WO2013021851A1 - High-purity epoxy compound and method for producing same - Google Patents

Abstract

Provided are: N,N,N',N'-tetraglycidyl-3,3'-diaminodiphenyl ether; and a method for producing same. N,N,N',N'-tetraglycidyl-3,3'-diaminodiphenyl ether is produced by an addition reaction step wherein 3,3'-diaminodiphenyl ether and epihalohydrin are reacted with each other in a solvent that contains a protic solvent, thereby producing N,N,N',N'-tetrakis(3-halo-2-hydroxypropyl)-3,3'- diaminodiphenyl ether and a cyclization reaction step wherein the N,N,N',N'-tetraglycidyl(3-halo-2-hydroxypropyl)-3,3'- diaminodiphenyl ether is treated with an alkali for dehydrohalogenation.

Description

High purity epoxy compound and method for producing the same

The present invention relates to an industrially useful novel epoxy compound and a method for producing the same.

Epoxy compounds are compounds widely used in the fields of organic chemistry and polymer chemistry, and are useful in a wide range of industrial applications such as fine chemicals, raw materials for medical and agricultural chemicals and resin materials, and electronic information materials and optical materials. A compound.

In addition, polyfunctional epoxy compounds are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, and electrical properties. It is used in a wide range of fields such as plates and composite materials. Among these, glycidylamine type epoxy compounds are excellent in heat resistance, and thus have widespread applications for composite materials and electronic materials (see, for example, Patent Documents 1 to 3). Among these, N, N, N ′, N′-tetraglycidyldiaminodiphenyl ethers are epoxy resin raw materials useful as fiber-reinforced composite materials.

Conventionally, as an epoxy compound having an N, N, N ′, N′-tetraglycidyldiaminodiphenyl ether skeleton, N, N, N ′, N′-tetraglycidyl-4,4′-diaminodiphenyl ether, N, N, N ′ , N′-tetraglycidyl-3,4′-diaminodiphenyl ether and its analogs have been known (see, for example, Patent Documents 4 to 6 and Non-Patent Documents 1 and 2). These N, N, N ′, N′-tetraglycidyldiaminodiphenyl ethers have excellent characteristics that the cured product has high mechanical properties (tensile strength and hardness) and high heat resistance. However, depending on the application, it may be required to increase the elastic modulus.

Japanese Unexamined Patent Publication No. 59-73577 Japanese Unexamined Patent Publication No. 60-16979 Japanese Unexamined Patent Publication No. 2001-247746 Japanese Laid-Open Patent Publication No. 3-26750 Japanese Laid-Open Patent Publication No. 4-335018 International Publication No. 97/13745

An object of the present invention is to provide a novel epoxy compound and a method for producing the same that can improve the performance of a cured epoxy resin.

As a result of intensive studies, the present inventors have found a novel epoxy compound that can improve the performance of a cured epoxy resin and a method for producing the same.

The novel epoxy compound of the present invention is an epoxy compound represented by the following formula (1).

The method for producing a novel epoxy compound of the present invention is obtained by an addition reaction step in which a compound represented by the following formula (2) is reacted with an epihalohydrin, and a cyclization reaction step in which the reaction mixture is treated with an alkali. An epoxy compound represented by (1) is obtained.

N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether represented by the above formula (1) of the present invention is a novel epoxy compound, and is cured by curing with a curing agent. A highly functional cured epoxy resin such as strength, high elastic modulus, high adhesiveness, high toughness, heat resistance, weather resistance, solvent resistance and impact resistance can be obtained. In particular, when a fiber reinforced composite material is used, the elastic modulus (at 5% strain) is maintained while maintaining the high strength and high heat resistance characteristics of conventional N, N, N ′, N′-tetraglycidyldiaminodiphenyl ethers. (Tensile stress) can be further increased. Moreover, when this novel epoxy compound and a normal epoxy resin are mixed and cured with an amine, a cured product that can be used for, for example, an adhesive or a paint can be obtained.

As an epoxy compound of this invention, it is preferable that content of the dimer which consists of an epoxy compound shown by said Formula (1) is 10% or less, the viscosity of an epoxy compound is made low, and the epoxy resin composition containing this The product can be easily made into a uniform composition, and its handleability and moldability can be improved.

In addition, the epoxy compound of the present invention preferably has a chemical purity of 75% or more of the compound represented by the formula (1). When used as a main component of the epoxy resin composition, the epoxy compound has high strength, high heat resistance and high elasticity. It is possible to obtain an excellent characteristic that the ratio is compatible at an excellent level.

The novel epoxy compound of the present invention is useful in various fields such as fine chemicals, raw materials for medical and agricultural chemicals, resin raw materials, fiber reinforced composite materials, electronic information materials, and optical materials.

In the process for producing an epoxy compound of the present invention, N, N, N ′, N′-tetrakis (3-halo-2-hydroxypropyl) -3,3′- is reacted with 3,3′-diaminodiphenyl ether and epihalohydrin. Addition reaction step for producing diaminodiphenyl ether, and cyclization reaction step for treating the produced N, N, N ′, N′-tetrakis (3-halo-2-hydroxypropyl) -3,3′-diaminodiphenyl ether with alkali Thus, N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether can be efficiently produced.

In addition, in the addition reaction step of reacting 3,3′-diaminodiphenyl ether and epihalohydrin, the reaction rate of 3,3′-diaminodiphenyl ether and epihalohydrin is improved by preferably using a solvent containing a protic solvent. , Improve productivity. The protic solvent is preferably at least one compound selected from water, alcohols, organic acids, inorganic acids, and phenols, and can allow the addition reaction to proceed rapidly. As the protic solvent, a hydroxyl group-containing compound can be preferably used. The temperature of this addition reaction is preferably 40 to 120 ° C., which can increase the reaction efficiency and suppress the formation of by-products.

Furthermore, the cyclization reaction step is preferably performed in the presence of a phase transfer catalyst comprising a quaternary ammonium salt and / or a quaternary phosphonium salt, and N, N, N ′, N′-tetraglycidyl- 3,3′-diaminodiphenyl ether can be efficiently produced.

1 is a hydrogen nuclear magnetic resonance spectrum chart of N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether obtained in Example 2. FIG. FIG. 2 is an enlarged view of the high magnetic field side of the hydrogen nuclear magnetic resonance spectrum chart of FIG. FIG. 3 is an enlarged view of the low magnetic field side of the hydrogen nuclear magnetic resonance spectrum chart of FIG. 4 is an infrared absorption spectrum chart of N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether obtained in Example 2. FIG. FIG. 5 is a mass spectrum of the main product obtained by liquid chromatography-mass spectrometry of N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether obtained in Example 2. is there.

Hereinafter, the novel epoxy compound of the present invention and the method for producing the epoxy compound will be described in detail.

The novel epoxy compound in the present invention is N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether represented by the following formula (1).

The epoxy compound represented by the formula (1) is a novel compound that has never been prepared. That is, N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether has not been described for its specific preparation method. Therefore, chemical analysis of the obtained epoxy compound has shown that The structure has never been confirmed.

N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether can obtain excellent characteristics when used as a main component of an epoxy resin composition. That is, it is possible to obtain an epoxy resin cured product excellent in high strength, high elastic modulus, high adhesion, high toughness, heat resistance, weather resistance, solvent resistance, impact resistance, and the like. Especially when producing fiber-reinforced composite materials using this epoxy compound as the main ingredient, other epoxy compounds characterized by high strength and high heat resistance, especially conventional N, N, N ′, N′-tetraglycidyldiaminodiphenyl ethers The elastic modulus (tensile stress at 5% strain) is increased while maintaining almost the same performance as the above.

The preparation of the epoxy compound of the present invention was confirmed for the first time, and the chemical purity of N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether is preferably 75% or more, more preferably 80%. As described above, the purity is extremely high as 85 to 100%. Since N, N, N ', N'-tetraglycidyl-3,3'-diaminodiphenyl ether has a very high chemical purity, it has high strength, high heat resistance and high resistance when used as the main component of an epoxy resin composition. It is possible to obtain an excellent characteristic of achieving both an elastic modulus and an excellent level. In the present invention, the chemical purity means the content of N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether in the epoxy compound, which will be described later by high performance liquid chromatography. Analyzed under analysis conditions (HPLC area%).

The epoxy compound of the present invention preferably has a dimer content comprising N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether of 10% or less, more preferably 7% or less, Preferably it is 5% or less. By setting the content of the dimer composed of N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether within such a range, the viscosity of the epoxy compound can be lowered. In the present invention, the dimer composed of N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether refers to a compound represented by the following formulas (4) and (5).

(In the formula, X represents halogen.)

Further, the content of the dimer represented by the above formulas (4) and (5) contained in the epoxy compound is the amount of the compound detected at an elution time of 56 to 72 minutes in the high performance liquid chromatography method described later. Calculated as (HPLC area%).

The epoxy compound of the present invention has a viscosity at 40 ° C. measured with an E-type viscometer, preferably 50 Pa · s or less, more preferably 40 Pa · s or less. By setting the viscosity of the epoxy compound to 50 Pa · s or less, it is easy to make the epoxy resin composition containing this uniform, and to improve the handling and molding processability of the epoxy resin composition. Can do. In addition, the viscosity of an epoxy compound is measured by the method mentioned later using an E-type viscometer.

As described above, the epoxy compound of the present invention has a high chemical purity of N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether and a low content of impurities, so that the storage stability is excellent. The viscosity rarely increases over time.

An epoxy compound composed of N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether is mixed with a normal epoxy resin and cured with an amine, for example, to an adhesive or a paint. A cured product that can be used can be obtained.

Furthermore, epoxy compounds composed of N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether are fine chemicals, medical and agrochemical raw materials, resin raw materials, fiber reinforced composite materials, electronic information materials, and optical materials. It is useful in a wide variety of industrial applications.

In the method for producing a novel epoxy compound of the present invention, 3,3′-diaminodiphenyl ether represented by the following formula (2) is reacted with epihalohydrin, and N, N, which is an epoxy compound precursor represented by the following formula (3): An addition reaction step for producing N ′, N′-tetrakis (3-halo-2-hydroxypropyl) -3,3′-diaminodiphenyl ether, and after completion of the addition reaction step, the obtained N, N, N ′, N'-tetrakis (3-halo-2-hydroxypropyl) -3,3'-diaminodiphenyl ether is treated with an alkali, and is carried out in two steps consisting of a cyclization reaction step in which dehydrohalogenation is carried out.

(In the formula, X represents halogen.)

That is, in the addition reaction step, 4 molecules of epihalohydrin are added to 1 molecule of 3,3′-diaminodiphenyl ether, and N, N, N ′, N′-tetrakis (3-halo-2-hydroxypropyl) which is an epoxy compound precursor. ) -3,3′-diaminodiphenyl ether is formed. In the subsequent cyclization reaction step, N, N, N ′, N′-tetrakis (3-halo-2-hydroxypropyl) -3,3′-diaminodiphenyl ether is dehydrohalogenated with an alkali to produce a tetrafunctional epoxy. N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether is produced.

In this way, N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether was produced by two steps consisting of an addition reaction step and a cyclization reaction step. While increasing the viscosity, the viscosity can be decreased. The reason for this is that the reaction between an intermediate having an active hydrogen of an amino group and an intermediate having an epoxy group, generated during the reaction, is suppressed, and by-products such as dimer and trimer are prevented. It is. On the other hand, N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether of the formula (1) is prepared in one step from 3,3′-diaminodiphenyl ether of the formula (2). Even if it does so, reaction of the intermediate body which has active hydrogen, and the intermediate body which has an epoxy group cannot be controlled, and high molecularization of an intermediate body progresses and the target epoxy compound cannot be obtained.

The epihalohydrin used in the addition reaction step of the present invention is a 3-halogeno 1,2-epoxide compound, and specific examples include epichlorohydrin and epibromohydrin.

In the addition reaction step, the amount of epihalohydrin used is preferably 5 mole times to 40 mole times, more preferably 8 mole times to 20 mole times, per mole of 3,3′-diaminodiphenyl ethers. It is. By setting the amount to 5 mol times or more, it is possible to suppress impureness such as high molecular weight in the addition reaction step, and by setting the amount to 40 mol times or less, less energy is required for removing epihalohydrin. It is economical because waste is reduced.

The method for producing an epoxy compound of the present invention can be carried out without a solvent or in the presence of a solvent. In particular, in the addition reaction step, a protic solvent is preferably used as the reaction solvent.

Preferred examples of the protic solvent include water, alcohol, organic acid, inorganic acid, and phenols. As the protic solvent, a hydroxyl group-containing compound can be suitably used. By using a protic solvent as the solvent, the addition reaction between the epihalohydrin and the amino group of the substrate proceeds rapidly.

Water is not particularly limited, but general industrial water can be used. That is, it is purified by precipitation, coagulation, filtration, distillation, ion exchange, ultrafiltration, reverse osmosis, etc. using rivers, groundwater, lakes, seawater, brine, etc. as water sources.

Examples of the alcohol include primary alcohols such as methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol and 1-hexanol, 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, Secondary alcohols such as 2-hexanol, cyclohexanol, 2-heptanol and 3-heptanol, tertiary alcohols such as tert-butanol and tert-pentanol, and others, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monome Ether, diethylene glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol mono-n-butyl ether, propylene glycol, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol monophenyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono- n-propyl ether, dipropi Glycol mono -n- butyl ether, tripropylene glycol, tripropylene glycol monomethyl ether and tripropylene glycol mono -n- butyl ether.

Organic acids include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, valeric acid, isovaleric acid, capcanic acid, 2-ethylbutyric acid, caprylic acid, 2-ethylhexanoic acid, oleic acid, acetic anhydride, Propionic acid anhydride, butyric acid anhydride, citric acid, lactic acid, oxalic acid, octylic acid, naphthenic acid, neodecanoic acid, capric acid, lauric acid, mycelotic acid, montanic acid, melicic acid, succinic acid, Linderic acid, tuzuic acid , Spermic acid, myristoleic acid, zomarinic acid, petrothelic acid, vaccenic acid, gadoleic acid, whale oil acid, erucic acid, shark oil acid, linoleic acid, hiragoic acid, eleostearic acid, bunicic acid, tricosanoic acid, linolenic acid , Moloctic acid, parinaric acid, arachidonic acid, sardine acid, hiragasiraic acid, nisic acid and the like.

Examples of inorganic acids include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, and hydrofluoric acid.

Examples of phenols include phenol, o-cresol, m-cresol, p-cresol, xylenol and the like.

Of the above solvents, water, methanol, ethanol, 1-propanol, 1-butanol, 2-propanol, 2-butanol, tert-butanol, phenol, formic acid, acetic acid, propionic acid, butyric acid and hydrochloric acid are particularly preferably used.

In addition, the protic solvent may be used alone or in combination of two or more.

The amount of the protic solvent used is preferably 0.05 to 40 times by weight, more preferably 0.1 to 20 times by weight with respect to 3,3′-diaminodiphenyl ether. By setting the weight to 0.05 times or more, the reaction between 3,3'-diaminodiphenyl ether and epihalohydrin proceeds rapidly. By making the weight 40 times or less, energy required for removing the protic solvent is reduced and waste is also reduced, which is economical.

The addition reaction solvent may contain a solvent other than the protic solvent as long as it does not inhibit the reaction between 3,3′-diaminodiphenyl ether and epihalohydrin.

Examples of types of solvents other than protic solvents include hydrocarbons, halogenated hydrocarbons, ethers, esters, ketones, nitrogen compounds, and sulfur compounds.

As hydrocarbons, hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, isooctane, nonane, trimethylhexane, decane, dodecane, benzene, toluene, xylene, ethylbenzene, cumene , Mesitylene, cyclohexylbenzene, diethylbenzene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane.

Examples of the halogenated hydrocarbon include methyl chloride, dichloromethane, chloroform, carbon tetrachloride, ethyl chloride, 1,1-dichloroethane, 1,2-dichloroethane, 1,1,1-trichloroethane, 1,1,2-trichloroethane, , 1,1,2-tetrachloroethane, 1,1,2,2-tetrachloroethane, pentachloroethane, hexachloroethane, propyl chloride, isopropyl chloride, 1,2-dichloropropane, 1,2,3-trichloropropane, chloride Butyl, sec-butyl chloride, isobutyl chloride, tert-butyl chloride, 1-chloropentane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-trichlorobenzene, o-chlorotoluene , P-chlorotoluene, 1-chloronaphtha , Chlorinated naphthalene, methyl bromide, bromoform, ethyl bromide, 1,2-dibromoethane, 1,1,2,2-tetrabromoethane, propyl bromide, isopropyl bromide, bromobenzene, o-dibromobenzene 1-bromonaphthalene, fluorobenzene, benzotrifluoride, hexafluorobenzene, chlorobromomethane, trichlorofluoromethane, 1-bromo-2- chloroethane 1,1,2-trichloro-1,2,2-trifluoroethane, Examples thereof include 1,1,2,2-tetrachloro-1,2-difluoroethane.

Examples of ethers include diethyl ether, di-n-propyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, anisole, phenetole, diphenyl ether, dioxane, trioxane, tetrahydrofuran, tetrahydropyran, ethylene glycol dimethyl ether, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, Examples include diethylene glycol diethyl ether and diethylene glycol dibutyl ether.

Esters include methyl formate, ethyl formate, propyl formate, butyl formate, isobutyl formate, pentyl formate, methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, pentyl acetate, isopentyl acetate , 3-methoxybutyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, benzyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, propionic acid Examples include isopentyl, methyl isobutyrate, methyl benzoate, ethylene glycol monoacetate, ethylene diacetate, ethylene glycol ester, and diethyl carbonate.

Ketones include acetone, 2-butanone, 2-pentanone, 3-pentanone, 2-hexanone, methyl isobutyl ketone, 2-heptanone, 4-heptanone, diisobutyl ketone, acetylacetone, acetonylacetone, cyclopentanone, cyclohexanone, methyl Examples include cyclohexanone and acetophenone.

Nitrogen compounds include nitromethane, nitroethane, 1-nitropropane, 2-nitropropane, nitrobenzene, acetonitrile, propionitrile, succinonitrile, butyronitrile, isobutyronitrile, valeronitrile, benzonitrile, α-tolunitrile, pyridine, α-picoline, β-picoline, γ-picoline, 2,4-lutidine, 2,6-lutidine, quinoline, isoquinoline, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, etc. I can list them.

Examples of sulfur compounds include carbon disulfide, dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, and sulfolane.

Of the addition reaction solvents other than the above protic solvents, cyclohexane, toluene, xylene, ethylbenzene, cumene, mesitylene and diethylbenzene are particularly preferably used.

The amount of the solvent other than the protic solvent is preferably 10 times by weight or less, more preferably 5 times by weight or less with respect to 3,3′-diaminodiphenyl ether. By setting it in such a range, energy required for removing a solvent other than the protic solvent is reduced and waste is reduced, which is economical.

As the raw material charging order and method, epihalohydrin and a protic solvent may be added to 3,3′-diaminodiphenyl ether, or epihalohydrin or epihalohydrin is added to a solution containing 3,3′-diaminodiphenyl ether and protic solvent. A protic solvent may be added. Conversely, 3,3′-diaminodiphenyl ether and a protic solvent may be added to epihalohydrin, or 3,3′-diaminodiphenyl ether and a protic solvent may be added to a solvent containing epihalohydrin and protic solvent. .

In the addition reaction step, the reaction in which three molecules of epihalohydrin are added to one molecule of 3,3′-diaminodiphenyl ether proceeds relatively quickly, and is a trifunctional halogenohydrin, that is, N, N, N represented by the following formula (6): '-Tris (3-halo-2-hydroxypropyl) -3,3'-diaminodiphenyl ether is formed.

(In the formula, X represents halogen.)

An epihalohydrin is further added to the N, N, N′-tris (3-halo-2-hydroxypropyl) -3,3′-diaminodiphenyl ether represented by the formula (6) to obtain an epoxy compound precursor, that is, the following formula The reaction for producing N, N, N ′, N′-tetrakis (3-halo-2-hydroxypropyl) -3,3′-diaminodiphenyl ether represented by (3) is a slow reaction.

(In the formula, X represents halogen.)

For this reason, the epoxy compound precursor represented by the above formula (3) partially undergoes a cyclization reaction unintentionally by heating until the addition reaction is completed, and is represented by the following formula (7). N, N, N′-tris (3-halo-2-hydroxypropyl) -N′-glycidyl-3,3′-diaminodiphenyl ether may be formed.

(In the formula, X represents halogen.)

The intermediate represented by the formula (7) reacts with the epoxy compound precursor represented by the formula (3) to produce a dimeric intermediate represented by the following formula (8). The intermediate of this dimer becomes a dimer of an epoxy compound represented by the following formula (5) by the cyclization reaction step.

(In the formula, X represents halogen.)

(In the formula, X represents halogen.)

The intermediate represented by the above (7) reacts with the trifunctional halogenohydrin represented by the above formula (6) to produce a dimeric intermediate represented by the following formula (9). The intermediate of this dimer becomes a dimer of an epoxy compound represented by the following formula (4) by the cyclization reaction step.

(In the formula, X represents halogen.)

The dimer of the epoxy compound represented by the above formulas (4) and (5) not only lowers the chemical purity of the target epoxy compound but also increases its viscosity. Therefore, in the addition reaction step, it is required that the intermediate of formula (7), which causes the dimerization of the epoxy compound as a by-product, is not generated.

The temperature of the addition reaction step in the present invention is preferably 40 to 120 ° C, more preferably 50 to 100 ° C. By setting the temperature to 40 ° C. or higher, the reaction proceeds promptly and the aging time can be shortened, which is economical. By setting the temperature to 120 ° C. or lower, it is possible to suppress the impurity resulting from the cyclization of the 3-halo-2-hydroxypropyl group, that is, the generation of the intermediate represented by the formula (7).

In the present invention, preferably, the residual amount of N, N, N′-tris (3-halo-2-hydroxypropyl) -3,3′-diaminodiphenyl ether of the above formula (6) contained in the reaction mixture is minimized. The point of time when it becomes can be used as a measure of the end of reaction.

At the end of the reaction, the content of N, N, N′-tris (3-halo-2-hydroxypropyl) -3,3′-diaminodiphenyl ether contained in the reaction solution was 10% (HPLC area%) The following is preferable, and more preferably when it is 7% (HPLC area%) or less. If the amount of N, N, N′-tris (3-halo-2-hydroxypropyl) -3,3′-diaminodiphenyl ether is 10% or less, formation of a dimer in the cyclization reaction step is suppressed. N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether having high purity and low viscosity is obtained. At the end of the addition reaction step, the amount of N, N, N ′, N′-tetrakis (3-halo-2-hydroxypropyl) -3,3′-diaminodiphenyl ether is preferably 90% (HPLC area%). Above, more preferably 93% (HPLC area%) or more.

In addition, after completion of the addition reaction step and before the start of the cyclization reaction step, at least a part of the protic solvent and epihalohydrin in the addition reaction step may be removed by a commonly used method.

In the present invention, in the cyclization reaction step, N, N, N ′, N′-tetrakis (3-halo-2-hydroxypropyl) -3,3′-diaminodiphenyl ether is reacted with an alkali to perform dehydrohalogenation. .

Examples of the alkali include lithium hydroxide, sodium hydroxide, potassium hydroxide, barium hydroxide, magnesium hydroxide, calcium hydroxide, lithium carbonate, sodium carbonate, potassium carbonate, barium carbonate, magnesium carbonate, calcium carbonate, and hydrogen carbonate. Lithium, sodium hydrogen carbonate, potassium hydrogen carbonate, lithium hydride, sodium hydride, potassium hydride, sodium methoxide, potassium methoxide, sodium ethoxide, potassium ethoxide, sodium n-propoxide, potassium n-propoxide, Sodium isopropoxide, potassium isopropoxide, sodium n-butoxide, potassium n-butoxide, sodium tert-butoxide, potassium tert-butoxide, sodium tert-amylate, Although potassium tert- amylate, sodium n- Hekishirato, and potassium n- Hekishirato and tetramethylammonium hydroxide can be exemplified. Among them, potassium hydroxide and sodium hydroxide are preferably used. These alkalis may be added as such or may be dropped as water or an alcohol solution.

Alkali may be used alone or in combination of two or more. The amount of alkali used is preferably 4 to 16 mol times, more preferably 5 to 12 mol times the amount of 3,3'-diaminodiphenyl ether. By making it 4 moles or more, the cyclization reaction of the 3-halo-2-hydroxypropyl group is completed. By adjusting the amount to 16 mol times or less, it is economical because excessive energy is not required when the generated salt and excess alkali are removed from the reaction mixture, and waste is reduced.

The cyclization reaction in the present invention is preferably performed in the presence of a phase transfer catalyst. Examples of the phase transfer catalyst include crown ethers, quaternary ammonium salts, and quaternary phosphonium salts.

Examples of the crown ether used in the present invention include dibenzo-18-crown-6, 18-crown-6, 15-crown-5, 12-crown-4, dicyclohexano-18-crown-6, and methylbenzo15-crown. -5, di-tert-butylbenzo-15-crown-5, methylbenzo-18-crown-6, tert-butylbenzo-18-crown-6, benzo-15-crown-5, cyclohexano-15-crown-5, tert-Butylbenzo-15-crown-5, nitrobenzo-15-crown-5, benzo-18-crown-6, dibenzo-24-crown-8, nitrobenzo18-crown-6, benzo-12-crown-4, 16 -Crown-5,2,2-dimethyl-1,3,6,9-tetraoxa-2-silane Cycloundecane, 1-phenyl-4,7,10,13-tetraoxa-1-azacyclopentadecane, 21-crown-7, 24-crown-8, 15- (2,5-dioxahexyl) -15-methyl -16-crown-5, 13-crown-4, 14-crown-4, 15-crown-4, 16-crown-4, dimethylsila-20-crown-7, dibenzo-20-crown-6, dibenzo-22 Crown-6, dibenzyl-14-crown-4, benzo-13-crown-4, 15,15-dimethyl-16-crown-5, dodecyloxymethyl-18-crown-6, 1,4,7,10 , 13, dibenzo-30-crown-10, dibenzo-14-crown-4, dicyclohexano-27-crown-9, dicyclohexano- 0-crown-10, benzo-9-crown-3, dibenzo-16-crown-5, 30-crown-10, perfluoro-15-crown-5, perfluoro-12-crown-4, perfluoro-18-crown- 6, perfluorodicyclohexano-24-crown-8, naphth-15-crown-5, 12-crown-3, 60-crown-20, 81-crown-27, di-tert-butyldibenzo-24-crown- 8, di-tert-butyldibenzo-14-crown-4, di-tert-butyldibenzo-18-crown-6, di-tert-butyldibenzo-16-crown-5, 18-crown-5, 19-crown -6, di-tert-butyldibenzo-21-crown-7, 9-crown-3, furanotribenzo -21-crown-7, N, N'-dimethylcyanodiaza-18-crown-6, 15-methylene-16-crown-5, 2,2-diphenyl-11-crown-4, 2,2-diphenyl -14-crown-5, 2,2-diphenyl-17-crown-6, 2,2-diphenyl-20-crown-7, dicyclohexano-21-crown-7, 1,5-naphth-22-crown -6, decyl-18-crown-6, benzyloxymethyl-12-crown-3, bis (m-phenylene) -32-crown-10, dibenzo-15-crown-5, tribenzo-18-crown-6, Tribenzo-21-crown-7, tetrabenzo-24-crown-8, 4 ', 5'-dibromobenzo-15-crown-5, benzo-24-crown-8, Zo-21-crown-7, 15-crown-3, 20-crown-4, 25-crown-5, 30-crown-6, 35-crown-7, 40-crown-8, 45-crown-9, 50-crown-10, 55-crown-11, 60-crown-12, 70-crown-14, methyl-18-crown-6, 2,3-dimethyl-18-crown-6, 1-methyl-1- Aza-18-crown-6, 1,10-dimethyl-1,10-diaza-18-crown-6, di-tert-butyldicyclohexano-18-crown-6, 36-crown-4, 40-crown -4, naphth-18-crown-6, bis-4,4 ′ (5 ′)-[tert-butylcyclohexano] -18-crown-6, 4,5′-di-tert-butyldicyclohexane Sano-18-crown-6, naphth-9-crown-3, naphth-12-crown-4, 4,4 ', 4' ', 5' ''-tetra-tert-butyltetrabenzo-24-crown- 8,4,4 ′, 4 ″, 5 ′ ″-tetra-tert-butyltetrabenzo-24-crown-8,4,5 ′, 4 ″, 5 ′ ″ tetra-tert-butyltetrabenzo -24-crown-8, dibenzo-27-crown-9, dibenzo-16-crown-4, benzo-30-crown-10, [2,8] dibenzo-30-crown-10, benzo-33-crown- 11, dibenzo-48-crown-16, [4,7] dibenzo-33-crown-11, benzo-27-crown-9, bisnaphth-9-crown-3, dibenzo-28-crown-6, naphtho -24-crown-8,4,5'-di-tert-butyldibenzo-18-crown-6, benzo-14-crown-4, benzo-17-crown-5, benzo-20-crown-6, dimethyl And dibenzo-24-crown-8.

As the quaternary ammonium salt used in the present invention, tetramethylammonium, trimethylethylammonium, dimethyldiethylammonium, triethylmethylammonium, tripropylmethylammonium, tributylmethylammonium, trioctylmethylammonium, tetraethylammonium, trimethylpropylammonium, Trimethylphenylammonium, benzyltrimethylammonium, benzyltriethylammonium, diallyldimethylammonium, n-octyltrimethylammonium, stearyltrimethylammonium, cetyldimethylethylammonium, tetrapropylammonium, tetra-n-butylammonium, β-methylcholine and phenyltrimethylammonium Odor Salt, chloride salt, iodine Casio, can be mentioned hydrogen sulfate and hydroxide, and the like.

As the quaternary phosphonium salt used in the present invention, tetramethylphosphonium, trimethylethylphosphonium, dimethyldiethylphosphonium, triethylmethylphosphonium, tripropylmethylphosphonium, tributylmethylphosphonium, trioctylmethylphosphonium, tetraethylphosphonium, trimethylpropylphosphonium, Trimethylphenylphosphonium, benzyltrimethylphosphonium, diallyldimethylphosphonium, n-octyltrimethylphosphonium, stearyltrimethylphosphonium, cetyldimethylethylphosphonium, tetrapropylphosphonium, tetra-n-butylphosphonium, phenyltrimethylphosphonium, methyltriphenylphosphonium, ethyltriphenyl Phosphoni Arm and bromide salts, such as tetraphenylphosphonium, chloride salt, iodine Casio, can be mentioned hydrogen sulfate and hydroxide, and the like.

Of the above phase transfer catalysts, quaternary ammonium salts and / or quaternary phosphonium salts are preferred, and quaternary ammonium salts are particularly preferred. In particular, trioctylmethylammonium, tetraethylammonium, benzyltrimethylammonium, benzyltriethylammonium, tetra-n-butylammonium bromide, chloride, hydrogen sulfate and hydroxide are more preferably used. Moreover, a phase transfer solvent may be used independently and may be used in mixture of 2 or more types.

The addition amount of the phase transfer catalyst may be a catalytic amount, and is 0.001 to 0.5 mol times, more preferably 0.01 to 0.1 mol times with respect to 3,3′-diaminodiphenyl ether. . By setting it to 0.001 mol times or more, the cyclization reaction proceeds promptly. By making it 0.5 mol times or less, the amount of catalyst used can be reduced, which is economical.

The reaction temperature of the cyclization reaction is preferably 0 to 90 ° C, more preferably 20 to 60 ° C. By setting the reaction temperature of the cyclization reaction to 0 ° C. or higher, the reaction proceeds promptly. Moreover, by setting it as 90 degrees C or less, the energy required for a heating can be reduced and it is economical.

In addition, the reaction time is preferably 0.5 to 10 hours, more preferably 1 to 6 hours after completion of the alkali addition. By setting the duration to 0.5 hours or longer, it is possible to prevent an increase in the easily saponifiable chlorine content caused by the 3-halo-2-hydroxypropyl group remaining without reacting. By setting it to 6 hours or less, the aging time can be shortened and it is economical.

As the solvent for the cyclization reaction, any one selected from alcohols, hydrocarbons and ethers is preferably used.

Alcohols as cyclization reaction solvents include primary alcohols such as methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol and 1-hexanol, 2-propanol, 2-butanol, 2-pentanol, 3 -Secondary alcohols such as pentanol, 2-hexanol, cyclohexanol, 2-heptanol and 3-heptanol, tert-butanol, tert-pentanol, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol Mono-n-propyl ether, ethylene glycol mono-n-butyl ether, ethylene glycol monophenyl ether, diethylene glycol, diethylene glycol monomethyl ether, diethyl Glycol monoethyl ether, diethylene glycol mono-n-propyl ether, diethylene glycol mono-n-butyl ether, triethylene glycol, triethylene glycol monomethyl ether, triethylene glycol mono-n-butyl ether, propylene glycol, propylene glycol monomethyl ether, propylene glycol Monoethyl ether, propylene glycol mono-n-propyl ether, propylene glycol mono-n-butyl ether, propylene glycol monophenyl ether, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol mono-n -Propyl ether, dipropylene glycol mono- - butyl ether, tripropylene glycol, tripropylene glycol monomethyl ether and tripropylene glycol mono -n- butyl ether and the like.

As hydrocarbons, hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, isooctane, nonane, trimethylhexane, decane, dodecane, benzene, toluene, xylene, ethylbenzene, cumene , Mesitylene, cyclohexylbenzene, diethylbenzene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane.

The ethers include diethyl ether, di-n-propyl ether, diisopropyl ether, dibutyl ether, dihexyl ether, cyclopentyl methyl ether, anisole, phenetole, diphenyl ether, tetrahydrofuran, tetrahydropyran, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl. Examples include ether and diethylene glycol dibutyl ether.

Of the cyclization reaction solvents, methanol, ethanol, 1-propanol, 1-butanol, 2-propanol, 2-butanol, tert-butanol, cyclohexane, toluene, xylene, ethylbenzene, cumene, mesitylene and diethylbenzene are particularly preferably used. It is done.

The amount of the solvent used in the cyclization reaction step is preferably 1 to 20 times by weight, more preferably 2 to 10 times by weight with respect to 3,3′-diaminodiphenyl ether. By setting it to 1 weight times or more, the viscosity of the reaction mixture is reduced, and the stirring efficiency is improved, whereby the reaction is completed quickly. By making the weight 20 times or less, energy required for removing the solvent is reduced and waste is reduced, which is economical.

The reaction mixture obtained in the cyclization reaction step described above contains N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether, a salt formed by dehydrohalogenation, and a solvent.

The salt produced by dehydrohalogenation can be removed, for example, by washing the reaction mixture with water and separating the aqueous layer. The desired product can be obtained by distilling off the solvent under heating and reduced pressure of the obtained oil layer.

Moreover, when distilling off the solvent, it is preferable to perform thin film distillation. Thin film distillation refers to an operation of distilling a liquid into a thin film in a high vacuum where the distance between the evaporation surface and the condensation surface is shorter than the mean free path of molecules. Under high vacuum, collisions between gas molecules can be ignored, and by making the liquid into a thin film, collisions between liquid molecules can be suppressed more than normal distillation operations. This is an effective operation. Examples of the apparatus used in the thin film distillation include a centrifugal molecular distillation apparatus and a falling film molecular distillation apparatus.

The N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether thus obtained is a fine chemical, a raw material for medical and agricultural chemicals, a sealant for electric / electronic parts, an electronic information material, and an optical material. In addition, it is preferably used for a wide variety of industrial applications such as insulating materials, adhesives, and resin raw materials constituting composite materials such as glass fibers and carbon fibers. Among them, it is preferably used for a sealing material for electric / electronic parts, an insulating material, an adhesive, a composite material with glass fiber, carbon fiber, or the like.

By impregnating a glass fiber, carbon fiber or the like with a resin composition containing N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether of the present invention and a curing agent, A highly functional cured epoxy resin such as strength, high elastic modulus, high adhesiveness, high toughness, heat resistance, weather resistance, solvent resistance and impact resistance can be obtained. In particular, while maintaining high strength and heat resistance at almost the same level as conventional N, N, N ′, N′-tetraglycidyldiaminodiphenyl ethers, high elastic modulus (high tensile stress at 5% strain) Can be higher. In the present invention, the elastic modulus of the epoxy compound is determined by measuring the cured product according to JIS K 6911-1995 thermosetting plastic general test method, 5.18 tensile strength, at 5% strain. A tensile stress (unit: MPa) is measured, and this is defined as an elastic modulus.

Further, when the N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether of the present invention is mixed with a normal epoxy resin and cured with an amine, it is used for, for example, an adhesive or a paint. The hardened | cured material which can be obtained can be obtained. These cured products are cured products having high mechanical properties and electrical properties, and high durability and reliability.

Hereinafter, although it demonstrates concretely by an Example, this invention is not restrict | limited only to an Example. In the following examples, the description “XX times by weight / diaminodiphenyl ether” means that each added amount is XX times the weight of 3,3′-diaminodiphenyl ether.

In the present invention, the content of N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether in the epoxy compound, that is, N, N, N ′, N′-tetraglycidyl-3,3 ′ The chemical purity of diaminodiphenyl ether is the one analyzed by the high performance liquid chromatography method (hereinafter abbreviated as “HPLC”) under the following analysis conditions (HPLC area%). The dimer content of N, N, N'-tris (3-halo-2-hydroxypropyl) -3,3'-diaminodiphenyl ether and epoxy compound was also measured under the same analytical conditions.

Column: YMC-Pack ODS-AM303 4.6φ × 250mm
-Column temperature: 40 ° C
・ Mobile phase:
A: 0.1% (v / v) phosphoric acid aqueous solution B: Methanol (gradient) 0 min. A: B = 45: 55
30 min. A: B = 45: 55
70 min. A: B = 30: 70
70.1 min. A: B = 45: 55
80 min. A: B = 45: 55
・ Flow rate: 1 ml / min
・ Injection volume: 2μl
・ Detection: Ultraviolet (UV) detection, wavelength 254nm
Analysis time: 80 minutes Analysis sample preparation: 0.02 g of sample was weighed and dissolved in about 25 ml of ethylene glycol dimethyl ether.

However, as long as the same result as the analysis result based on the above analysis condition is obtained, the analysis condition is not limited to this.

In the present invention, the viscosity of the epoxy compound is analyzed by the following method.
Viscometer: RE85R (manufactured by Toki Sangyo Co., Ltd.), rotor code No. 38
・ Temperature: 40 ℃
・ Rotation speed: 1rpm
However, as long as the same result as the analysis result based on the above analysis condition is obtained, the analysis condition is not limited to this.

(Example 1)
In a four-necked flask equipped with a thermometer, a condenser and a stirrer, 1110 g (12.0 mol) of epichlorohydrin, 501 g of toluene (2.5 times by weight / diaminodiphenyl ether), 50.4 g of water (0.25 wt.) Double / diaminodiphenyl ether), and 201 g (1.0 mol) of 3,3′-diaminodiphenyl ether was added thereto. This mixture was stirred at a temperature of 80 ° C. for 15 hours to carry out an addition reaction. The amount of N, N, N′-tris (3-halo-2-hydroxypropyl) -3,3′-diaminodiphenyl ether contained in the reaction solution was 2.0% (HPLC area%). 10.1 g (0.03 mol) of tetrabutylammonium hydrogen sulfate was added to the reaction mixture, followed by dropwise addition of 500 g (6.0 mol) of 48% aqueous sodium hydroxide solution at a temperature of 30 ° C. over 30 minutes. The mixture was aged with stirring at temperature for 4 hours to carry out a cyclization reaction. After completion of the cyclization reaction, the produced salt was dissolved in 600 g (3.0 times by weight / diaminodiphenyl ether) of water, and the aqueous layer and the oil layer were separated. The oil layer was further washed with 600 g (3.0 times by weight / diaminodiphenyl ether) of water, and the water layer and the oil layer were separated. When toluene and epichlorohydrin were distilled off from the oil layer under reduced pressure, a brown viscous liquid mainly composed of N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether was obtained. The yield of this epoxy compound was 418 g (99% of the theoretical yield). Moreover, when the chemical purity of the epoxy compound was measured by the method mentioned above using HPLC, it was 83% (HPLC area%). The dimer detected at an elution time of 56 to 72 minutes was 5.8% (HPLC area%), the epoxy equivalent was 122 g / eq, and the viscosity was 46 Pa · s.

(Example 2)
In Example 1, except that the addition reaction temperature was changed from 80 ° C. to 70 ° C. and the addition reaction time was changed from 15 hours to 21 hours, N, N, N ′, N′− A brown viscous liquid mainly composed of tetraglycidyl-3,3′-diaminodiphenyl ether was obtained. The amount of N, N, N′-tris (3-halo-2-hydroxypropyl) -3,3′-diaminodiphenyl ether contained in the reaction solution at the end of the addition reaction is 1.7% (HPLC area%). there were. The yield of this epoxy compound was 414 g (97% of the theoretical yield).

The hydrogen nuclear magnetic resonance ( ¹ H-NMR) measurement result of the epoxy compound obtained in Example 2 and the m / z value of the main product obtained by LC-MS measurement are shown below.
¹ H-NMR (CDCl ₃ , 400 MHz) δ 2.54 (dd, 4H), 2.76 (dd, 4H), 3.13 (m, 4H), 3.41 (ddd, 4H), 3.71 ( ddd, 4H), 6.35 (d, 2H), 6.48 (s, 2H), 6.52 (d, 2H), 7.14 (t, 4H).
MS (ESI ^<+> ) m / z 425 ([M + H] ^< +>).

1, 2 and 3 show the hydrogen nuclear magnetic resonance ( ¹ H-NMR) spectrum chart obtained in Example 2, FIG. 4 shows the infrared (IR) absorption spectrum chart, and FIG. 5 shows the liquid chromatograph-mass spectrometry method. The mass spectrum of the main product obtained by (LC-MS) is shown.

Based on the above results, the obtained compound was identified as N, N, N ′, N′-tetraglycidyl-3,3′-diaminodiphenyl ether. When the chemical purity of this epoxy compound was measured by the method mentioned above using HPLC, it was 86% (HPLC area%). The dimer detected at an elution time of 56 to 72 minutes was 4.1% (HPLC area%), the epoxy equivalent was 120 g / eq, and the viscosity was 39 Pa · s.

(Reference Example 1)
The same procedure as in Example 1 was performed except that 3,3′-diaminodiphenyl ether was changed to 3,4′-diaminodiphenyl ether in Example 1. N, N, N ′, N′-tetraglycidyl-3 A brown viscous liquid mainly composed of 4,4'-diaminodiphenyl ether was obtained. The yield of this epoxy compound was 425 g (100% of the theoretical yield). The chemical purity of the epoxy compound was 87% (HPLC area%) as measured by the above-described method using high performance liquid chromatography (hereinafter referred to as “HPLC”). The epoxy equivalent was 122 g / eq, and the viscosity measured at 40 ° C. using an E-type viscometer was 36 Pa · s.

(Comparative Example 1)
Epichlorohydrin, toluene, water, and 3,3'-diaminodiphenyl ether are charged into a four-necked flask equipped with a thermometer, condenser, and stirrer, and immediately followed by tetrabutylammonium hydrogen sulfate and 48% sodium hydroxide aqueous solution. Was added, and the reaction was conducted by stirring for 18 hours at a temperature of 80 ° C., and an experiment was conducted in the same manner as in Example 1. As a result, a brown lumpy substance was obtained. Since this brown lump was not dissolved in ethylene glycol dimethyl ether, HPLC analysis could not be performed, and since it was solid, viscosity could not be measured.

(Reference Example 1)
A liquid composition was prepared by uniformly mixing 60 parts by weight of m-xylylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.) as a curing agent with 100 parts by weight of the epoxy compound obtained in Example 2. This liquid composition was defoamed by stirring under reduced pressure, poured into a Teflon (registered trademark) mold, cured at room temperature for 16 hours or more, then cured by heating at 60 ° C. for 2 hours, and a test piece. It was. Using this test piece, a tensile test and a hardness measurement were performed. The test methods were in accordance with JIS K 6911-1995 General Test Methods for Thermosetting Plastics, 5.18 Tensile Strength, and 5.16 Hardness, respectively. Further, in the tensile test, when measuring the tensile strength described above, the tensile stress at 5% strain is obtained as an elastic modulus (unit: MPa) and the elongation (unit: mm) when the test piece is broken is measured. did. However, the specimen used for the tensile test has the shape described in 5.18.2 (2) FIG. 31 of JIS K 6911-1995, and ASKER TYPE D (Polymer Keiki Co., Ltd.) is used as the hardness meter. It was.

The cured product of Reference Example 1 had a tensile strength of 83.4 MPa, an elongation at break of the test piece of 4.6 mm, an elastic modulus (tensile stress at 5% strain) of 47.5 MPa, and a hardness of 83. .

(Reference Example 2)
A cured product was prepared in the same manner as in Reference Example 1 except that the epoxy compound in Reference Example 1 was changed to tetraglycidyldiaminodiphenylmethane (trade name: MY721, manufactured by HUNTSMAN), and a tensile test and a hardness test were performed. It was. The cured product of Reference Example 2 had a tensile strength of 33.6 MPa, an elongation of 3.7 mm when the test piece broke, an elastic modulus (tensile stress at 5% strain) of 26.6 MPa, and a hardness of 82. It was.

While the cured product of Reference Example 1 has the same hardness as Reference Example 2, the tensile strength is 2.5 times or higher, the elongation when the test piece breaks is 20% or higher, and the elastic modulus (5 % Strain tensile stress) increased 1.5 times or more.

(Reference Example 3)
A cured product as in Reference Example 1 except that the epoxy compound in Reference Example 1 was changed to N, N, N ′, N′-tetraglycidyl-3,4′-diaminodiphenyl ether obtained in Reference Example 1. Were prepared and subjected to a tensile test and a hardness test. The cured product of Reference Example 3 had a tensile strength of 85.6 MPa, an elongation of 5.6 mm when the test piece broke, an elastic modulus (tensile stress at 5% strain) of 35.9 MPa, and a hardness of 83. It was.

The cured product of Reference Example 1 had a modulus of elasticity (tensile stress at 5% strain) of 30% or more higher than that of Reference Example 3, and the tensile strength, tensile elongation at break and hardness were almost the same level.

Claims (11)

1. An epoxy compound represented by the following formula (1).
   

   

   @ 0015
2. The epoxy compound according to claim 1, wherein the content of the dimer composed of the epoxy compound represented by the formula (1) is 10% or less.
3. The epoxy compound according to claim 1 or 2, wherein the chemical purity of the epoxy compound represented by the formula (1) is 75% or more.
4. A method for producing an epoxy compound represented by the following formula (1) obtained from an addition reaction step for reacting a compound represented by the following formula (2) with epihalohydrin and a cyclization reaction step for treating the reaction mixture with an alkali .
   

   

   @ 0016
   

   

   @ 0017
5. The method for producing an epoxy compound according to claim 4, wherein an epoxy compound precursor represented by the following formula (3) is produced by the addition reaction step and cyclized.
   

   

   @ 0018
   (In the formula, X represents halogen.)
6. The method for producing an epoxy compound according to claim 4 or 5, wherein the addition reaction step is carried out at a temperature of 40 to 120 ° C.
7. The method for synthesizing an epoxy compound according to claim 4, 5 or 6, wherein in the addition reaction step, the compound represented by the formula (2) is reacted with epihalohydrin in a solvent containing a protic solvent. .
8. The method for producing an epoxy compound according to claim 7, wherein the hydroxyl group-containing compound is at least one compound selected from water, alcohols, organic acids, inorganic acids, and phenols.
9. The method for producing an epoxy compound according to claim 7, wherein the protic solvent is a hydroxyl group-containing compound.
10. The method for producing an epoxy compound according to any one of claims 4 to 9, wherein a phase transfer catalyst is used in the cyclization reaction step.
11. The method for producing an epoxy compound according to claim 10, wherein the phase transfer catalyst is a quaternary ammonium salt and / or a quaternary phosphonium salt.

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