KR0150006B1 - Process for glycidyl compounds - Google Patents

Abstract

Closing the halohydrin intermediate obtained by the addition reaction of an alcohol compound, a phenol compound, a carboxylic acid compound and an amine compound with an epihalohydrin compound and / or a halohydrin compound in the presence of a dehalogenated hydrogen agent In the method for producing a glycidyl compound, after the ring closure reaction,

(1) a neutralization step of neutralizing the reaction mixture by introducing carbon dioxide into the reaction mixture;

(2) A method for producing a glycidyl compound, comprising contacting the reaction mixture after the completion of the neutralization step with a solid acid containing silica and alumina as a main component.

Description

Method for preparing a glycidyl compound

The present invention relates to a method for producing a glycidyl compound which is highly purified by using a method for seeding a glycidyl compound, and more particularly, an industrially advantageous method.

Conventionally, glycidyl compounds have been generally produced by the following method.

That is, an alcohol compound, a phenol compound, a carboxylic acid compound, an amine compound and the like, and an epihalohydrin compound and / or a halohydrin compound are present in the presence or absence of a solvent and, if desired, in the presence of an acidic compound or a basic compound as a catalyst. The reaction is carried out by heating to obtain a halohydrin intermediate, and then the halohydrin intermediate is subjected to dehalogenation using a basic compound such as sodium hydroxide to ring-close. Thereafter, the by-product salts and residues of the basic compound used as a catalyst or a dehalogenated hydrogen agent were washed with water or filtered, followed by heating and distillation under reduced pressure, followed by filtration to obtain the target product.

However, in the case of producing a glycidyl compound having a relatively hydrophilic property and having a property that is easily dissolved in water or easily emulsified with water, the conventionally used washing operation for dissolving or emulsifying the generated donor glycidyl compound in an aqueous system This is difficult, and furthermore, the resulting glycidyl compound is eluted in water for washing, whereby the yield of the target product is lowered.

In the case of dehydration and desolvation only by filtration after the ring closure reaction or when the remaining basic compound is dehydrated and desolvented under heating conditions without being completely washed with water, the epoxy group of the glycidyl compound remains. When the basic compound reacts to produce a polymer or cleavage of an epoxy group, the epoxy equivalent or viscosity of the final product is increased, resulting in a decrease in product quality. On the other hand, as a method of neutralizing the basic compound remaining after the ring-closure reaction using inorganic liver such as phosphoric acid or hydrochloric acid, there is a risk of complicated manufacturing process or deterioration of product quality. That is, when the addition amount of an inorganic acid is too large, this excess inorganic acid will cleave the epoxy group of a glycidyl compound, and may be a cause of the fall of product quality, Therefore, it is basic in order to add a basic compound and a considerable amount of inorganic acid which remain | survived. It was necessary to measure the residual amount of the compound in advance.

For this reason, the development of the method of efficiently removing the residual basic compound as a post-treatment technique following a ring-closure reaction for the purpose of obtaining a high quality glycidyl compound with a good yield was desired.

MEANS TO SOLVE THE PROBLEM The present inventors discovered these facts as a result of solving this problem and earnestly examining. In other words,

(1) After the completion of the ring closure reaction, the basic compound remaining in the system is removed by dissolving or removing the by-product salt with the minimum amount of water necessary for saturating and dissolving the by-product salt, or by removing the by-product salt by filtration or centrifugation. According to the method for neutralizing, the epoxy equivalent and the increase of the viscosity are not increased at the time of the subsequent dehydration and desolvent process.

(2) In the case of neutralization treatment using carbon dioxide, even if excessive carbon dioxide is introduced into the system, since it is itself vaporized and discharged out of the system, deterioration of product quality hardly occurs, and color reaction such as phenolphthalein is performed. Continue to introduce carbon dioxide until neutralization is confirmed. Therefore, the manufacturing process is simplified.

(3) By using the adsorption treatment using a solid acid mainly composed of silica and alumina, dehydration and desolvation after neutralization treatment using carbon dioxide can reduce the basic compound not removed only by filtration to 1 ppm or less. have.

The present invention has been completed based on these findings, and provides a novel method for producing glycidyl compounds in high quality and high yield under relatively simple and industrially advantageous conditions.

The manufacturing method of the glycidyl compound which concerns on this invention is a compound (henceforth generically called "raw material I") chosen from an alcohol compound, a phenol compound, a carboxylic acid, and an amine compound, and an epihalohydrin compound. And / or ring-closing the halohydrin intermediate obtained by addition reaction with a halohydrin compound in the presence of a dehalogenated hydrogen agent to produce a glycidyl compound.

(1) a neutralization step of neutralizing the reaction mixture by introducing carbon dioxide into the reaction mixture;

(2) after completion of the neutralization step, the reaction mixture is characterized in that it comprises a step of contacting with a solid acid composed mainly of silica and alumina.

The addition reaction between the raw material I and the epihalohydrin compound and / or the halohydrin compound in the present invention, and the halohydrin intermediate obtained thereby are closed in the presence of a dehalogenated hydrogen agent to produce a glycidyl compound. The process itself is known. These processes are described in, for example, Japanese Patent Application Publication No. 1-151567, pages 20-94 of "New Epoxy Resin" published by Hidaki Kachichi (published May 10, 1985). Japanese Patent Application Laid-Open No. 61-178974 and the like, and any of the above addition reaction step and ring closure reaction step are well known to those skilled in the art.

Therefore, any of the raw materials I used in the present invention can be used as long as they are conventionally used for addition reactions with epihalohydrin compounds and / or halohydrin compounds in the production of glycidyl compounds. The specific example is as follows.

As an alcohol compound which becomes a raw material of a glycidyl compound, about C2-C30, Preferably about 4-20 aliphatic monoalcohol, aliphatic polyhydric alcohol, alicyclic alcohol, these alkylene oxide adducts (addition number: 1) It is conventionally used in this field such as about 50 moles) can be used in a wide range without particular limitation.

Preferred alcohols include aliphatic monoalcohols such as butanol, pentanol, hexanol, octanol and allyl alcohol (especially aliphatic monohydric alcohols having 4 to 20 carbon atoms), ethylene glycol, propylene glycol, tetramethylene glycol, 1,5- Aliphatic polyhydric alcohols such as pentanediol, 3-methyl-1,5-pentanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol (especially aliphatic divalent, trivalent and Tetrahydric alcohol), cyclohexanol, cyclohexanediol, 1,4-cyclohexanedimethanol, 2,2-bis (4-hydroxycyclohexyl) propane [ie hydrogenated bisphenol A], bis (4-hydroxy Alicyclic alcohols such as cyclohexyl) methane and cyclohexanetriol (particularly alicyclic monovalent, divalent and trivalent alcohols having 6 to 20 carbon atoms) and carbon atoms such as ethylene oxide and propylene oxide of these alcohols. Alkylene oxide adducts can be illustrated. In addition, polyalkylene glycols (particularly those having a degree of polymerization of 2 to 50) such as polyethylene glycol, polypropylene glycol, and polytetramethylene glycol can also be used. In addition to these, a C2-C4 alkylene oxide adduct (addition mole number: about 1-20 mol), such as a phenol compound, carboxylic acid compound, and isocyanuric acid which are described below, can also be used.

Any phenolic compound may be used as long as it is used in this field, but preferred examples thereof include phenol, alkylphenol (especially phenol having 1 to 2 carbon atoms of 1 to 12 carbon atoms), resorcin, bisphenol A, and the like. do.

As for a carboxylic acid compound, various wide ranges are used, Preferably, it is aliphatic of C1-C22, such as acetic acid, a propionic acid, acrylic acid, methacrylic acid, 2-ethylhexanoic acid, lauric acid, stearic acid, oleic acid, etc. Monocarboxylic acid: C2-C22 aliphatic dicarboxylic acid, such as oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, dodecane diacid, octadecane diacid, maleic acid, and fumaric acid, and Their anhydrides; Aromatic carboxylic acids and their anhydrides such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, benzoic acid and tert-butylbenzoic acid; Alicyclic carboxylic acids, such as hexahydrophthalic acid, tetrahydrophthalic acid, methylhexahydrophthalic acid, methyltetrahydrophthalic acid, dimer acid, and those anhydrides, etc. are illustrated.

Amine compounds may also be used in this field without particular limitation, but preferred examples include aniline, aminophenol, and alkyl-substituted aminophenols (in particular, those having 1 to 12 alkyl groups on the benzene ring). , 4,4'-diaminodiphenylmethane, benzylamine, xylylenediamine, triaminobenzene and the like are exemplified. Moreover, heterocyclic compounds containing NH groups, such as isocyanuric acid, ethylene urea and hydantoin, can also be used.

The epihalohydrin compound and the halohydrin compound, which are other raw materials, can also be used without particular limitation in the conventional art in this field. Preferred epihalohydrin compounds and halohydrin compounds are represented by the following general formula.

Epihalohydrin Compound

Halohydrin compounds

or

[Wherein R represents a hydrogen atom, an alkyl group of 1 to 2 carbon atoms or a fluorinated alkyl group of 1 to 2 carbon atoms, and X represents a halogen atom such as a fluoro atom, a chlorine atom, a bromine atom or an iodine atom.]

Among them, epichlorohydrin, epibromohydrin, β-methyl epichlorohydrin, β-methyl epibromohydrin, glycerol-1,3-dichlorohydrin and the like are representative examples. These are used individually or in combination of 2 or more types. In addition, in the addition reaction of the present invention, the halohydrin compound is epihalohydrin in the system when a compound having a dehalogenated hydrogen effect such as an alkali (alkaline earth) metal hydroxide is used as a catalyst as described later. It is converted into, and this reacts with the raw material I in addition.

In addition reaction, a catalyst can be used as desired. Such catalysts include hydroxides of alkali metals or alkaline earth metals such as Lewis acid, sodium hydroxide, barium hydroxide, potassium carbonate, such as ditin, chloride and its hydrates, boron trifluoride, boron trichloride and their complex salts, and Friedel-Craft catalysts. Various compounds such as basic compounds such as salts and carbonates, and quaternary ammonium salts such as tetramethylammonium chloride and benzyltrimethylammonium chloride are exemplified, and their catalysts are appropriately selected according to the type of raw material I to which the method of the present invention is applied. Used. For example, Lewis acid is used with respect to an alcohol compound. In this case, it is preferable that the moisture in the raw material is removed as much as possible. In addition, a basic compound and / or a quaternary ammonium salt are used with respect to a phenol compound, a carboxylic acid compound, and an amine compound. These catalysts are also known, and those skilled in the art can appropriately select the use conditions such as the type and the amount of the catalyst, depending on the kind of raw materials.

As the dehalogenated hydrogenating agent used in the ring-closing step of the present invention, those used in this field can be used without particular limitation, and include a basic compound such as hydroxides of alkali metals such as sodium potassium, magnesium, calcium, and alkaline earth metals. , Carbonates, oxides, alcoholates and the like. They are used in the form of solids or solutions.

The carbon dioxide used in the present invention can be used either in the form of carbon dioxide itself or a gas mainly containing carbon dioxide. More specifically, carbon dioxide gas or dry ice, or a mixture of air, nitrogen, argon and the like with carbon dioxide gas is exemplified, and the form or concentration of carbon dioxide is not particularly limited as long as the predetermined effects of the present invention are not impaired.

As the solid acid mainly composed of silica and alumina used in the present invention, any basic compound or quaternary ammonium salt remaining in the neutralized product can be adsorbed and removed. Specifically, bentonite, perlite, kaolin Natural minerals such as zeolite, activated clay, or other solid silicic acid-based minerals having similar properties derived therefrom, and solid silicic acid-based materials having properties similar to those of artificially synthesized natural minerals; Highly acidic compounds such as aluminum are recommended. The preferable addition amount of the said solid acid is about 0.05 to 3 weight% with respect to the glycidyl compound made into the objective. Solid acids, such as these synthetic aluminum silicates, are commercially available, for example, it can obtain from brand names, such as "Kyoword 700SL" and "Kyoword 700SN." Since the trivalent A1 is homozygous at the place of tetravalent Si, the charges are insufficient, and since A1 is added and the cation as a diion has a structure which is easy to coordinate, it adsorbs a basic compound or a quaternary ammonium salt. Excellent performance

In this invention, a glycidyl compound is manufactured as follows normally.

That is, a solvent is suitably added to a suitable reactor according to the raw material I, epihalohydrin (or halohydrin), an addition reaction catalyst and, if desired, and generally the boiling point of epihalohydrin (e.g., For example, when epichlorohydrin is used, addition reaction is performed under heating stirring at about 30 to 100 ° C. As the solvent, those which are inert to the raw material and the resulting halohydrin intermediate, for example, benzene, toluene, xylene, methyl isobutyl ketone, butyl acetate, and the like can be used, but the reaction can be performed even without a solvent. It is preferable that the equivalence ratio of epihalohydrin to the active hydrogen of raw material I shall be about 0.8-2 normally. Moreover, epihalohydrin can be used excessively, and this can also be used as a reaction solvent. This reaction is normally performed at normal pressure, and is completed in about 0.5 to 6 hours, and the halohydrin intermediate corresponding to raw material I is obtained. If this addition reaction is schematically represented by an equation, it can be expressed as follows.

[Wherein, A represents a moiety excluding hydrogen atoms from the hydroxyl groups, phenolic hydroxyl groups, carboxyl groups and amino groups of the alcohol compound, phenol compound, carboxylic acid compound and amine compound as raw material I, and R represents a hydrogen atom An alkyl group of 2 or a fluorinated alkyl group of 1 to 2 carbon atoms, and X represents a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom or an iodine atom.]

In addition, when using the raw material I which has several active hydrogens, such as a polyhydric alcohol, the number of the halohydrin residues in the halohydrin intermediate (III) produced | generated according to the quantity of epihalohydrin or halohydrin used Becomes 2 or more.

Anyway, in the addition reaction process of this invention, the halohydrin intermediate represented by the said General formula (III) is produced regardless of the kind of raw material I used.

Subsequently, about 1.0-2. 0 times equivalent of a basic compound is added as a dehalogenation hydrogen agent with respect to the hydrolyzable halogen atom (X) of this halohydrin intermediate (III). At this time, in order to promote the ring closure reaction, the phase transfer catalyst may be added in an amount of about 0.05 to 2% by weight, preferably about 0.05 to 0.5% by weight, based on the halohydrin intermediate (III). Examples of such phase transfer catalysts include crown ethers such as quaternary ammonium salts such as benzyltrimethylammonium chloride, tetramethylammonium chloride, tetraethylammonium chloride and bromide thereof, 12-crown-4-ether and 15-crown-5-ether. Etc. are illustrated. Subsequently, hydrogenation under dehalation is carried out under reduced pressure (usually, up to about 20 mmHg) to atmospheric pressure, at about 0.5 to 6 hours at about 30 to 100 ° C, to carry out a ring reaction.

In any case, in this ring-closure reaction step, regardless of the type of raw material I used, alkali (B) between the hydrolyzable halogen atom (X) of the halohydrin intermediate (III) and the basic compound which is a dehalogenated hydrogenated agent is used. Alkaline earth) metal halides are formed as by-product salts.

In addition, since the basic compound which is generally a dehalogenated hydrogen agent is used in an equivalent equivalent or more with respect to the active hydrogen of the halohydrin intermediate (III), an excess of a basic compound will remain in the reaction mixture after completion | finish of a ring closure reaction. In addition, this quaternary ammonium will remain in this reaction mixture when a quaternary ammonium salt is used as a catalyst in an addition reaction process and / or a ring closure reaction process.

When the glycidyl compound produced from the reaction mixture containing such a basic compound is isolated, the present invention is intended to reduce the amount of incorporation of the basic compound and the like as much as possible. It can also be called the purification method of a dill compound.

In the present invention, the reaction mixture after the ring closure reaction thus obtained may be continuously provided to the neutralization step using the carbon dioxide of the present invention. In general, however, it is preferable to remove the by-product salts by filtration, centrifugation, washing with water, etc. and then to provide them to the neutralization step. The by-product salt is preferably removed as precipitated as a solid and then used in the neutralization step. Since the by-product salt precipitates as a solid under the conditions which precipitate as a solid, it is preferable to remove it by filtration or centrifugation. When the crude product of the glycidyl compound obtained at that time has a high melting point or high viscosity, a solvent inert to the crude product (for example, benzene, toluene, xylene, hexane, Heptane, octane, methyl ethyl ketone, methyl isobutyl ketone and the like) are preferably added. This also has the advantage of easy contact with carbon dioxide in the subsequent neutralization step. Alternatively, it is preferable to add the minimum water necessary to saturate the by-product salt to the crude product to dissolve the by-product salt and to separate off the by-product salt dissolved in hydrocephalus. By using minimal water in this way, it is possible to suppress the loss of dissolution into water and the occurrence of emulsification. Moreover, when water is used in this way, there exists an advantage that some basic compounds in a reaction mixture are also removed.

Thereafter, carbon dioxide is introduced into the reaction mixture and the reaction mixture is neutralized. This neutralizes the remaining basic compound. As the operation of injecting carbon dioxide, introduction may be continued in the system until it is confirmed that neutralization is completed by color reaction of phenolphthalein or the like, and it is not particularly necessary to control the amount of carbon dioxide. The temperature at the time of introduction of carbon dioxide is not specifically limited, either, For example, what is necessary is just to employ | adopt a temperature of about 0-60 degreeC.

After neutralization is completed, it is preferable to distill off the volatile substance, specifically water or water, the volatile solvent used in the said process, etc. under heating and pressurization. By performing this operation, active loss of the solid acid used continuously can be more effectively avoided.

Subsequently, the predetermined amount of the silica-alumina solid acid is added to the system, and the mixture is stirred for about 30 minutes under a reduced pressure of about 3 to 20 mmHg, preferably at a temperature of 50 to 100 ° C. In this process, traces of basic compounds which are not neutralized in the process and still remain are adsorbed on the solid acid.

The system is then filtered or centrifuged to remove solids and to obtain a highly purified glycidyl compound in high yield.

In the case of dehydration and desolventing under heating and depressurization without carrying out a neutralization step using carbon dioxide after the ring-closure reaction, polymerization or cleavage of epoxy groups occurs, and the epoxy equivalent and viscosity of the final product increase. On the other hand, when not using together the adsorption process by the solid acid which concerns on this invention, a comparatively large amount of basic compounds remain and it is difficult to obtain the predetermined effect of this invention.

The method for producing a glycidyl compound according to the present invention can easily and reliably inactivate the basic compound remaining after the ring closure reaction, thereby reducing the content of the remaining basic compound and remarkably improving the quality of the epoxy equivalent or viscosity of the final product. In addition, the yield can be improved.

EXAMPLE

An Example is given to the following and this invention is demonstrated in detail. In addition, the evaluation method in each example is as follows.

Epoxy equivalent weight. . . By perchloric acid method.

Organochlorine content. . . By the Volhard method.

Sodium content. . . By salt light analysis

Nitrogen content. . . It is based on an all-nitrogen analyzer (manufactured by Mitsubishi Chemical Co., Ltd.).

Example 1

a) pretreatment process for dehydration of raw materials

When rotating, 134 g (1.0 mole) of trimethylolpropane and 41 g of xylene were added to a reactor equipped with a stirring device, a decanter, a thermometer, and a gas introducing pipe, and dehydrated at 100 ° C. under reduced pressure for 1 hour, followed by 20 minutes at 100 ° C. and 20 mm Hg. Talcylene was performed.

b) addition reaction process

After cooling the mixture subjected to the pretreatment to 60 ° C., 4.3 g of boron trifluoride ether complex salt was added and 277 g (3.0 mol) of epichlorohydrin was added dropwise at 60 ° C. over 1 hour, and stirring was continued for 30 minutes. The reaction was terminated.

c) ring-closure reaction process

Subsequently, after cooling the reaction mixture to 40 degreeC, 120 g of solid sodium hydroxide was added at 40 degreeC for 30 minutes, stirring was continued at 40 degreeC for 1 hour, and the ring closing reaction was complete | finished.

d) removal and neutralization of by-product salts

Byproduct sodium chloride and unreacted solid sodium hydroxide were filtered off. Thereafter, carbon dioxide was blown at 40 ° C. until the filtrate did not appear red by phenolphthalein (about 10 minutes) to neutralize the sodium hydroxide remaining in the form of an aqueous solution in the filtrate. The reason why sodium hydroxide is present in the form of an aqueous solution is that water is a by-product by the ring reaction.

e) adsorption process by solid acid

The filtrate after neutralization was distilled at 80 degreeC and 3 mmHg for 2 hours, and it dehydrated and desolvented.

Then, 3 g of synthetic aluminum silicate (brand name "Kyoword 700 SL", Kyogawa Chemical Co., Ltd. synthetic aluminum silicate) was added, and the mixture was stirred at 80 ° C and 3 mmHg for 30 minutes, and then a solid (solid sodium chloride, synthetic Aluminum silicate and sodium carbonate from the neutralization process).

As a result, 301 g of the target trimethylolpropanepolyglycidyl ether having an epoxy equivalent of 122, an organochlorine content of 7.0%, and a viscosity (the viscosity at 25 ° C, the same as described in the examples and comparative examples below) 110 cP (Yield 99.7%) was obtained. In addition, the sodium content in the said glycidyl compound was below a detection limit (0.1 ppm, the same in the following description).

Example 2

492 g (1.0 mol) of bisphenol A ethylene oxide 6 mol adducts and 76 g of xylene were put into the same reactor as Example 1, and dehydrated for 1 hour at 100 ° C under reduced pressure.

After cooling to 80 ° C., 3.2 g of ditin chloride pentahydrate was added, and 194 g (2.1 mol) of epichlorohydrin was added dropwise at 80 ° C. over 30 minutes, followed by stirring at 100 ° C. for 30 minutes, followed by addition reaction. Terminated.

Subsequently, after cooling to 80 degreeC, after adding 0.7 g of benzyl trimethylammonium chloride, 177g of 50% sodium hydroxide aqueous solution was added at 80 degreeC for 30 minutes, stirring was continued at 80 degreeC for 2 hours, and the ring closing reaction was complete | finished.

250 g of distilled water was added and stirred at 60 ° C. for 30 minutes to dissolve by-product sodium chloride, and then allowed to stand to remove the brine layer, and the carbon dioxide gas was blown in until the oil layer did not become red by phenolphthalein (about 10 minutes). Sodium hydroxide was neutralized.

After dehydrating and desolventing at 120 ° C. and 3 mmHg for 2 hours, 3 g of synthetic aluminum silicate (brand name “Kyoword 700 SN” manufactured by Kyowa Chemical Co., Ltd.) was added and 30 g at 80 ° C. and 3 mmHg. Stirred for a minute.

Thereafter, 601 g (yield 98.6%) of glycidyl ether of bisphenol A ethylene oxide 6 mole adduct having an epoxy equivalent of 365 and an organochlorine content of 1.7% having a viscosity of 1100 cP was obtained by filtration.

In addition, the sodium content in the glycidyl compound was below the detection limit. Moreover, the nitrogen content derived from benzyl trimethyl ammonium chloride was 0.7 ppm.

Example 3

168 g (1 mol) of 4-methylhexahydrophthalic anhydride, 250 g (2.7 mol) of epichlorohydrin, 3.3 g of tetramethylammonium chloride, and 30 g of distilled water were added to the same reactor as in Example 1, followed by stirring at 80 ° C. for 5 hours. The reaction was terminated.

Subsequently, 149 g of toluene was added to the reaction mixture. Subsequently, azeotropic dehydration was carried out dropwise with 213 g of 45% aqueous sodium hydroxide solution added dropwise at 80 ° C. over 2 hours to terminate the ring closure reaction.

Thereafter, the ring-closing reactant was stirred at 40 ° C while adding dry ice until phenolphthalein did not show a red color to neutralize the remaining sodium hydroxide ring.

After dehydrating and desolventing at 120 ° C. and 3 mmHg for 2 hours, 3 g of GW 700 was added and stirred at 80 ° C. and 3 mmHg for 30 minutes.

Then, 298 g (yield 93.3%) of 4-methylhexahydro phthalic anhydride diglycidyl esters which have an epoxy equivalent of 171, an organic chlorine content of 0.6%, and a viscosity of 520 cP were obtained by filtration. In addition, the sodium content in the glycidyl compound was below the detection limit. In addition, the nitrogen content derived from benzyl trimethylammonium chloride was 0.8 ppm.

Comparative Example 1

Except not blowing carbon dioxide gas, the process was carried out in accordance with Example 1, whereby 291 g (yield 96.4%) of the desired trimethylolpropanepolyglycidyl ether was obtained.

Incidentally, its epoxy equivalent was 190, the organic chlorine content was 6.9%, and the viscosity was 220 cP.

Comparative Example 2

The reaction was carried out in accordance with Example 2 except that no carbon dioxide gas was blown, and after the ring-closure reaction, washing with water was repeated until the red color was not indicated by phenolphthalein, but residual sodium hydroxide was removed in the second and subsequent washing operations. The emulsification of the oil layer was remarkable and it took a long time to separate the aqueous layer. Furthermore, after dehydrating and desolventing at 120 degreeC and 3 mmHg for 2 hours, it filtered and 565g (yield 92.7%) of the target diglycidyl ethers of the 6-mole addition product of the bisphenol A ethylene oxide were obtained.

Incidentally, its epoxy equivalent was 364, the organic chlorine content was 1.8%, and the viscosity was 1080 cP.

Comparative Example 3

The reaction was carried out in accordance with Example 3, except that the carbon dioxide gas was not blown, and after the ring closure reaction, water washing was repeated until the red color was not indicated by phenolphthalein to remove the remaining sodium hydroxide. After further dehydrating and desolventing at 120 ° C., 3 mmHg for 2 hours, and filtered, 254 g (yield 79.4%) of the target 4-methylhexahydro phthalic anhydride diglycidyl ester was obtained.

Incidentally, its epoxy equivalent was 164, the organic chlorine content was 0.6%, and the viscosity was 510 cP.

[Comparative Example 4]

After dehydration and desolvent, the resultant was filtered in accordance with Example 2, except that filtered 700 SN was not added thereto, whereby 603 g of diglycidyl ether of the desired bisphenol A-ethylene oxide 6 mol adduct was obtained (yield 99.0%). ) Was obtained.

Incidentally, its epoxy equivalent was 364, the organochlorine content was 1.7%, and the viscosity was 1100 cP. In addition, the sodium content in the said glycidyl compound was 4.3 ppm. Moreover, the nitrogen content derived from benzyl trimethyl ammonium chloride was 27.8 ppm.

Claims (4)

Closing the halohydrin intermediate obtained by the addition reaction of an alcohol compound, a phenol compound, a carboxylic acid compound and an amine compound with an epihalohydrin compound or a halohydrin compound in the presence of a dehalogenated hydrogenating agent In the method for producing a glycidyl compound, after the end of the ring closure reaction, (1) a neutralization step of introducing carbon dioxide into the reaction mixture to neutralize the reaction mixture, and (2) the reaction mixture after the completion of the neutralization step is silica and A method for producing a glycidyl compound, comprising the step of contacting alumina with a solid acid as a main component. The production process according to claim 1, wherein after removing the by-product salt from the reaction mixture after the end of the ring closure reaction, a neutralization step is performed. The method according to claim 1, wherein water or a solvent is distilled off from the reaction mixture after the neutralization step is completed, and then contacted with a solid acid mainly composed of silica and alumina. The production process according to claim 1, wherein the reaction mixture after the neutralization step is brought into contact with a solid acid mainly composed of silica and alumina under a temperature condition of about 50 to 100 ° C and a reduced pressure of about 3 to 20 mmHg.