WO2018083881A1

WO2018083881A1 - Method for producing polyvalent glycidyl compound

Info

Publication number: WO2018083881A1
Application number: PCT/JP2017/032355
Authority: WO
Inventors: 千佳山下; 圭孝石橋
Original assignee: 昭和電工株式会社
Priority date: 2016-11-07
Filing date: 2017-09-07
Publication date: 2018-05-11
Also published as: TW201825469A; JPWO2018083881A1; CN109689634A; KR20190034610A; TWI679196B; KR102204653B1; JP2022087349A

Abstract

Provided is a method for efficiently producing a polyvalent glycidyl compound by oxidizing a polyvalent allyl compound using hydrogen peroxide as an oxidizing agent. A method for producing a polyvalent glycidyl compound in which the carbon-carbon double bonds of the allyl groups of a polyvalent allyl group having at least three allyl groups are epoxidated using aqueous hydrogen peroxide as an oxidizing agent, wherein said method for producing a polyvalent glycidyl compound is characterized in that an epoxidation reaction is performed in one step, and the reaction is stopped when the ratio of hydrolyzate (rate of hydrolysis) of a produced glycidyl group is within a range of 0.5 to 10%.

Description

Method for producing polyvalent glycidyl compound

The present invention relates to a method for producing a polyvalent glycidyl (epoxy) compound. More specifically, the present invention relates to a method for producing a polyvalent glycidyl compound which is excellent in optical properties, hardness, strength and heat resistance, and which is a raw material for a curable resin composition particularly suitable for the field of electronic materials.

Glycidyl compounds are used in many applications such as the paint field, civil engineering field, and electrical field because of their excellent electrical properties, adhesion, and heat resistance. In particular, aromatic glycidyl (epoxy) compounds such as bisphenol A type diglycidyl ether, bisphenol F type diglycidyl ether, phenol novolac type epoxy resin, and cresol novolac type epoxy resin are water resistant, adhesive, mechanical properties, heat resistance, It is widely used in combination with various curing agents because of its excellent electrical insulation and economy.

As a conventionally known method for producing a glycidyl ether compound, which is a representative example of a glycidyl (epoxy) compound, a corresponding alcohol is reacted with epichlorohydrin under basic conditions in the presence or absence of a catalyst, There is a method for obtaining a glycidyl ether compound. In this method, the organic chlorine compound always remains in the glycidyl ether compound, and is not preferred for use in some applications, for example, electronics applications because of the disadvantage that the insulating properties are lowered. In particular, in the case of aliphatic alcohols, the ring-opening addition product produced by the reaction with epichlorohydrin has an alcoholic hydroxyl group, which is not desirable for further reaction with epichlorohydrin or during ring-opening addition. Since the reaction at the position may occur, there is a problem that the content of the organic chlorine compound is high. Furthermore, in the polyhydric alcohol which has multiple reaction points, the said problem becomes remarkable and it is known that the purity of a target object will be remarkably low.

Therefore, as a method of synthesizing a glycidyl ether compound that does not use epichlorohydrin, which is a halogen compound, it is obtained by using an oxidizing agent such as hydrogen peroxide after allylation of the starting alcohol (first step). The direct glycidylation of the carbon-carbon double bond of the allyl group of the allyl ether compound (second step) has been studied.

One method for glycidyl (epoxy) conversion of allyl ether compounds using hydrogen peroxide as an oxidizing agent (second step) is in the presence of basic salt compounds such as alkali metal carbonates and hydrogen carbonates. In addition, a method of reacting hydrogen peroxide and an organic nitrile compound with a carbon-carbon double bond of an allyl ether compound is known. For example, Patent Document 1 (Japanese Patent Laid-Open No. 59-227872) discloses the production of an epoxy compound in which a polyallyl ether compound is reacted with hydrogen peroxide while adjusting the pH of the reaction system to 7.5 or higher in the presence of acetonitrile. A method is disclosed. Patent Document 2 (Japanese Patent Application Laid-Open No. 2008-239579) discloses the production of an epoxy compound having an adamantane skeleton in which an allyloxy compound having an adamantane skeleton, a nitrile compound, and a hydrogen peroxide solution are reacted in the presence of a basic compound. A method is disclosed. Patent Document 3 (International Publication No. 2011/078091) has a carbon-carbon double bond using hydrogen peroxide as an oxidizing agent while controlling the inside of the reaction system to a predetermined acetonitrile concentration using a solvent containing alcohol. A method for producing an epoxy compound in which the carbon-carbon double bond of an organic compound is epoxidized is disclosed. Patent Document 4 (Japanese Patent Application Laid-Open No. 2013-112649) discloses a method for producing a polyvalent glycidyl compound comprising a step of stopping the epoxidation reaction in the middle of the reaction to remove water in the reaction solution and restarting the epoxidation reaction. Is disclosed.

JP 59-227872 A JP 2008-239579 A International Publication No. 2011/078091 JP 2013-112649 A

Patent Documents 1 to 3 are all water-based reactions carried out under basic conditions. However, Patent Documents 1 to 3 do not recognize the problem of suppressing hydrolysis of the glycidyl ether compound produced. On the other hand, in Patent Document 4, in the reaction of epoxidation using a polyvalent allyl compound having three or more allyl groups as a substrate, the hydrolysis reaction of the glycidyl group of the reaction intermediate proceeds during the reaction, epoxy It is described that a polyvalent glycidyl compound is produced by a method including a step of stopping the reaction in the middle of the conversion reaction, removing water in the reaction solution, and then performing an epoxidation reaction again. However, in the method described in Patent Document 4, the epoxidation reaction is performed in multiple stages, and the manufacturing process is complicated.

The formation of hydrolyzate of glycidyl group is one of the most important factors in reducing the yield and purity of the target product in the production method of epoxy compound that uses an aqueous reactant such as hydrogen peroxide to glycidylate allyl ether compound. One. Furthermore, when a hydrolyzate of a glycidyl group is included as an impurity in the target product, the diol group of the hydrolyzate and the glycidyl group react and self-polymerize, so there is a problem that the stability of the product is not sufficient. . Since the diol compound functions as a curing agent for the epoxy compound, it affects the reactivity at the time of resin curing and the physical properties after resin curing, which is not preferable in terms of product management. Therefore, in order to produce an epoxy compound efficiently in the above production method, it is important to suppress the formation of a glycidyl group hydrolyzate.

The formation of a hydrolyzate of a glycidyl group is particularly remarkable when an allyl compound having three or more allyl groups in the molecule is used as a substrate. While the epoxidation reaction of a substrate having one or two allyl groups in the molecule proceeds rapidly, allyl compounds having three or more allyl groups in the molecule can be converted to three or more glycidyl groups in the molecule. In the case of producing the glycidyl compound having a large number of reaction substituents, it takes a longer time to react until all the allyl groups are epoxidized. Therefore, a part of the reaction intermediate (n (n ≧ 3)) allyl groups (for example, one or two) formed by epoxidation reaction of allyl group during a long reaction became glycidyl group ) Hydrolysis of the glycidyl group proceeds simultaneously. Moreover, the stronger the polarity of the compound, the easier it is to be distributed to the water system, and the hydrolysis reaction tends to proceed. A compound having more glycidyl groups in the molecule tends to have higher polarity and higher solubility in water. Therefore, it is difficult to obtain a product having many glycidyl groups in a high yield.

The object of the present invention is to provide a method for efficiently producing a polyvalent glycidyl compound in a high yield from a polyvalent allyl compound having three or more allyl groups in the molecule.

As a result of intensive studies and repeated experiments to solve the above problems, the present inventors oxidized a polyvalent allyl compound having three or more allyl groups in the molecule using an aqueous hydrogen peroxide solution as an oxidizing agent. In the method for producing a polyvalent glycidyl compound having three or more glycidyl groups in the molecule by (epoxidation), the ratio of the hydrolyzate of the generated glycidyl group is in the range of 0.5 to 10%. When the reaction was stopped sometimes, it was found that the content of hydrolyzate of glycidyl group was small and a polyvalent glycidyl compound could be obtained with high efficiency, and the present invention was completed.

That is, the present invention is as follows.
[1] Epoxidation in a method for producing a polyvalent glycidyl compound in which a carbon-carbon double bond of an allyl group of a polyvalent allyl compound having three or more allyl groups is epoxidized using an aqueous hydrogen peroxide solution as an oxidizing agent A polyvalent glycidyl compound characterized in that the reaction is stopped in one stage and the reaction is stopped when the ratio of the glycidyl group hydrolyzate produced (hydrolysis rate) is in the range of 0.5% to 10%. Manufacturing method.
[2] The method for producing a polyvalent glycidyl compound according to [1], wherein the epoxidation reaction is performed in the presence of acetonitrile and alcohol.
[3] The method for producing a polyvalent glycidyl compound according to [2], wherein the alcohol is an alcohol having 1 to 4 carbon atoms.
[4] The polyaryl group according to any one of [1] to [3], wherein the allyl group is bonded to an oxygen atom to form an allyl ether group, or is bonded to an amino group to form an allylamino group. For producing a monovalent glycidyl compound.
[5] The polyvalent allyl compound is trimethylolpropane triallyl ether, glyceryl triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, ditrimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, diglycerin tri Allyl ether, diglycerin tetraallyl ether, erythritol triallyl ether, erythritol tetraallyl ether, xylitol triallyl ether, xylitol tetraallyl ether, xylitol pentaallyl ether, dipentaerythritol triallyl ether, dipentaerythritol tetraallyl ether, dipenta Erythritol pentaallyl ether, dipentaerythritol hexa Ril ether, sorbitol triallyl ether, sorbitol tetraallyl ether, sorbitol pentaallyl ether, sorbitol hexaallyl ether, inositol triallyl ether, inositol tetraallyl ether, inositol pentaallyl ether, inositol hexaallyl ether, phenol novolac polyallyl ether, cresol A polyaryl ether, naphthalene-containing novolak polyallyl ether, tetraallyl diaminodiphenyl methane, triallyl isocyanurate, diallyl aminophenol allyl ether, or any one of [1] to [4] For producing a monovalent glycidyl compound.

According to the method for producing a polyvalent glycidyl compound of the present invention, a polyvalent glycidyl compound can be efficiently produced in a high yield from a polyvalent allyl compound having three or more allyl groups in the molecule.

Hereinafter, the present invention will be described in detail.
The method for producing a polyvalent glycidyl compound of the present invention is a method for producing a glycidyl compound in which an organic compound having a carbon-carbon double bond is epoxidized using an aqueous hydrogen peroxide solution as an oxidizing agent. In which the epoxidation reaction is carried out in one step using a polyvalent allyl compound having three or more allyl groups as the organic compound, and the ratio of the hydrolyzate of glycidyl group produced is in the range of 0.5 to 10% It is characterized by stopping the reaction when it is inside.

In the present invention, an aqueous hydrogen peroxide solution is used as the oxidizing agent. The concentration of the aqueous hydrogen peroxide solution is not particularly limited, but is generally selected from the range of 1 to 80% by mass, preferably 10 to 60% by mass. From the viewpoint of industrial productivity and the energy cost of separation, a high concentration of the aqueous hydrogen peroxide solution is preferable. On the other hand, an excessively high concentration and / or an excessive amount of the aqueous hydrogen peroxide solution is required. It is preferable not to use it from the viewpoints of economy and safety.

There are no particular restrictions on the amount of aqueous hydrogen peroxide used. The hydrogen peroxide concentration in the reaction system decreases as the reaction proceeds. It is preferable to keep the hydrogen peroxide concentration in the reaction system within the range of 0.1 to 30% by mass, more preferably within the range of 0.2 to 10% by mass. If it is 0.1% by mass or more, the productivity is good. On the other hand, if it is 30% by mass or less, when alcohol is used as a solvent, the reaction is safe by suppressing the explosive property in the mixed composition of alcohol and water. Can be done. In addition, if a large amount of hydrogen peroxide is charged into the reaction system at the beginning of the reaction, the reaction may proceed rapidly and may be dangerous. Therefore, it is preferable to slowly add hydrogen peroxide into the reaction system as described later.

The epoxidation reaction in the method for producing a polyvalent glycidyl compound of the present invention is not particularly limited as long as it is a reaction in which a polyvalent allyl compound having three or more allyl groups is epoxidized with an aqueous hydrogen peroxide solution. A method in which hydrogen peroxide and a nitrile compound such as acetonitrile are reacted with a carbon-carbon double bond of an allyl compound in the presence of a basic salt compound such as a metal carbonate or hydrogen carbonate, and tungstic acid, phosphoric acid and quaternary And a method of epoxidizing a carbon-carbon double bond of an allyl compound using hydrogen peroxide as an oxidizing agent in the presence of a quaternary ammonium salt. The method of epoxidizing the polyvalent allyl compound with an aqueous hydrogen peroxide solution can be appropriately selected depending on the properties of the substrate.

Hereinafter, a method for epoxidizing a polyvalent allyl compound using hydrogen peroxide and acetonitrile will be described in detail.

Considering industrially stable production, hydrogen peroxide is consumed in the reaction while acetonitrile and the substrate polyvalent allyl compound are first charged into the reactor and the reaction temperature is kept as constant as possible. It is preferable to add gradually while confirming the above. By adopting such a method, even if hydrogen peroxide is abnormally decomposed in the reactor and oxygen gas is generated, the amount of hydrogen peroxide accumulated is small and the pressure rise can be minimized.

It is preferable to control the concentration of acetonitrile in the reaction system during the reaction so that it is in the range of 5 to 50 mol / L. In another embodiment, the concentration of acetonitrile in the reaction system is preferably controlled during the progress of the reaction so as to be in the range of 1 to 10 mol / L. In a method for producing a glycidyl compound in which an organic compound having a carbon-carbon double bond is epoxidized using hydrogen peroxide as an oxidizing agent in the presence of acetonitrile, acetonitrile and hydrogen peroxide React with each other to produce an oxidation active species (perimidic acid), and it is considered that the carbon-carbon double bond is oxidized by the oxidation active species. Therefore, the theoretical required amount of acetonitrile in this reaction is equivalent to the amount of carbon-carbon double bonds of the organic compound (equal mole), and the concentration of acetonitrile in the reaction system decreases as the reaction proceeds. The concentration of acetonitrile in the reaction system can be appropriately selected according to the amount of carbon-carbon double bonds of the organic compound. If the concentration in the reaction system is 1 mol / L or more, or 5 mol / L or more, the reaction rate is appropriate, and thus the productivity is good. On the other hand, if the concentration is 10 mol / L or less, or 50 mol / L or less, peroxidation occurs. The hydrogen epoxidation selectivity is good and the cost is also appropriate. Therefore, the initial concentration at the start of the reaction is set in the above concentration range, the concentration during the reaction is monitored, and the concentration is added by adding within the range not exceeding the upper limit before the concentration falls below the lower limit. It is preferable to control. The concentration is more preferably 6 mol / L or more, and more preferably 40 mol / L or less. In another embodiment, the concentration is more preferably 1.5 mol / L or more, further preferably 5 mol / L or more, and more preferably 10 mol / L or less.

As described above, when the epoxy (glycidyl) -forming reaction is performed using acetonitrile, it is preferable that alcohol be present in the reaction system as a solvent. The alcohol functions as a solvent for the substrate and also as a viscosity diluent to increase the rate of transfer of hydrogen peroxide to the substrate when the viscosity of the substrate is high. In addition, when the substrate has low hydrophilicity, the alcohol has an action of increasing the reaction rate by making the organic layer containing the substrate and acetonitrile and the aqueous layer containing hydrogen peroxide uniform. If no alcohol is allowed to coexist or if the amount used is insufficient, two-layer separation may occur in the reaction system, and as a result, the epoxidation selectivity of hydrogen peroxide may decrease. The alcohol is preferably an alcohol having 1 to 4 carbon atoms, more preferably a primary alcohol having 1 to 4 carbon atoms, still more preferably methanol, ethanol or 1-propanol. The alcohol used in the reaction is preferably in the range of 0.1 to 5 times, more preferably 0.2 to 4 times, more preferably 0.2 to 4 times the mass ratio of the charged amount to the amount of acetonitrile used. A range of 3 to 3 times is more preferable. By making the amount of alcohol charged relative to the amount of acetonitrile used in the above range, the stability of the perimidic acid, which is an oxidatively active species, in the reaction system can be increased and the reaction can be carried out efficiently.

The amount of acetonitrile charged at the start of the reaction is preferably in the range of 1.2 to 5 molar equivalents based on the number of carbon-carbon double bonds of the organic compound having a carbon-carbon double bond. ˜3 molar equivalents are more preferred. If it is 1.2 molar equivalents or more, the yield is good, while if it is 5 molar equivalents or less, the epoxidation selectivity of hydrogen peroxide is good, and the cost is also appropriate. The amount of acetonitrile charged at the start of the reaction is preferably 5 to 50 mol / L, more preferably 6 to 40 mol / L, which is the concentration range in the reaction system during the reaction. In another embodiment, the amount of acetonitrile charged at the start of the reaction is preferably 1 to 10 mol / L, more preferably 1.5 to 10 mol / L, and 5 to 10 mol / L. Further preferred. When acetonitrile is added during the reaction, the ratio of the total amount of acetonitrile used to the total amount of substrate used in the reaction (acetonitrile / substrate carbon-carbon double bond (molar ratio)) is also in the above range, that is, 1. It is preferable to satisfy 2 to 5, more preferably 1.5 to 3.

The ratio of the amount of hydrogen peroxide used to the amount of acetonitrile used (hydrogen peroxide / acetonitrile (molar ratio) is preferably 0.1 or more, and preferably 1.1 or less, 1.0 By setting it within the above range, hydrolysis can be suppressed and the reaction can be performed in a homogeneous system, and the reaction can be performed efficiently.

The reaction can be performed with the substrate completely dissolved. In particular, when the organic layer in which the substrate is dissolved and the aqueous layer in which the hydrogen peroxide is dissolved are not separated into two layers, the reaction can be efficiently performed.

In the method for producing a polyvalent glycidyl compound of the present invention, the pH of the reaction solution is preferably 9 to 11, more preferably 9.5 to 11, and still more preferably 10 to 11. If the pH is 9 or more, the reaction rate is appropriate, and thus the productivity is good. On the other hand, if the pH is 11 or less, the risk of the reaction proceeding rapidly is extremely low, which is preferable. Since hydrogen peroxide decomposes actively in a highly alkaline atmosphere, the pH is set to about 9 to 10 at the initial stage of the reaction, and the pH of the reaction solution is gradually set to about 10 to 11 as necessary with the addition of hydrogen peroxide. More preferably, it is controlled. When a polyvalent allyl compound having 3 or more carbon-carbon double bonds is used as a substrate, the yield and selectivity of the polyvalent glycidyl compound are affected by the pH of the reaction system, but the pH is in the range of 10-11. Within the range, both the yield and selectivity of the polyvalent glycidyl compound are preferred.

Examples of the basic salt compound used for pH adjustment in the reaction system include, for example, potassium carbonate, potassium hydrogen carbonate, potassium hydroxide, sodium hydroxide, cesium hydroxide and other inorganic basic salts, potassium methoxide, potassium ethoxide, Organic base salts such as sodium methoxide, sodium ethoxide, tetramethylammonium hydroxide and the like can be mentioned. Potassium carbonate, potassium hydrogen carbonate, potassium hydroxide, sodium hydroxide, potassium methoxide, potassium ethoxide, sodium methoxide, and sodium ethoxide are preferable in terms of easy pH adjustment. Potassium hydroxide and sodium hydroxide are more preferable because of their high solubility in water and alcohol and good reactivity.

The basic salt compound can be used as an aqueous solution or an alcohol solution. Examples of the alcohol used as the solvent of the alcohol solution include methanol, ethanol, propanol, butanol and the like, and it is preferable to use the same reaction solvent as that described above. The solution of the basic salt compound is preferably added so that the pH of the reaction solution does not fall below 9 with the addition of hydrogen peroxide. At this time, the temperature of the reaction solution is preferably in the range of 20 to 100 ° C., more preferably It is preferable to add such that the range of 25 to 60 ° C. is maintained.

In the method for producing a polyvalent glycidyl compound of the present invention, the reaction temperature is usually in the range of 20 to 100 ° C., preferably in the range of 25 to 60 ° C. The reaction time depends on the reaction temperature and cannot be determined generally, but is usually in the range of 4 to 100 hours, preferably in the range of 8 to 80 hours.

After the epoxidation reaction, a step of stopping the reaction is performed as a post-process. The step of stopping the reaction can be performed by quenching the reaction solution with an aqueous solution containing a reducing agent. After the reaction is stopped, water in the reaction system can be removed. The determination of termination of the reaction of the present invention is made based on the ratio (hydrolysis rate) in the system of hydrolyzate of glycidyl group generated in the later stage of the epoxidation reaction. In the reaction of epoxidation using a polyvalent allyl compound having three or more allyl groups as a substrate, the epoxidation reaction requires a longer time than in the case of using an allyl compound having one or two allyl groups as a substrate. And the polarity of the reaction intermediate obtained is strong. Therefore, during the reaction, it is confirmed that the hydrolysis reaction of the glycidyl group of the reaction intermediate produced as the reaction proceeds proceeds. Formation of a hydrolyzate of a glycidyl group can be confirmed by spectroscopic analysis such as gas chromatography (GC), high performance liquid chromatography (LC), and ¹ H-NMR. It is considered that the progress of the hydrolysis reaction is greatly influenced by the increase in water in the reaction solution due to the aqueous hydrogen peroxide solution added as an oxidizing agent. In order to suppress the ratio of hydrolyzate of glycidyl group, the ratio of the amount of hydrolyzate generated in the latter stage of the reaction is 0.5 to 10%, preferably 0.5 to 8%, more preferably 0.5 to The next post-treatment step, that is, the step of stopping the reaction is carried out within the range of 5%. By setting the hydrolysis rate to be within 10% as the standard for the next step, the production of a glycidyl group hydrolyzate as a by-product can be suppressed. Moreover, the target polyvalent glycidyl compound can be obtained with a favorable yield by setting the hydrolysis rate to 0.5% or more.

The ratio of the glycidyl group hydrolyzate in the system (hydrolysis rate) was determined by, for example, identifying the polyvalent glycidyl compound by ¹ H-NMR analysis and then analyzing the polyvalent glycidyl compound by GC or LC analysis. Then, the reaction solution can be subjected to GC or LC analysis, and can be determined from the ratio of the signal integral intensity of the hydrolyzate to the total signal integral intensity. In GC and LC, a retention time is obtained from a standard substance. For example, in a reverse phase column, a signal observed in a time shorter than the retention time of the target product is attributed to the signal of the hydrolyzate. For the analysis, for example, ACQUITY UPLC (TM) BEH C18 manufactured by Japan Waters Corporation can be used, and acetonitrile and water can be used as an elution solvent.

The step of stopping the reaction is preferably performed when it is confirmed that the production rate of the hydrolyzate of the glycidyl group exceeds the consumption rate of the allyl group of the polyvalent allyl compound of the substrate. Therefore, the method for producing a polyvalent glycidyl compound may further include a step of confirming that the production rate of the hydrolyzate of the glycidyl group exceeds the consumption rate of the allyl group of the polyvalent allyl compound. The rate of formation of the hydrolyzate of the glycidyl group relative to the consumption rate of the allyl group of the polyvalent allyl compound is, for example, that the reaction solution is analyzed every 30 minutes by gas chromatography, and the peak area of the substrate is This can be confirmed by comparing the decrease rate with the increase rate of the peak area of the hydrolyzate.

Since the reaction solution usually contains hydrogen peroxide, it is necessary to reduce and remove hydrogen peroxide when removing water in the reaction solution. Examples of the reducing agent used include sodium sulfite and sodium thiosulfate, but are not limited to these reducing agents. At this time, in order to efficiently separate and remove the water in the reaction system from the organic layer containing the reaction intermediate, it is preferable to add an appropriate amount of an organic solvent having low compatibility with water to the reaction solution. Examples of the organic solvent to be used include toluene, ethyl acetate, dichloromethane and the like, but are not limited to these organic solvents. This treatment removes hydrogen peroxide remaining in the reaction solution, separates the aqueous layer and the organic layer (organic solvent), collects and concentrates the reaction product contained in the organic layer (organic solvent), if necessary The desired polyvalent glycidyl compound can be obtained by purification by a known method (distillation, chromatographic separation, recrystallization, sublimation, etc.). If the yield of the target polyvalent glycidyl compound is 50% or more, it is good for industrial use.

In the method for producing a polyvalent glycidyl compound of the present invention, an epoxidation reaction is performed in one step. “One stage” means that the epoxidation reaction is not resumed after the epoxidation reaction is stopped. Therefore, the yield can be increased by minimizing the loss of reaction product due to the termination of the epoxidation reaction and the step of removing water in the reaction solution.

The substrate used in the method for producing a polyvalent glycidyl compound of the present invention is not particularly limited as long as it is an organic compound having three or more carbon-carbon double bonds, but an allyl group is bonded to an oxygen atom to form an allyl ether group. Or an organic compound which is bonded to an amino group to form an allylamino group. In another embodiment, the substrate used in the method for producing a polyvalent glycidyl compound is preferably a compound having three or more allyl ether groups. As used herein, “allyl ether group” means a “C═C—C—O—” bond, that is, an allyloxy group, and “allylamino group” means

Alternatively, it means a group represented by “C═C—C—NH—”. The number of carbon-carbon double bonds contained in the compound may be 3, or 4 or more. Examples of the compound having three carbon-carbon double bonds include trimethylolpropane triallyl ether, glycerin triallyl ether, pentaerythritol triallyl ether, ditrimethylolpropane triallyl ether, diglyceryl triallyl ether, erythritol triallyl ether, Examples include xylitol triallyl ether, dipentaerythritol triallyl ether, sorbitol triallyl ether, inositol triallyl ether, triallyl isocyanurate, diallylaminophenol allyl ether and the like. Examples of the compound having 4 or more carbon-carbon double bonds include pentaerythritol tetraallyl ether, ditrimethylolpropane tetraallyl ether, diglycerin tetraallyl ether, erythritol tetraallyl ether, xylitol tetraallyl ether, xylitol pentaallyl. Ether, dipentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipentaerythritol hexaallyl ether, sorbitol tetraallyl ether, sorbitol pentaallyl ether, sorbitol hexaallyl ether, inositol tetraallyl ether, inositol pentaallyl ether, inositol hexaallyl ether Allyl ether, phenol novolac type polyallyl ether, creso Poly-allyl ether, naphthalene-containing novolac polyallyl ether, tetraallyl diaminodiphenylmethane and the like.

The organic compound having 3 or more carbon-carbon double bonds is preferably a chain, monocyclic or condensed ring compound. The organic compound having three or more carbon-carbon double bonds is preferably an aliphatic compound, more preferably a chain or monocyclic aliphatic compound. Among them, trimethylolpropane triallyl ether, glycerin triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, ditrimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, diglyceryl triallyl ether, diglycerin tetraallyl Ether, erythritol triallyl ether, erythritol tetraallyl ether, xylitol triallyl ether, xylitol tetraallyl ether, xylitol pentaallyl ether, dipentaerythritol triallyl ether, dipentaerythritol tetraallyl ether, dipentaerythritol pentaallyl ether, dipenta Erythritol hexaallyl ether, sol Tall triallyl ether, sorbitol tetra allyl ether, sorbitol penta allyl ether, sorbitol hexa allyl ether, inositol triallyl ether, inositol tetra allyl ether, inositol penta allyl ether, inositol hexaallyl ether, triallyl isocyanurate is preferred. The method for producing a polyvalent glycidyl compound of the present invention is particularly preferably used for a compound that is easily distributed to an aqueous system and easily undergoes a hydrolysis reaction, and such a compound can be obtained in a high yield.

The reaction tank is not particularly limited, and batch type, continuous type and the like can be mentioned. In the case of the batch type, when the hydrolyzate of glycidyl group in the reaction tank is in the range of 0.5 to 10%, the liquid is transferred to the next tank. In the case of a continuous type, the glycidyl group hydrolyzate is within the range of 0.5 to 10% at the end point of the reaction vessel.

Hereinafter, the present invention will be specifically described by way of examples. However, the present invention is not limited to the following examples.

[Reaction conditions]
-Hydrogen peroxide concentration Referring to the method described in JP-A-6-130051, potassium iodide and free iodine were titrated with a sodium thiosulfate standard solution to measure the peracetic acid concentration. A large excess of aqueous potassium iodide solution, dilute sulfuric acid, and aqueous ammonium molybdate solution are added, and the liberated iodine is titrated using a sodium thiosulfate standard solution and a starch solution as a color reagent to measure the hydrogen peroxide concentration.
Hydrolysis rate First, the polyvalent glycidyl ether compound in the reaction solution was isolated by column chromatography (silica gel 60 (spherical), manufactured by Kanto Chemical Co., Inc.) and identified by ¹ H-NMR analysis, followed by UHPLC analysis (Japan Waters, ACQUITY UPLC (TM) BEH C18, elution solvent: acetonitrile and water, gradient method), and the detection time of the polyvalent glycidyl ether compound is determined. Next, the reaction solution was subjected to UHPLC analysis (manufactured by Waters Japan, ACQUITY UPLC (TM) BEH C18, elution solvent: acetonitrile and water, gradient method), and the following (a) to (c) based on the polyvalent glycidyl ether compound. Are obtained by integrating the areas of the three regions.
(A) Area shorter than the detection time of the polyvalent glycidyl ether compound: glycidyl group hydrolyzate of the target product (a) Peak of the polyvalent glycidyl ether compound (U) Longer than the detection time of the polyvalent glycidyl ether compound Region: Allyl ether hydrolysis rate estimated as a reaction intermediate is obtained from the following formula.
Hydrolysis rate = {(A) area} / {(A) (I) (U) total area}

[Evaluation]
-Crude yield Calculated from the following formula.
Crude yield = (acquired amount of product obtained after post-treatment) / (theoretical acquired amount calculated from the charged amount)
-Substrate purity First, the substrate was isolated by column chromatography (manufactured by Kanto Chemical Co., Inc., silica gel 60 (spherical)) and identified by ¹ H-NMR analysis, followed by UHPLC analysis (manufactured by Waters, Japan, ACQUITY UPLC (TM ) BEH C18, elution solvent: acetonitrile and water, gradient method) and determine substrate detection time. Next, the reaction solution was subjected to UHPLC analysis (manufactured by Japan Waters Co., Ltd., ACQUITY UPLC (TM) BEH C18, elution solvent: acetonitrile and water, gradient method), and the following three regions (a) to (c) were used based on the substrate. Calculate the area by integrating each area.
(A) Region shorter than substrate detection time (A) Substrate peak (C) Region longer than substrate detection time The purity of the substrate is calculated from the following equation.
Substrate purity = {(A) area} / {(A) (A) (U) area total}

-Purity of polyvalent glycidyl ether compound First, the polyvalent glycidyl ether compound was isolated by column chromatography (silica gel 60 (spherical) manufactured by Kanto Chemical Co., Inc.) and identified by ¹ H-NMR analysis, followed by UHPLC analysis (Japan Waters, ACQUITY UPLC (TM) BEH C18, elution solvent: acetonitrile and water, gradient method), and the detection time of the polyvalent glycidyl ether compound is determined. Next, the reaction solution was subjected to UHPLC analysis (manufactured by Waters Japan, ACQUITY UPLC (TM) BEH C18, elution solvent: acetonitrile and water, gradient method), and the following (a) to (c) based on the polyvalent glycidyl ether compound. Are obtained by integrating the areas of the three regions.
(A) Area shorter than the detection time of the polyvalent glycidyl ether compound: glycidyl group hydrolyzate of the target product (a) Peak of the polyvalent glycidyl ether compound (U) Longer than the detection time of the polyvalent glycidyl ether compound Region: The purity of the allyl ether polyvalent glycidyl ether compound estimated as a reaction intermediate is calculated from the following formula.
Purity of polyvalent glycidyl ether compound = {area of (A)} / {total area of (A) (I) (U)}
-Net yield of polyvalent glycidyl ether compound Calculated from the following formula.
Pure yield = crude yield of polyvalent glycidyl ether compound x purity of polyvalent glycidyl ether compound

[Substrate synthesis]
Synthesis Example 1 (Synthesis of pentaerythritol tetraallyl ether)
A 2.0-liter three-necked round bottom flask was charged with 400.0 g (1.57 mol) of Neoallyl (registered trademark) P-30M (pentaerythritol triallyl ether, manufactured by Daiso Corporation), and the inside of the reactor system was replaced with nitrogen gas. . 300 g (3.8 mol) of sodium hydroxide aqueous solution (50% by mass, manufactured by Junsei Chemical Co., Ltd.) was added and heated to 80 ° C., and the reaction system was stirred at about 80 ° C. for 1 hour, and then the reaction system was about 40 ° C. Until cooled. While maintaining the reaction system at about 40 ° C., 55.6 g (0.2 mol) of tetrabutylammonium bromide (manufactured by Tokyo Chemical Industry Co., Ltd.) and 366 g (4.0 mol) of allyl chloride (manufactured by Wako Pure Chemical Industries, Ltd.) The mixture was further stirred for 20 hours. After completion of the reaction, 200 g of ethyl acetate and 100 g of water were added for liquid separation, and the organic layer was washed with pure water at 50 mL / time until neutral. The organic solvent (ethyl acetate) in the obtained organic layer was distilled off to obtain 487.8 g of substrate A (pentaerythritol tetraallyl ether) having a purity of 96%.

Synthesis Example 2 (Synthesis of trimethylolpropane triallyl ether)
In a 2.0-liter three-necked round bottom flask, 2000.0 g (9.4 mol) of Neoallyl (registered trademark) T-20 (trimethylolpropane diallyl ether, manufactured by Daiso Corporation) was placed, and the inside of the reactor system was replaced with nitrogen gas. . Sodium hydroxide aqueous solution (50 mass%) 4500g (56.3mol) was added, and the reaction system was stirred at about 80 ° C for 1 hour, and then cooled to about 40 ° C. While maintaining the reaction system at about 40 ° C., 200.0 g (0.6 mol) of tetrabutylammonium bromide and 2400 g (31.4 mol) of allyl chloride were added and stirred for 20 hours. After completion of the reaction, 2000 g of ethyl acetate and 1000 g of water were added to carry out a liquid separation treatment, and the organic layer was washed with pure water at 500 mL / time until neutral. The organic solvent (ethyl acetate) in the obtained organic layer was distilled off to obtain 2444.3 g of substrate B (trimethylolpropane triallyl ether) having a purity of 94% as measured by gas chromatography.

Synthesis Example 3 (Synthesis of glyceryl triallyl ether)
184.2 g (2.0 mol) of glycerin (manufactured by Tokyo Chemical Industry Co., Ltd.) was placed in a 2.0 liter three-necked round bottom flask, and the inside of the reactor system was replaced with nitrogen gas. 711 g (9.0 mol) of an aqueous sodium hydroxide solution (50% by mass) was added, and the reaction system was stirred at about 80 ° C. for 1 hour, and then cooled to about 40 ° C. While maintaining the reaction system at about 40 ° C., 70.8 g (0.26 mol) of tetrabutylammonium bromide and 659 g (7.2 mol) of allyl chloride were added and stirred for 16 hours. After completion of the reaction, 400 g of ethyl acetate and 300 g of water were added for liquid separation treatment, and the organic layer was washed with pure water at 200 mL / time until neutral. The organic solvent (ethyl acetate) in the obtained organic layer was distilled off to obtain 198.2 g of substrate C (glycerin triallyl ether) having a purity of 97% as measured by gas chromatography.

Synthesis Example 4 (Synthesis of dipentaerythritol hexaallyl ether)
Dipentaerythritol (manufactured by Tokyo Chemical Industry Co., Ltd.) 254.3 g (1.0 mol) was placed in a 2.0 liter three-necked round bottom flask, and the inside of the reactor system was replaced with nitrogen gas. Sodium hydroxide aqueous solution (50 mass%) 632g (8.0mol) was added, and the reaction system was stirred at about 80 ° C for 1 hour, and then cooled to about 40 ° C. While maintaining the reaction system at about 40 ° C., 70.8 g (0.26 mol) of tetrabutylammonium bromide and 659 g (7.2 mol) of allyl chloride were added and stirred for 62 hours. After completion of the reaction, 400 g of ethyl acetate and 300 g of water were added for liquid separation treatment, and the organic layer was washed with pure water at 200 mL / time until neutral. The organic solvent (ethyl acetate) in the obtained organic layer was distilled off to obtain 396.7 g of substrate D (dipentaerythritol hexaallyl ether) having a purity of 92% as measured by gas chromatography.

[Synthesis of polyvalent glycidyl ether compound]
Example 1 (Synthesis of pentaerythritol tetraglycidyl ether)
Two 200 g (0.67 mol) of pentaerythritol tetraallyl ether obtained in Synthesis Example 1, 220 g (5.36 mol) of acetonitrile (manufactured by Junsei Chemical Co., Ltd.), and 100 g (3.12 mol) of methanol (manufactured by Junsei Chemical Co., Ltd.) A liter three-necked flask was charged. The acetonitrile concentration in the system at this stage was 8.84 mol / L. Subsequently, after adding a small amount of 50% by mass potassium hydroxide aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.) to adjust the pH in the reaction system to about 10.5, a 45% by mass hydrogen peroxide aqueous solution (with an internal temperature of 35 ° C.) 160 g (2.12 mol) manufactured by Nippon Peroxide Co., Ltd. was added dropwise over 18 hours so that the internal temperature did not exceed 45 ° C. In addition, since pH fell when hydrogen peroxide aqueous solution was added, 50 mass% potassium hydroxide aqueous solution was also dripped separately so that pH might be maintained at 10.5. The reaction solution was subjected to UHPLC analysis, 30 hours after the start of dropping, when the hydrolysis rate was 5%, 2.11 g of sodium sulfite (manufactured by Wako Pure Chemical Industries, Ltd.) and 1000 g of toluene were added to the reaction solution to stop the reaction, The mixture was stirred for 30 minutes, and the aqueous layer (including sodium sulfite and by-product acetamide) and the organic layer (including the final target product and reaction intermediate) were separated. The acetonitrile concentration in the system at the end of the reaction, calculated as 100% of the consumed acetonitrile reacted with the substrate, was 3.78 mol / L. Thereafter, the organic layer was washed twice with 150 g of pure water to remove residual impurities such as sodium sulfite and by-product acetamide, and the solvent was distilled off to obtain a purity of 89%, a yield of 190.14 g, and a crude yield of 78. A reaction product (target product) was obtained at 2%.

Example 2 (Synthesis of trimethylolpropane triglycidyl ether)
75 g (0.295 mol) of trimethylolpropane triallyl ether obtained in Synthesis Example 2, 75 g (1.83 mol) of acetonitrile, and 72.5 g (2.26 mol) of methanol were charged into a 2-liter three-necked flask. The acetonitrile concentration in the system at this stage was 6.99 mol / L. Subsequently, after adding 50% by mass potassium hydroxide aqueous solution and adjusting the pH of the reaction solution to about 10.5, an inner temperature of 35 ° C. was added with 45 g% hydrogen peroxide aqueous solution 116 g (1.54 mol), and the internal temperature was 45%. It was added dropwise over 30 hours so as not to exceed ° C. In addition, since pH fell when hydrogen peroxide aqueous solution was added, 50 mass% potassium hydroxide aqueous solution was also dripped separately so that pH might be maintained at 10.5. The reaction solution was subjected to UHPLC analysis. After 48 hours from the start of dropping, when the hydrolysis rate was 5%, 3.06 g of sodium sulfite and 200 g of toluene were added to the reaction solution to stop the reaction, followed by stirring at room temperature for 30 minutes. Sodium sulfite, by-product acetamide and the like) and the organic layer (including final product and reaction intermediate) were separated. The acetonitrile concentration in the system at the end of the reaction, calculated as 100% of the consumed acetonitrile reacted with the substrate, was 2.72 mol / L. Thereafter, the organic layer was washed twice with 80 g of pure water to remove residual impurities such as sodium sulfite and by-product acetamide, and then the solvent was distilled off to obtain a purity of 89%, a yield of 66.76 g, and a crude yield of 72. The reaction product (target product) was obtained at .8%.

Example 3 (Synthesis of glycerin triglycidyl ether)
106 g (0.50 mol) of glycerin triallyl ether obtained in Synthesis Example 3, 380 g (3.1 mol) of acetonitrile, and 70.5 g (2.2 mol) of methanol were charged into a 1-liter three-necked flask. The acetonitrile concentration in the system at this stage was 4.59 mol / L. Subsequently, after adding 50% by mass potassium hydroxide aqueous solution and adjusting the pH of the reaction solution to about 10.5, 170 g (2.0 mol) of 45% by mass hydrogen peroxide aqueous solution at an internal temperature of 35 ° C. The solution was added dropwise over 8 hours so as not to exceed ° C. In addition, since pH fell when hydrogen peroxide aqueous solution was added, 50 mass% potassium hydroxide aqueous solution was also dripped separately so that pH might be maintained at 10.5. The reaction solution was analyzed by UHPLC, and 10 hours after the start of dropping, when the hydrolysis rate was 5%, 3.2 g of sodium sulfite and 400 g of toluene were added to the reaction solution to stop the reaction, followed by stirring at room temperature for 30 minutes. Sodium sulfite, by-product acetamide and the like) and the organic layer (including final product and reaction intermediate) were separated. The acetonitrile concentration in the system at the end of the reaction, which was calculated on the assumption that consumed acetonitrile was 100% reacted with the substrate, was 1.97 mol / L. Thereafter, the organic layer was washed twice with 120 g of pure water to remove residual impurities such as sodium sulfite and by-product acetamide, and then the solvent was distilled off to obtain a purity of 92%, a yield of 108 g, and a crude yield of 82.9. %, The reaction product (target product) was obtained.

Example 4 (Synthesis of dipentaerythritol hexaglycidyl ether)
102 g (0.20 mol) of dipentaerythritol hexaallyl ether obtained in Synthesis Example 4, 294 g (2.4 mol) of acetonitrile, and 32.1 g (1.0 mol) of methanol were charged into a 1-liter three-necked flask. The acetonitrile concentration in the system at this stage was 4.67 mol / L. Subsequently, after adding 50% by mass potassium hydroxide aqueous solution and adjusting the pH of the reaction solution to about 10.5, 135 g (1.6 mol) of 45% by mass hydrogen peroxide aqueous solution at an internal temperature of 35 ° C. The solution was added dropwise over 48 hours so as not to exceed ℃. In addition, since pH fell when hydrogen peroxide aqueous solution was added, 50 mass% potassium hydroxide aqueous solution was also dripped separately so that pH might be maintained at 10.5. The reaction solution was subjected to UHPLC analysis. After 50 hours from the start of dropping, when the hydrolysis rate was 5%, 2.5 g of sodium sulfite and 400 g of toluene were added to the reaction solution to stop the reaction, followed by stirring at room temperature for 30 minutes, Sodium sulfite, by-product acetamide and the like) and the organic layer (including final product and reaction intermediate) were separated. The acetonitrile concentration in the system at the end of the reaction, calculated as 100% of the consumed acetonitrile reacted with the substrate, was 2.00 mol / L. Thereafter, the organic layer was washed twice with 120 g of pure water to remove residual impurities such as sodium sulfite and by-product acetamide, and then the solvent was distilled off to obtain a purity of 88%, a yield of 86.9 g, and a crude yield of 71. The reaction product (target product) was obtained at .8%.

Comparative Example 1 (Synthesis of pentaerythritol tetraglycidyl ether)
200 g (0.67 mol) of pentaerythritol tetraallyl ether obtained in Synthesis Example 1, 220 g (5.36 mol) of acetonitrile, and 100 g (3.12 mol) of methanol were charged into a 2-liter three-necked flask. The acetonitrile concentration in the system at this stage was 8.86 mol / L. Subsequently, a small amount of 50% by mass potassium hydroxide aqueous solution was added to adjust the pH in the reaction system to about 10.5, and then 160 g (2.12 mol) of 45% by mass hydrogen peroxide aqueous solution was added at an internal temperature of 35 ° C. Was added dropwise over 60 hours so as not to exceed 45 ° C. In addition, since pH fell when hydrogen peroxide was added, 50 mass% potassium hydroxide aqueous solution was also dripped separately so that pH might be maintained at 10.5. The reaction solution was subjected to UHPLC analysis, and 68 hours after the start of dropping, when the hydrolysis rate was 14%, 16.3 g of sodium sulfite and 800 g of toluene were added and stirred for 30 minutes to stop the reaction. The acetonitrile concentration in the system at the end of the reaction, calculated as 100% of the consumed acetonitrile reacted with the substrate, was 4.39 mol / L. After washing twice with 150 g of pure water, the reaction product obtained by distilling off the solvent had a purity of 72%, a yield of 93.0 g, and a crude yield of 38.2%.

Comparative Example 2 (Synthesis of trimethylolpropane triglycidyl ether)
75 g (0.295 mol) of trimethylolpropane triallyl ether obtained in Synthesis Example 2, 75 g (1.83 mol) of acetonitrile, and 73 g (2.26 mol) of methanol were charged into a 1-liter three-necked flask. The acetonitrile concentration in the system at this stage was 6.96 mol / L. Subsequently, 50% by mass aqueous potassium hydroxide solution was added to adjust the pH in the reaction system to about 10.5. Then, 116 g (1.54 mol) of 45% by mass hydrogen peroxide aqueous solution at an internal temperature of 35 ° C. The solution was added dropwise over 66 hours so as not to exceed 45 ° C. In addition, since pH fell when hydrogen peroxide was added, 50 mass% potassium hydroxide aqueous solution was also dripped separately so that pH might be maintained at 10.5. The reaction solution was subjected to UHPLC analysis. 72 hours after the start of dropping, 50 g of toluene and 1 g of sodium sulfite were added when the hydrolysis rate was 22%, and the reaction was stopped by stirring for 30 minutes. The acetonitrile concentration in the system at the end of the reaction, calculated as 100% of the consumed acetonitrile reacted with the substrate, was 3.13 mol / L. After washing twice with 20 g of pure water and distilling off the solvent, the reaction product was obtained in a purity of 69%, a yield of 29.4 g, and a crude yield of 32.1%.

Comparative Example 3 (Synthesis of pentaerythritol tetraglycidyl ether)
The reaction was started with the same procedure and charging ratio as in Comparative Example 1. The reaction solution was subjected to UHPLC analysis 20 hours after the start of dropwise addition of hydrogen peroxide, and it was confirmed that the hydrolysis rate was 0.5%. 16.3 g of sodium sulfite and 800 g of toluene were added and stirred for 30 minutes to stop the reaction. The acetonitrile concentration in the system at the end of the reaction, which was calculated on the assumption that consumed acetonitrile was 100% reacted with the substrate, was 5.83 mol / L. After washing twice with 150 g of pure water, the reaction product obtained by distilling off the solvent was 30% pure, 227 g in yield, and 93.3% in crude yield.

Table 1 shows the results of Examples 1 to 4 and Comparative Examples 1 to 3.

Examples 1 to 4 in which the reaction was stopped when the hydrolysis rate was 10% or less had good pure yields. On the other hand, Comparative Examples 1 and 2, which stopped the reaction after the hydrolysis reaction proceeded, and Comparative Example 3 having a hydrolysis rate of less than 0.5% had low purity and pure yield.

The method for producing a polyvalent glycidyl compound according to the present invention comprises a polyvalent glycidyl compound which is safe and easy in a simple operation from a reaction between a polyvalent allyl compound having three or more allyl groups and hydrogen peroxide, in a high yield and at a low cost. Is industrially useful.

Claims

In the method for producing a polyvalent glycidyl compound in which a carbon-carbon double bond of an allyl group of a polyvalent allyl compound having three or more allyl groups is epoxidized using an aqueous hydrogen peroxide solution as an oxidizing agent, A method for producing a polyvalent glycidyl compound, characterized in that the reaction is stopped when the ratio (hydrolysis rate) of the glycidyl group hydrolyzate produced is in the range of 0.5% to 10%. .
The method for producing a polyvalent glycidyl compound according to claim 1, wherein the epoxidation reaction is carried out in the presence of acetonitrile and alcohol.
The method for producing a polyvalent glycidyl compound according to claim 2, wherein the alcohol is an alcohol having 1 to 4 carbon atoms.
The production of a polyvalent glycidyl compound according to any one of claims 1 to 3, wherein the allyl group is bonded to an oxygen atom to form an allyl ether group, or is bonded to an amino group to form an allylamino group. Method.
The polyvalent allyl compound is trimethylolpropane triallyl ether, glycerin triallyl ether, pentaerythritol triallyl ether, pentaerythritol tetraallyl ether, ditrimethylolpropane triallyl ether, ditrimethylolpropane tetraallyl ether, diglyceryl triallyl ether, Diglycerin tetraallyl ether, erythritol triallyl ether, erythritol tetraallyl ether, xylitol triallyl ether, xylitol tetraallyl ether, xylitol pentaallyl ether, dipentaerythritol triallyl ether, dipentaerythritol tetraallyl ether, dipentaerythritol pentaallyl Ether, dipentaerythritol hexaary Ether, sorbitol triallyl ether, sorbitol tetraallyl ether, sorbitol pentaallyl ether, sorbitol hexaallyl ether, inositol triallyl ether, inositol tetraallyl ether, inositol pentaallyl ether, inositol hexaallyl ether, phenol novolac type polyallyl ether, cresol 5. The polyvalent glycidyl according to any one of claims 1 to 4, which is any one of the group consisting of a polyallyl ether, a naphthalene-containing novolak polyallyl ether, tetraallyldiaminodiphenylmethane, triallyl isocyanurate, and diallylaminophenol allyl ether. Compound production method.