to liquid chromatography analysis, the content of the compound having a 2-hydroxy-3-chloropropyl group contained in the obtained liquid product was 1% or less. Step (C): The entire amount of the liquid product obtained in step (B) was washed three times with water. The first time, the mixture was stirred with 90 kg of water and allowed to stand for 24 hours.
After stirring with 15 kg of a 15% by weight aqueous solution, the mixture was allowed to stand for 24 hours,
Finally, the mixture was stirred with 90 kg of water and allowed to stand for 24 hours. The last washed epichlorohydrin layer was recovered as a purified liquid product.

Step (D): The total amount of the final epichlorohydrin layer obtained in step (C) was divided into small portions, supplied to a rotary evaporator, and heated under reduced pressure to distill off epichlorohydrin, and one hour before the end point, 2 mmHg 140 ° C under reduced pressure
And heated. After cooling to room temperature, the contents were taken out of the evaporator, and this was repeated to obtain 26.7 kg of a product. This product amount was calculated to be 90% yield based on the starting cyanuric acid used in step (A). The product had an epoxy equivalent of 104. The product gave a clear liquid when melted at 140 ° C.

Step (E): After melting the product obtained in the step (D), 100 g of the melt is placed in a flask in a flask.
By gradually adding to 0 g of methanol with stirring,
A methanol solution of the product is formed, and the solution is further heated to the reflux temperature of methanol, and the methanol solution is cooled to 5 ° C. over 12 hours, whereby a white solution is formed in the solution. Crystals were deposited. The white crystals were filtered off and dried, yielding 82 g of the final product. The final product had an epoxy equivalent of 100.

Comparative Example 3 The steps (A) and (B) were carried out in the same manner as in Example 24 except that the steps (A) and (B) were carried out in a reactor equipped with a stirrer having paddle blades. In (2), precipitated sodium chloride adhered to the side wall of the reactor, and the reaction mixture was not maintained homogeneous. Steps (C) and (D) were carried out as in Example 24, yielding 25.2 kg of product from the evaporator, which had an epoxy equivalent of 109. This product was treated in the same manner as in the step (E) of Example 24 to obtain 80 g of white crystals as a dried final product. The final product had an epoxy equivalent of 101.

Example 25 Step (A): 300 g of water and 5 g of a 20-liter glass reactor equipped with a stirrer having paddle blades were added.
12. 5 g of tetramethylammonium chloride;
A reaction mixture was formed by charging and stirring 88 kg of epichlorohydrin and 1.29 kg of cyanuric acid. Then, the reaction mixture was heated with stirring to raise the temperature.

When the temperature of the reaction mixture reached 89 ° C., the reaction mixture began to boil under atmospheric pressure, but continued to be heated. The generated vapor is cooled in a condenser, and all of the liquefied epichlorohydrin is continuously refluxed into the reactor, and the liquefied water is discharged out of the reactor for 5 hours, thereby lowering the temperature of the reaction mixture. 120 ° C. was reached. At this point, the heating was stopped and the reaction mixture was cooled to obtain a reaction product having a temperature of 45 ° C. Unreacted cyanuric acid was not detected in this reaction product.

Step (B): While maintaining the total amount of the above reaction product at 50 ° C. under vigorous stirring, 2.56 kg of a 50% by weight aqueous solution of sodium hydroxide was added dropwise to the reaction product under reduced pressure of 100 mmHg. To form a reaction mixture. At the same time as the start of the dropwise addition, water and epichlorohydrin were evaporated from the reaction mixture.

While gradually increasing the degree of pressure reduction, the steam was cooled in a condenser, all the liquefied epichlorohydrin was continuously refluxed into the reactor, and the liquefied water was continuously discharged out of the reactor. When the degree of pressure reduction reached 60 mmHg, the dropping was completed to obtain a liquid product containing precipitated sodium chloride. It took 6 hours from the start of the dropping to the completion. After continuing the above reflux for another 5 minutes, the reduced pressure in the reactor was released and stirring was stopped.

According to liquid chromatography analysis, the content of the compound having a 2-hydroxy-3-chloropropyl group contained in the obtained liquid product was 1% or less. The whole amount of the slurry obtained by repeating the above steps (A) and (B) four times was prepared for step (C). Step (C): The above liquid product in a container is added to distilled water 24
The precipitated sodium chloride in the liquid product is dissolved in the added water by adding liter and stirring gently, and then the liquid in the container is allowed to stand for 24 hours, and then the entire liquid product layer is recovered. As a result, a crude liquid product was obtained.

The water washing apparatus used in Example 14 was prepared for precisely purifying the above crude liquid product. After supplying the roughly purified liquid product to the middle of the liquid storage section on the upper side of the washing device, the rotating shaft was continuously rotated at a speed of 110 reciprocations per minute. A 3% by weight aqueous solution of sodium dihydrogen phosphate was supplied from the liquid supply conduit of the lower liquid storage section at a rate of 0.0
The liquid product is supplied at a speed of 78 liters, and after the discharge of the aqueous solution after contact with the liquid product starts from the liquid outlet of the upper liquid reservoir, the liquid product is discharged from the bottom of the lower liquid reservoir. And the supply of the crude liquid product was started at a rate of 0.51 liter per minute from the liquid supply conduit on the upper side of the washing device. Since the liquid product obtained at the beginning of the discharge was not purified, it was returned to the storage tank for the crude liquid product. The supplied aqueous solution of sodium dihydrogen phosphate is
Droplets having a size of about 0.3 to 7 mm were observed to be dispersed in the epichlorohydrin layer. After the discharge of the finely purified transparent liquid product started, the entire amount of the discharged liquid was recovered as a finely purified liquid product.

The finely purified liquid product was then washed with distilled water. A second transparent liquid is supplied by continuously supplying the liquid product at 0.45 liters per minute and the water at 0.19 liters per minute while rotating the rotating shaft at a speed of 110 reciprocations per minute. The product was obtained. The epichlorohydrin layer obtained in the second washing was recovered as a liquid product which was precisely purified in the step (B). The yield of triglycidyl isocyanurate was 90%.

Step (D): 5 kg of the liquid product recovered in the step (C) is put into a rotary evaporator having an internal volume of 10 liters, and distillation of epichlorohydrin is started under reduced pressure at a temperature of 60 ° C .; By increasing the temperature while sequentially increasing the degree of vacuum and continuing the distillation of epichlorohydrin, 4
The liquid at a temperature of 150 ° C. was reached under reduced pressure of mmHg. The liquid contained 500 ppm epichlorohydrin and exhibited an epoxy equivalent of 104. The product was clear at 140 ° C. when melted.

Example 26 In the same manner as in the steps (A) and (B) of Example 25, except that in the step (A), 55 g of ethyltriphenylphosphonium bromide was used instead of 55 g of tetramethylammonium chloride. A liquid product containing precipitated sodium chloride was prepared, and the steps (A) and (B) were repeated four times, and the whole amount of the slurry obtained was prepared for the step (C).

In step (C), a crude liquid product was first obtained in the same manner as in Example 25, and then the crude liquid product was purified using the same washing apparatus used in Example 14. Precision refined. In the first washing with the above washing equipment,
The rotating shaft was continuously rotated at a speed of 90 reciprocations per minute. A 3% by weight aqueous solution of sodium dihydrogen phosphate is supplied at a rate of 0.052 liters per minute from the liquid supply conduit of the lower liquid storage unit, and the liquid product and the liquid product are discharged from the liquid discharge port of the upper liquid storage unit. After the discharge of the aqueous solution after the contact is started, the discharge of the liquid product is started from the bottom of the lower liquid storage part, and the crude product is discharged at a rate of 0.34 liters per minute from the upper liquid supply conduit of the washing device. The supply of the purified liquid product was started. The liquid product obtained at the beginning of the discharge was returned to the storage tank for the crude liquid product. The supplied aqueous solution of sodium dihydrogen phosphate was observed to be dispersed in the epichlorohydrin layer as droplets having a size of 0.3 to 3 mm. After the discharge of the finely purified transparent liquid product started, the entire amount of the discharged liquid was recovered as a finely purified liquid product.

The finely purified liquid product was washed a second time with distilled water. The second transparent liquid is supplied by continuously supplying the liquid product at 0.30 liters per minute and the water supply at 0.13 liters per minute while rotating the rotating shaft at a speed of 90 reciprocations per minute. The product was obtained. The epichlorohydrin layer obtained in the second washing is subjected to step (C).
And recovered as a liquid product that was precisely purified by

Step (D): Epichlorohydrin was distilled off from the liquid product recovered in step (C) in the same manner as in Example 25 to obtain a solution under reduced pressure of 4 mmHg.
A liquid at a temperature of 0 ° C. was reached. This liquid is 460
It contained ppm of epichlorohydrin and showed an epoxy equivalent of 105. The product was clear at 140 ° C. when melted.

Example 27 Step (A): 300 g in a 20-liter glass reactor equipped with a stirrer having paddle blades and a baffle
Of water, 55 g of tetramethylammonium chloride, 13.88 kg of epichlorohydrin, 1.29
kg of cyanuric acid and charged and stirred to form a reaction mixture. Then, the reaction mixture was heated with stirring to raise the temperature. When the temperature of the reaction mixture reached 89 ° C., the reaction mixture began to boil under atmospheric pressure but continued to heat. The generated vapor is cooled in a condenser, and all of the liquefied epichlorohydrin is continuously refluxed into the reactor, and the liquefied water is discharged out of the reactor for 5 hours, thereby lowering the temperature of the reaction mixture. 120 ° C. was reached. At this point, the heating was stopped and the reaction mixture was cooled to obtain a reaction product having a temperature of 45 ° C. Unreacted cyanuric acid was not detected in this reaction product.

Step (B): While maintaining the whole amount of the above reaction product at 50 ° C. with vigorous stirring, 2.56 kg of a 50% by weight aqueous solution of sodium hydroxide was added dropwise to the reaction product under reduced pressure of 100 mmHg. To form a reaction mixture. At the same time as the start of the dropwise addition, water and epichlorohydrin were evaporated from the reaction mixture.

While gradually increasing the degree of pressure reduction, the steam was cooled in a condenser, all the liquefied epichlorohydrin was continuously refluxed into the reactor, and the liquefied water was continuously discharged out of the reactor. When the degree of pressure reduction reached 60 mmHg, the dropping was completed to obtain a liquid product containing precipitated sodium chloride. It took 6 hours from the start of the dropping to the completion. After continuing the above reflux for another 5 minutes, the reduced pressure in the reactor was released and stirring was stopped.

According to liquid chromatography analysis, the content of the compound having a 2-hydroxy-3-chloropropyl group contained in the obtained liquid product was 1% or less. Step (C): The entire amount of the liquid product obtained in step (B) was washed three times with water. Firstly, the mixture was stirred with 6 kg of distilled water for 24 hours after being stirred. Secondly, with 6 kg of a 5% by weight aqueous solution of sodium dihydrogen phosphate, the mixture was left for 24 hours after stirring.
Finally, the mixture was stirred with 8 kg of distilled water and left standing for 24 hours. The epichlorohydrin layer obtained in this last wash was recovered as a purified liquid product.

Step (D): The liquid product recovered in step (C) was treated with a flash evaporator to obtain a concentrated liquid having an epichlorohydrin concentration of 50% by weight. A triglycidyl isocyanurate product having a reduced epichlorohydrin concentration was obtained by using the evaporator used in Example 15 as an evaporator to form a coating film from this liquid and evaporate epichlorohydrin. . The yield of triglycidyl isocyanurate was 90% based on the starting cyanuric acid.

[0168] Heated steam was passed through the jacket of the evaporator, the rotating shaft was rotated at a speed of 200 revolutions per minute, and the pressure reducing device was operated. A concentrate of the liquid product having an epichlorohydrin concentration of 50% by weight obtained by the flash evaporator was supplied to the evaporator. First
When the evaporator was operated at the liquid supply rate and the degree of decompression shown in the table, after the film thickness (micron) and the average liquid residence time shown in the table, the evaporator bottom outlet liquid temperature shown in the table, Epoxy equivalent and epichlorohydrin concentration (ECHppm)
(P ₁ ) and (p ₂ ) were recovered from the outlet at the bottom of the evaporator. Each of the recovered products was a transparent liquid containing no insoluble foreign matter.

Next, the recovered liquid product (p ₁ ) was treated again with the evaporator to obtain a product (Q ₁ ) having a lower epihalohydrin concentration. This time, 14.0 per hour
The liquid was supplied at a speed of kg and the rotating shaft was rotated at a speed of 200 revolutions per minute. When the evaporator was operated at the degree of reduced pressure shown in Table 1, after the film thickness (micron) and the average liquid residence time shown in the table, the liquid temperature at the bottom outlet of the evaporator shown in the table and the epoxy equivalent And a product (Q ₁ ) having a contained epichlorohydrin concentration (ECH ppm) was recovered from the outlet at the bottom of the evaporator. The recovered product was a transparent liquid containing no insoluble foreign matter.

Table 1 Evaporation conditions and product properties recovered products p ₁ p ₂ Q ₁ Supply liquid Concentrate Concentrate p ₁ Liquid supply rate (kg / Hr) 21.7 7.3 14.0 Decompression (mmHg) 10 10 0.2 Thickness (μ) 450 150 170 Residence time (sec) 15 15 18 Drain Outlet liquid temperature (° C) 120 137 150 Product epoxy equivalent 103 103 103 Product ECH concentration (ppm) 3800 2000 80 Step (E): 100 g of the melt of the product (Q ₁ ) obtained in step (D) is 400 g in a flask Of methanol was slowly added with stirring to form a methanol solution of the product. The solution was further heated to the reflux temperature of methanol. By cooling to ℃, white crystals were precipitated in the solution. The white crystals were filtered off and dried to give a final product (Z ₁ ) having an epoxy equivalent of 99 in a yield of 82 g.

Comparative Example 4 A purified liquid product was obtained in the same manner as in steps (A) to (C) of Example 27, and a concentrated liquid having an epichlorohydrin concentration of 50% by weight was obtained from a flash evaporator. . Next, 5 kg of this concentrated liquid was put into a rotary evaporator having an internal volume of 10 liters, and the pressure was reduced to 60 mm under a pressure of 100 mmHg.
The distillation of epichlorohydrin was started at a temperature of ℃, and the temperature was raised while increasing the degree of vacuum sequentially, and the distillation of epichlorohydrin was continued. The liquid in the evaporator passed for 4 hours from the start of the distillation. At this point, the temperature reached 150 ° C. under a reduced pressure of 4 mmHg. This liquid material is 500pp
m of epichlorohydrin and exhibited an epoxy equivalent of 104. Further reduce the pressure and reduce the pressure to 2 mmHg.
The epichlorohydrin was evaporated at 0 ° C. for 4 hours, at which point the liquid contained 200 ppm epichlorohydrin and the epoxy equivalent rose to 107.

Example 28 In this example, Example 24 was performed on a 25-fold scale using a reactor having an internal volume of 5 m ³ . Step (A)
Was performed smoothly as in Example 24. Also in the step (B), the precipitated sodium chloride did not adhere to the side wall of the reactor as in Comparative Example 3, and the reaction mixture could be maintained uniform.

The product was obtained in a yield of 90% through steps (C) and (D) in the same manner as in Example 24. The product had an epoxy equivalent of 104. Step (E) was also performed in the same manner as in Example 24, and a product was obtained with a yield of 82%. This product exhibited an epoxy equivalent of 100. Example 29 In the same manner as in Step (A) and Step (B) of Example 13,
A slurry containing precipitated sodium chloride was prepared.

Next, 90 kg of water was added to the whole amount of the slurry, and the mixture was gently stirred to dissolve the precipitated sodium chloride in the slurry in the added water. A transparent liquid was obtained by collecting the entire amount of the layer. The liquid was then washed with the water washing apparatus used in step (C) of Example 14, and the first time using an aqueous solution not containing sodium toluenesulfonate but containing 3% by weight of sodium dihydrogen phosphate. And a second time using distilled water to purify each, thereby preparing a purified liquid.

From this purified liquid, a concentrated solution was prepared by a flash evaporator in the same manner as in step (D) of Example 15 except that the treatment amount was increased, and the evaporator was used to evaporate from the coating film. Removal of epichlorohydrin yielded 26.7 kg of a product having an epoxy equivalent of 104 and an epichlorohydrin concentration of 60 ppm.

When this product was melted at 140 ° C., the melt was clear.

[0177]

According to the present invention, a compound having 2 to 4 carboxyl groups or a compound having 1 to 3 amide groups is converted to a 2,3-epoxypropyl derivative or 2
-Methyl-2,3-epoxypropyl derivative can be produced as a highly pure product. This product has a high oxirane oxygen content, high transparency when melted, and high thermal stability with little change in epoxy equivalent when heated at 150 ° C. for 24 hours. A product having such high purity and thermal stability can be suitably used particularly as a transparent sealing material for a semiconductor device such as a light-emitting element, a light-receiving element, or a photoelectric conversion element.

According to the production method of the present invention, the product yield and the recovery of epihalohydrin or 2-methylepihalohydrin are high, purification can be performed in a short time, and epihalohydrin or 2-methyl contained in wastewater during purification. Since the amount of epihalohydrin, epoxy compound, and the like is small, the treatment is easy, and the high-purity product can be manufactured with high production efficiency.

 ──────────────────────────────────────────────────続 き Continued on the front page (31) Priority claim number Japanese Patent Application No. Hei 8-293769 (32) Priority date Hei 8 (1996) November 6 (33) Priority claim country Japan (JP) (31) Priority Claim No. Japanese Patent Application No. 8-293770 (32) Priority Date Hei 8 (1996) November 6 (33) Priority Claiming Country Japan (JP) (31) Priority Claim No. Japanese Patent Application No. 8-314682 (32) Priority Japanese Hei 8 (1996) November 26 (33) Priority claiming country Japan (JP) (31) Priority claim number Japanese Patent Application 8-314683 (32) Priority Japanese Hei 8 (1996) November 26 (33) ) Priority claiming country Japan (JP) (72) Inventor Motohiko Hidaka 722-1, Tsuboi-cho, Funabashi-shi, Chiba Pref. Nissan Chemical Industry Co., Ltd.

Claims (26)

[Claims] 1. A carboxyl group having 2 to 4 carboxyl groups or 1
From a compound having up to three amide groups, a molecular structure in which all the active hydrogen atoms of the carboxyl group or the amide group are substituted with a 2,3-epoxypropyl group or a 2-methyl-2,3-epoxypropyl group 2 of the above compounds having
3-epoxypropyl derivative or 2-methyl-2,3-
An epoxypropyl derivative was prepared by adding an epoxy equivalent of 1.0 to 1.1 times the theoretical epoxy equivalent of the derivative and 10 ppm
Manufactured as a highly pure product having a ionic halogen content of below, forms a clear liquid when melted, and exhibits a 3% or less increase in epoxy equivalent weight when stored at 150 ° C. for 24 hours. For the following step (A),
(B), (C) and (D): (A) a compound having 2 to 4 carboxyl groups or 1 to 3 amide groups in the molecule, 1 mol of active hydrogen atom of the carboxyl group or amide group of the compound 1.2 to 6
In a reaction mixture containing 0 moles of epihalohydrin or 2-methyl epihalohydrin and a tertiary amine, quaternary ammonium base, quaternary ammonium salt, trisubstituted phosphine or quaternary phosphonium salt as a catalyst, By reacting the compound with epihalohydrin or 2-methyl epihalohydrin, the compound 2
Forming a reaction product containing a -hydroxy-3-halopropyl derivative or a 2-hydroxy-2-methyl-3-halopropyl derivative; (B) adding the reaction product obtained in the step (A) to the reaction product; The alkali metal hydroxide is gradually added in an amount of 1 to 2 mol per 1 mol of the active hydrogen atom of the carboxyl group or the amide group of the compound contained in the reaction product before the reaction in the step (A). By causing the above derivative to undergo a dehydrohalogenation reaction, and forming a slurry containing the precipitated alkali metal halide and completing the dehydrohalogenation reaction while stirring the slurry, 2,3-epoxypropyl derivative or 2-methyl-2,3-epoxypropyl derivative and alkali metal halide produced by this reaction (C) a slurry prepared in the step (B) or a liquid obtained by removing the alkali metal halide from the slurry is used as a purification aid in an amount of 1 wt. % Of a sulfonic acid, a sulfonate, a carboxylate having 7 or more carbon atoms in a molecule, an alcohol sulfate having 4 or more carbon atoms in a molecule, or a mixture thereof, A step of preparing a purified liquid material containing the derivative produced in step (B) by washing with an aqueous solution containing the same; and (D) converting the purified liquid material prepared in step (C) into Evaporation and removal of epihalohydrin or 2-methylepihalohydrin gives the compound 2,3
A process comprising the step of producing an epoxypropyl derivative or a 2-methyl-2,3-epoxypropyl derivative as a high-purity product. 2. The method according to claim 1, wherein the alkali metal hydroxide is added as an aqueous solution of 20 to 70% by weight, and the added water and the generated water are evaporated from the slurry at 10 to 80 ° C. under reduced pressure. As the slurry is removed, the slurry is circulated from the bottom of the reactor along the side walls of the reactor to a liquid level that rises to the liquid level, where it is reversed and entrained toward the lower center of the reactor, The step (B) is carried out by a method comprising maintaining the slurry uniform by maintaining the mixture under agitation causing shearing.
Is carried out in a reactor. 3. The method according to claim 1, wherein the aqueous solution is introduced into the column of the liquid material as liquid particles having an average diameter of 0.1 to 10 mm, and the liquid particles are raised in the column. Combining the liquid particles to form an aqueous solution layer, repeating a cycle consisting of introducing, ascending, and combining the liquid particles in a column upward in a stepwise manner; The purification in the step (C) by purifying the liquid material by continuing to supply 0.01 to 5 parts by weight of a purification aid with respect to 100 parts by weight of the derivative. A method for producing the derivative according to claim 1, which is carried out on 4. The method according to claim 1, wherein the film of the purified liquid material or the concentrated liquid thereof obtained in the step (C) having a thickness of 30 to 500 μm by coating on the surface of the base material has the highest evaporating component concentration at one end of the film. And formed so that the concentration of the evaporating component decreases sequentially toward the lowest evaporating component concentration at the opposite end thereof, and evaporates the evaporating component from the film at a temperature of 100 to 165 ° C. under a pressure of 5 mmHg or less of the evaporating component. While the purified liquid or its concentrated liquid is continuously supplied to one end of the membrane having the highest concentration of the evaporating component, the liquid under the thickness is gradually moved toward the opposite end, and The method for producing a derivative according to claim 1, wherein the evaporation in the step (D) is performed by a method comprising continuously collecting a liquid having a reduced concentration of an evaporating component from the opposite end. 5. The method according to claim 3, wherein the alkali metal hydroxide is added as a 20 to 70% by weight aqueous solution, and the added water and the generated water are reduced under reduced pressure by 10 to 80%. The slurry is removed from the slurry while being removed by evaporation at a temperature of ℃ C. A circulating flow which rises from the bottom of the reactor to a liquid level along the side wall of the slurry, and a reverse flow toward the lower center of the reactor where the slurry flows, Maintaining the slurry homogeneous by maintaining it under agitation to cause shearing across it,
A method for producing a derivative according to claim 3 or 4, wherein step (B) is performed in a reactor. 6. The method according to claim 2, wherein the aqueous solution is introduced as a liquid particle having an average diameter of 0.1 to 10 mm into a liquid material column, and the liquid particle is raised in the column. That the liquid particles are then combined in a column to form an aqueous solution layer, a cycle consisting of introducing, ascending, and combining the liquid particles in the column is repeated stepwise upwards; and The supply of the aqueous solution by the above-mentioned introduction to 0.1 part by weight with respect to 100 parts by weight of the above derivative
The washing in step (C) is performed on the liquid material by a method comprising purifying the liquid material by continuing until the purification aid of 01 to 5 parts by weight is supplied. For producing derivatives of 7. The film according to claim 2 or 3, wherein the film of the purified liquid or the concentrate thereof obtained in the step (C) having a thickness of 30 to 500 μm by coating on the surface of the substrate is the highest at one end of the film. The film is formed to have a concentration of the evaporating component and to gradually decrease the concentration of the evaporating component toward the lowest concentration of the evaporating component at the opposite end, and from the film at a temperature of 100 to 165 ° C. under a pressure of 5 mmHg or less of the evaporating component. While evaporating the evaporating component, the purified liquid or its concentrated liquid is continuously supplied to one end of the film having the highest evaporating component concentration, and the liquid under the film thickness is gradually moved toward the opposite end, The derivative according to claim 2 or 3, wherein the step (D) is carried out by a method comprising continuously recovering a liquid having a reduced concentration of the evaporating component from the opposite end of the film. Way to elephants. 8. The method according to claim 2, wherein the aqueous solution is introduced into the liquid column as liquid particles having an average diameter of 0.1 to 10 mm, and the liquid particles are raised in the column. Combining the liquid particles to form an aqueous solution layer, repeating a cycle consisting of introducing, ascending, and combining the liquid particles in a column upward in a stepwise manner; The purification in the step (C) by purifying the liquid material by continuing to supply 0.01 to 5 parts by weight of a purification aid with respect to 100 parts by weight of the derivative. And the evaporation in the step (D) is performed by applying a film of the purified liquid substance or the concentrated liquid thereof in the step (C) having a thickness of 30 to 500 μm by coating on the surface of the substrate at one end of the film. Having a high concentration of the evaporating component and decreasing in order toward the lowest evaporating component concentration at the opposite end thereof, and from the film at a temperature of 100 to 165 ° C. under a pressure of 5 mmHg or less of the evaporating component. While evaporating the evaporating component at a temperature, the purified liquid or its concentrated liquid is continuously supplied to one end of the film having the highest evaporating component concentration, and the liquid under the thickness is gradually moved toward the opposite end. 3. A process for producing a derivative according to claim 2, wherein the process comprises the step of continuously recovering a liquid having a reduced concentration of evaporated components from the opposite end of the membrane. 9. The process according to claim 1, wherein the reaction in the step (A) is continued until 90% or more of active hydrogen atoms in the reaction mixture have disappeared. the method of. 10. The purification auxiliary in the step (C) is benzenesulfonic acid, toluenesulfonic acid, benzenesulfonic acid salt, toluenesulfonic acid salt, vinylsulfonic acid salt, a polymer of vinylsulfonic acid salt, naphthalenesulfonic acid salt. A process for producing a derivative according to any one of claims 1 to 9, which is a formaldehyde condensate, tetrahydrophthalate, lauryl sulfate, phthalate, salicylate, or cinnamate. 11. The compound in step (A) is terephthalic acid, and the derivative obtained in step (D) is bis (2,3-epoxypropyl) terephthalate or bis (2-methyl-2,3- A process for producing a derivative according to any one of claims 1 to 10 which is (epoxypropyl) terephthalate. 12. The compound in step (A) is isocyanuric acid and the derivative obtained in step (D) is tris (2,3-epoxypropyl) isocyanurate or tris (2-methyl-2,3- An epoxypropyl) isocyanurate according to any one of claims 1 to 10.
A method for producing the derivative according to the paragraph. 13. The process (D) according to claim 11, wherein bis (2,3-epoxypropyl) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate is used.
A solution of the product obtained by dissolving the product obtained in the step (D) of the step (D) in a solvent for producing the product further purified from the product obtained in the step (E): Preparing the derivative as crystals from the solution, and separating and drying the precipitate from the solution to the step (D) of claim 11. 14. Tris (2,3-epoxypropyl)
The following step (E) for producing isocyanurate or tris (2-methyl-2,3-epoxypropyl) isocyanurate as a product further purified from the product obtained in step (D) of claim 12. (E) dissolving the product obtained in the step (D) of claim 12 in a solvent to prepare a solution of the product, depositing the derivative as crystals from the solution, and separating the precipitate from the solution; 13. A method comprising separating from the solution and drying, adding to step (D) of claim 12. 15. Tris (2,3-epoxypropyl)
Isocyanurate or tris (2-methyl-2,3-epoxypropyl) isocyanurate has an epoxy equivalent of 1.0 to 1.1 times the theoretical epoxy equivalent of the isocyanurate and forms a clear liquid when molten. The following process (A) for producing as a high-purity product
(B), (C) and (D): (A) isocyanuric acid, an epihalohydrin or 2 in an amount of 1.2 to 60 mol per mol of active hydrogen atoms thereof.
-Methyl-epihalohydrin and a tertiary amine, quaternary ammonium base or quaternary ammonium salt, trisubstituted phosphine or quaternary phosphonium salt as a catalyst in a reaction mixture containing the epihalohydrin or 2-methyl-epihalohydrin And isocyanuric acid to produce tris (2-hydroxy-
3-halopropyl) isocyanurate or tris (2-
(B) forming a reaction product containing (hydroxy-2-methyl-3-halopropyl) isocyanurate; (B) the reaction product contained in the reaction product in a reactor before the reaction of step (A) in the reaction product; 1 to 2 mol of an alkali metal hydroxide is slowly added as an aqueous solution of 20 to 70% by weight based on 1 mol of active hydrogen atoms of the isocyanuric acid thus prepared, so that The isocyanurate undergoes a dehydrohalogenation reaction and forms a slurry containing the precipitated alkali metal halide, and the slurry is added to the slurry from the bottom of the reactor until the dehydrohalogenation reaction is complete. A circulating flow that rises along the side wall to the liquid level, where it is reversed and entrained toward the lower center of the reactor and sheared across it Maintaining a uniform slurry by maintaining the stirring of causing while, water added and under reduced pressure 10 to 80 ° C. The formed water from the slurry
The resulting tris (2,2)
Preparing a final slurry containing 3-epoxypropyl) isocyanurate or tris (2-methyl-2,3-epoxypropyl) isocyanurate and the alkali metal halide produced by the above reaction; A step of preparing a purified liquid containing the above isocyanurate by washing the slurry obtained from the above or the slurry obtained by removing the alkali metal halide from the slurry with water; and (D) purifying the purified liquid containing the isocyanurate. By removing the epihalohydrin or 2-methyl-epihalohydrin therein from the liquid by evaporation, tris (2,3-epoxypropyl) isocyanurate or tris (2-methyl-2,
A method comprising the step of producing (3-epoxypropyl) isocyanurate as the high-purity product. 16. Tris (2,3-epoxypropyl)
Isocyanurate or tris (2-methyl-2,3-epoxypropyl) isocyanurate has an epoxy equivalent of 1.0 to 1.1 times the theoretical epoxy equivalent of the isocyanurate and forms a clear liquid when molten. The following process (A) for producing as a high-purity product
(B), (C) and (D): (A) isocyanuric acid, an epihalohydrin or 2 in an amount of 1.2 to 60 mol per mol of active hydrogen atoms thereof.
-Methyl-epihalohydrin and a tertiary amine, quaternary ammonium base or quaternary ammonium salt, trisubstituted phosphine or quaternary phosphonium salt as a catalyst in a reaction mixture containing the epihalohydrin or 2-methyl-epihalohydrin And isocyanuric acid to produce tris (2-hydroxy-
3-halopropyl) isocyanurate or tris (2-
(B) forming a reaction product containing (hydroxy-2-methyl-3-halopropyl) isocyanurate; (B) the reaction product contained in the reaction product in a reactor before the reaction of step (A) in the reaction product; The alkali metal hydroxide is gradually added in an amount of 1 to 2 moles per 1 mole of active hydrogen atoms of the isocyanuric acid to cause a dehydrohalogenation reaction, and the precipitated alkali metal halide is removed. The resulting tris (2,3-epoxypropyl) isocyanurate or tris ( 2-methyl-2,3-epoxypropyl) isocyanurate and the alkali metal halide produced by this reaction A step of preparing a final slurry having: (C) a liquid having an average diameter of 0.1 to 10 mm in a column of liquid obtained by removing alkali metal halide from the final slurry; Introducing the particles as particles, raising the liquid particles in the column, then combining the liquid particles in the column to form an aqueous layer, a cycle consisting of introducing, rising, and combining the liquid particles in the column Is repeated stepwise upwards, and the supply of water by the introduction into the liquid is 50 to 50 parts by weight of the isocyanurate.
Preparing a purified liquid containing the above isocyanurate by continuing until 5000 parts by weight of water is supplied; and (D) removing epihalohydrin or 2-methyl from the purified liquid obtained in the step (C). By removing the epihalohydrin by evaporation to obtain tris (2,3-epoxypropyl) isocyanurate or tris (2-methyl-
(2,3-epoxypropyl) isocyanurate as the high-purity product. 17. Tris (2,3-epoxypropyl)
Isocyanurate or tris (2-methyl-2,3-epoxypropyl) isocyanurate has an epoxy equivalent of 1.0 to 1.1 times the theoretical epoxy equivalent of the isocyanurate and forms a clear liquid when molten. The following process (A) for producing as a high-purity product
(B), (C) and (D): (A) isocyanuric acid, an epihalohydrin or 2 in an amount of 1.2 to 60 mol per mol of active hydrogen atoms thereof.
-Methyl-epihalohydrin and a tertiary amine, quaternary ammonium base or quaternary ammonium salt, trisubstituted phosphine or quaternary phosphonium salt as a catalyst in a reaction mixture containing the epihalohydrin or 2-methyl-epihalohydrin And isocyanuric acid to produce tris (2-hydroxy-
3-halopropyl) isocyanurate or tris (2-
(B) forming a reaction product containing (hydroxy-2-methyl-3-halopropyl) isocyanurate; (B) the reaction product contained in the reaction product in a reactor before the reaction of step (A) in the reaction product; The alkali metal hydroxide is gradually added in an amount of 1 to 2 moles per 1 mole of active hydrogen atoms of the isocyanuric acid to cause a dehydrohalogenation reaction, and the precipitated alkali metal halide is removed. The resulting tris (2,3-epoxypropyl) isocyanurate or tris (2) is formed by stirring the slurry containing the precipitated alkali metal halide until the completion of the dehydrohalogenation reaction. 2-methyl-2,3-epoxypropyl) isocyanurate and the alkali metal halide produced by this reaction (C) a purified liquid containing the isocyanurate by washing the final slurry or a liquid obtained by removing the alkali metal halide from the slurry with water; (D) coating the purified liquid material or the concentrated liquid film thereof obtained in the step (C) having a thickness of 30 to 500 μm by coating on the surface of a substrate with the highest concentration of an evaporating component at one end of the film. And formed so that the concentration of the evaporating component decreases sequentially toward the lowest concentration of the evaporating component at the opposite end thereof, and 100 to 1 mm under a pressure of 5 mmHg or less of the evaporating component from the film.
While evaporating the evaporating component at a temperature of 65 ° C., the purified liquid or its concentrated liquid is continuously supplied to one end of the membrane having the highest evaporating component concentration, and the liquid under the thickness is directed toward the opposite end. From the purified liquid from step (C) in a manner that comprises gradually recovering the liquid having a reduced concentration of evaporating constituents from the opposite end of the membrane. By removal, tris (2,3-epoxypropyl) isocyanurate or tris (2-methyl-2,3
-A process comprising the step of producing (epoxypropyl) isocyanurate as said high purity product. 18. The method according to claim 15, wherein water is introduced into the liquid column as liquid particles having an average diameter of 0.1 to 10 mm, and the liquid particles are raised in the column. Combining the liquid particles with each other to form an aqueous layer, repeating a cycle consisting of introducing, ascending and assembling the liquid particles in a column upward in a stepwise manner, and adding water to the liquid material by the introduction. Is supplied to 50 to 100 parts by weight of the isocyanurate.
The tris (2,3-epoxypropyl) isocyanurate or tris (2) according to claim 15, wherein the washing in step (C) is performed on the liquid by a method comprising continuing until 5000 parts by weight of water is supplied. -Methyl-2,
Process for producing 3-epoxypropyl) isocyanurate. 19. The method of claim 15, claim 16 or claim 1.
In 8, the composition is coated on the substrate surface by 30 to 500 μm.
The film of the purified liquid or the concentrate thereof obtained in the step (C) having the thickness of (C) is formed by sequentially evaporating the concentration of the evaporating component toward the lowest evaporating component concentration at one end of the membrane and at the opposite end thereof. From the above film, and 100 to 1 under a pressure of 5 mmHg or less of the evaporation component from the film.
While evaporating the evaporating component at a temperature of 65 ° C., the purified liquid or its concentrated liquid is continuously supplied to one end of the membrane having the highest evaporating component concentration, and the liquid under the thickness is directed toward the opposite end. 17. The evaporation in the step (D) by a method comprising gradually moving the liquid material having a reduced concentration of the evaporated component from the opposite end of the film and continuously collecting the liquid material. A method for producing tris (2,3-epoxypropyl) isocyanurate or tris (2-methyl-2,3-epoxypropyl) isocyanurate according to claim 18. 20. The following step (E): (E) preparing a solution of the product obtained by dissolving the product obtained in the step (D) according to any one of claims 15 to 19 in a solvent. Depositing the derivative as crystals from the solution, and separating and drying the precipitate from the solution to the employed step (D). Epoxypropyl) isocyanurate or tris (2-methyl-2,
A process for producing (3-epoxypropyl) isocyanurate as a more purified product than the product according to step (D) employed above. 21. Bis (2,3-epoxypropyl) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate is converted to an epoxy equivalent of 1.0 to 1.1 times the theoretical epoxy equivalent of the terephthalate. The following steps (A), (B) and (C) for producing as a high-purity product having a transparent liquid upon melting
And (D): (A) terephthalic acid, epihalohydrin or 2-methyl-epihalohydrin in an amount of 1.2 to 60 mol per mol of active hydrogen atom thereof, and tertiary amine, quaternary ammonium base as a catalyst Or in a reaction mixture containing a quaternary ammonium salt, a trisubstituted phosphine, a quaternary phosphonium salt or an alkali metal halide,
Bis (2-hydroxy-3-halopropyl) terephthalate or bis (2-hydroxy-2-methyl-3-halopropyl) terephthalate generated by reacting the epihalohydrin or 2-methyl-epihalohydrin with terephthalic acid (B) adding 1 mole of the above-mentioned reaction product in the reactor to 1 mole of active hydrogen atoms of terephthalic acid contained in the reaction product before the reaction in step (A). The terephthalate in the above reaction product is caused to undergo a dehydrohalogenation reaction by gradually adding an alkali metal hydroxide in an amount of about 2 to 2 mol% as an aqueous solution of 20 to 70% by weight thereof. Is formed and the slurry is decanted until the dehydrohalogenation reaction is completed. Under agitation, the slurry is circulated from the bottom of the reactor along the side wall of the reactor to a liquid level, where it is reversed and entrained toward the lower center of the reactor and sheared across the entrained flow. The bis (2,3-epoxypropyl) formed by removing the added water and the generated water from the slurry by evaporation at reduced pressure at 10-80 ° C. while keeping the slurry uniform by maintaining Terephthalate or bis (2-methyl-
(C) preparing a final slurry containing (2,3-epoxypropyl) terephthalate and the alkali metal halide produced by the above reaction, and (C) obtaining the final slurry or removing the alkali metal halide from this slurry. Washing the obtained liquid with water to prepare a purified liquid containing terephthalate; and (D) evaporating epihalohydrin or 2-methyl-epihalohydrin therein from the purified liquid. A process of producing bis (2,3-epoxypropyl) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate as the above-mentioned high-purity product. 22. An epoxy equivalent of bis (2,3-epoxypropyl) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate which is 1.0 to 1.1 times the theoretical epoxy equivalent of the terephthalate. The following steps (A), (B) and (C) for producing as a high-purity product having a transparent liquid upon melting
And (D): (A) terephthalic acid, epihalohydrin or 2-methyl-epihalohydrin in an amount of 1.2 to 60 mol per mol of active hydrogen atom thereof, and tertiary amine, quaternary ammonium base as a catalyst Or in a reaction mixture containing a quaternary ammonium salt, a trisubstituted phosphine, a quaternary phosphonium salt or an alkali metal halide,
Bis (2-hydroxy-3-halopropyl) terephthalate or bis (2-hydroxy-2-methyl-3-halopropyl) terephthalate generated by reacting the epihalohydrin or 2-methyl-epihalohydrin with terephthalic acid (B) adding 1 mole of the above-mentioned reaction product in the reactor to 1 mole of active hydrogen atoms of terephthalic acid contained in the reaction product before the reaction in step (A). ~ 2 moles of alkali metal hydroxide is slowly added to cause a dehydrohalogenation reaction, and a slurry containing precipitated alkali metal halide is formed, and the dehydrohalogenation reaction is completed. The slurry containing the precipitated alkali metal halide is stirred until the bis (2,3- (C) preparing a final slurry containing (oxypropyl) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate and the alkali metal halide produced by this reaction; Introducing water as liquid particles having an average diameter of 0.1 to 10 mm into a liquid column obtained by removing the metal halide, raising the liquid particles in the column, Combining the liquid particles in a column to form an aqueous layer, repeating a cycle consisting of introducing, ascending, and combining the liquid particles in the column upward in a stepwise manner; Is supplied to 50 to 5 parts by weight based on 100 parts by weight of the terephthalate.
By continuing until 000 parts by weight of water are supplied,
Preparing a purified liquid material containing the above terephthalate, and (D) removing the epihalohydrin or 2-methyl-epihalohydrin from the purified liquid material obtained by the step (C) by evaporating to obtain bis (2,2). 3-epoxypropyl) terephthalate or bis (2-methyl-2,3-
(Epoxypropyl) terephthalate as the high-purity product. 23. An epoxy equivalent of bis (2,3-epoxypropyl) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate which is 1.0 to 1.1 times the theoretical epoxy equivalent of the terephthalate. The following steps (A), (B) and (C) for producing as a high-purity product having a transparent liquid upon melting
And (D): (A) terephthalic acid, epihalohydrin or 2-methyl-epihalohydrin in an amount of 1.2 to 60 mol per mol of active hydrogen atom thereof, and tertiary amine, quaternary ammonium base as a catalyst Or in a reaction mixture containing a quaternary ammonium salt, a trisubstituted phosphine, a quaternary phosphonium salt or an alkali metal halide,
Bis (2-hydroxy-3-halopropyl) terephthalate or bis (2-hydroxy-2-methyl-3-halopropyl) terephthalate generated by reacting the epihalohydrin or 2-methyl-epihalohydrin with terephthalic acid (B) adding 1 mole of the above-mentioned reaction product in the reactor to 1 mole of active hydrogen atoms of terephthalic acid contained in the reaction product before the reaction in step (A). ~ 2 moles of alkali metal hydroxide is slowly added to cause a dehydrohalogenation reaction, and a slurry containing precipitated alkali metal halide is formed, and the dehydrohalogenation reaction is completed. The slurry containing the precipitated alkali metal halide is stirred until the bis (2,3- (C) preparing a final slurry containing (oxypropyl) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate and the alkali metal halide produced by this reaction; A step of preparing a purified liquid containing terephthalate by washing the liquid obtained by removing the alkali metal halide from the slurry with water; and (D) coating the liquid on the surface of the substrate by 30 to 500 μm. The membrane of the purified liquid or the concentrate thereof according to the step (C) having a thickness of (c) is formed by sequentially evaporating the vaporized component having the highest concentration of the vaporized component at one end of the film and the lowest concentration of the vaporized component at the opposite end. The film is formed so as to have a reduced concentration, and is subjected to a pressure of less than 5 mmHg of the vaporized component from the film under 100 mmHg. ~ 1
While evaporating the evaporating component at a temperature of 65 ° C., the purified liquid or its concentrated liquid is continuously supplied to one end of the membrane having the highest evaporating component concentration, and the liquid under the thickness is directed toward the opposite end. From the purified liquid from step (C) in a manner that comprises gradually recovering the liquid having a reduced concentration of evaporating constituents from the opposite end of the membrane. A method comprising the step of producing bis (2,3-epoxypropyl) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate as said high-purity product by removing said compound. 24. The method according to claim 21, wherein water is introduced into the liquid material column as liquid particles having an average diameter of 0.1 to 10 mm, and the liquid particles are raised in the column. Combining the liquid particles with each other to form an aqueous layer, repeating a cycle consisting of introducing, ascending and assembling the liquid particles in a column upward in a stepwise manner, and adding water to the liquid material by the introduction. Is supplied to 50 to 5 parts by weight based on 100 parts by weight of the terephthalate.
22. The bis (2,3-epoxypropyl) terephthalate or bis (2-epoxypropyl) terephthalate according to claim 21, wherein the washing in step (C) is performed on the liquid material by a method comprising continuing until water of 000 parts by weight is supplied. A process for producing (methyl-2,3-epoxypropyl) terephthalate. 25. The method according to claim 21, 22 or 2.
4. In 4 to 30 to 500 μm by coating on the substrate surface
The film of the purified liquid or the concentrate thereof obtained in the step (C) having the thickness of (C) is formed by sequentially evaporating the concentration of the evaporating component toward the lowest evaporating component concentration at one end of the membrane and at the opposite end thereof. From the above film, and 100 to 1 under a pressure of 5 mmHg or less of the evaporation component from the film.
While evaporating the evaporating component at a temperature of 65 ° C., the purified liquid or its concentrated liquid is continuously supplied to one end of the membrane having the highest evaporating component concentration, and the liquid under the thickness is directed toward the opposite end. 23. The method according to claim 21, wherein the step (D) is carried out by a method comprising gradually moving the liquid material and continuously recovering a liquid material having a reduced concentration of the evaporated component from the opposite end of the film. A method for producing bis (2,3-epoxypropyl) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate according to claim 24. 26. The following step (E): (E) dissolving the product obtained in step (D) according to any one of claims 21 to 25 in a solvent to prepare a solution of the product. Depositing the derivative as crystals from the solution, and separating and drying the precipitate from the solution to the employed step (D). A process for producing (epoxypropyl) terephthalate or bis (2-methyl-2,3-epoxypropyl) terephthalate as a more purified product than the product according to step (D) adopted above.