JP2013184955A - Epoxy compound and method for production thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide N,N,N',N'-tetraglycidyl-2,3'-diaminodiphenylether and to provide a method for production thereof.SOLUTION: N,N,N',N'-tetraglycidyl-2,4'-diaminodiphenylether is produced by: an addition reaction process of reacting 2,4'-diaminodiphenylether and epihalohydrin in the solvent including a protic solvent to generate N,N,N',N'-tetrakis(3-halo-2-hydroxypropyl)-2,4'-diaminodiphenylether, and a cyclization reaction process of treating with alkali, the N,N,N',N'-tetrakis(3-halo-2-hydroxypropyl)-2,4'-diaminodiphenylether to remove hydrogen halide.

Description

  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 are used for composite materials and electronic materials (see, for example, Patent Documents 1 to 3). Among them, N, N, N ′, N′-tetraglycidyldiaminodiphenyl ethers are epoxy resin raw materials useful as composite materials and electronic 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 analogs thereof 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 Unexamined Patent Publication No. 4-335018 International Publication No. 97/13745

European Polymer Journal, Vol. 31, No. 4, pp. 313-320 (1995) Journal of Applied Polymer Science, Vol. 77, 2430-2436 (2000)

  The objective of this invention is providing the novel epoxy compound and its manufacturing method which make it possible to improve the performance of a cured epoxy resin.

  As a result of intensive studies, the present inventors have found a novel epoxy compound capable of improving 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 comprises an addition reaction step in which a compound represented by the following formula (2) is reacted with 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-2,4′-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, by using this epoxy compound, the elastic modulus (at 5% strain) is maintained, while maintaining the characteristics of conventional N, N, N ′, N′-tetraglycidyldiaminodiphenyl ethers such as high strength and high heat resistance. (Tensile stress) can be further increased. Moreover, when this novel epoxy compound and a normal epoxy compound 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.

  In addition, the novel epoxy compound of the present invention is useful in a wide variety of industrial applications such as fine chemicals, medical and agricultural chemical raw materials, resin raw materials, electronic information materials, and optical materials.

  In the process for producing a novel epoxy compound of the present invention, 2,4′-diaminodiphenyl ether is reacted with epihalohydrin to produce N, N, N ′, N′-tetrakis (3-halo-2-hydroxypropyl) -2,4 ′. -Addition reaction step for producing diaminodiphenyl ether, and cyclization reaction for treating the produced N, N, N ', N'-tetrakis (3-halo-2-hydroxypropyl) -2,4'-diaminodiphenyl ether with alkali By the process, N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether can be efficiently produced.

  In addition, in the addition reaction step in which epihalohydrin is reacted with 2,4′-diaminodiphenyl ether, the reaction rate of 2,4′-diaminodiphenyl ether and epihalohydrin is preferably improved by using a solvent containing a protic solvent, Productivity is improved. The protic solvent is preferably at least one hydroxy group-containing compound selected from water, alcohols, and phenols, and can allow the addition reaction to proceed rapidly. 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 carried out 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- 2,4'-diaminodiphenyl ether can be produced efficiently.

1 is a hydrogen nuclear magnetic resonance spectrum chart of N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether obtained in Example 2. FIG. 2 is an enlarged view of the high magnetic field side of the hydrogen nuclear magnetic resonance spectrum chart of N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether obtained in Example 2. FIG. FIG. 3 is an enlarged view of the low magnetic field side of the hydrogen nuclear magnetic resonance spectrum chart of N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether obtained in Example 2. 4 is an infrared absorption spectrum chart of N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether obtained in Example 2. FIG.

  Below, the novel epoxy compound of this invention and the manufacturing method of the epoxy compound are described in detail.

The novel epoxy compound in the present invention is N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether represented by the following formula (1).

  When N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether is used as a main component of an epoxy resin composition, excellent characteristics can be obtained. 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. In particular, by using this epoxy compound as the main component, the cured product of the epoxy resin composition based on the conventional N, N, N ′, N′-tetraglycidyldiaminodiphenyl ethers has the characteristics of high strength and high heat resistance. The elastic modulus (tensile stress at 5% strain) can be further increased while maintaining substantially the same.

  In the epoxy compound of the present invention, the chemical purity of N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether is preferably 70% or more, more preferably 80 to 100%. As described above, when the chemical purity of N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether is made extremely high, when used as a main component of an epoxy resin composition, it has high strength and high heat resistance. And a high elastic modulus can be achieved at an excellent level. In the present invention, the chemical purity means the content of N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether in the epoxy compound, which will be described later by high performance liquid chromatography. Analyzed under analytical conditions (HPLC area%).

  The epoxy compound of the present invention preferably has a viscosity at 40 ° C. measured with an E-type viscometer of 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-2,4′-diaminodiphenyl ether and a low impurity content, so that it has excellent storage stability and viscosity. Rarely increases over time.

  An epoxy compound composed of N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether is blended with a normal epoxy compound and cured with an amine, for example, for 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-2,4′-diaminodiphenyl ether are used for industrial applications such as fine chemicals, medical and agrochemical raw materials, resin raw materials, electronic information materials, and optical materials. Useful in a wide variety of fields.

（式中、Ｘはハロゲンを表す。） In the process for producing a novel epoxy compound of the present invention, epihalohydrin is reacted with 2,4′-diaminodiphenyl ether represented by the following formula (2), and N, N, N ′, N′— represented by the following formula (3) is reacted. An addition reaction step for producing tetrakis (3-halo-2-hydroxypropyl) -2,4'-diaminodiphenyl ether, followed by the N, N, N ', N'-tetrakis (3 -Halo-2-hydroxypropyl) -2,4'-diaminodiphenyl ether is treated with an alkali and is carried out in two steps in which the cyclization reaction step of dehydrohalogenation proceeds.

(In the formula, X represents halogen.)

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

  In the addition reaction step of the present invention, the amount of epihalohydrin used is preferably 5 mole times to 40 mole times, more preferably 8 mole times to 20 moles, per mole of 2,4'-diaminodiphenyl ether. Double the amount. 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.

  An example of the protic solvent is a hydroxyl group-containing compound. Preferred examples of the hydroxyl group-containing compound include water, alcohols and phenols. By using the hydroxyl group-containing compound as a solvent, the addition reaction between the epihalohydrin and the amino group of the substrate proceeds rapidly.

  Although it does not specifically limit as water, 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 monomethyl 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, dipropylene Glycol mono -n- butyl ether, tripropylene glycol, tripropylene glycol monomethyl ether and tripropylene glycol mono -n- butyl ether.

  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 and phenol are particularly preferably used.

  Moreover, a protic solvent may be used independently and may be used in mixture of 2 or more types.

  The amount of the protic solvent used is preferably 0.05 to 40 times by weight and more preferably 0.1 to 20 times by weight with respect to 2,4′-diaminodiphenyl ether. By making it 0.05 times weight or more, the reaction of 2,4′-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 2,4′-diaminodiphenyl ether and epihalohydrin.

  Examples of the solvent other than the protic solvent 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, , 1,1,2-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-chloronaphthalene , 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, 1 , 1,2,2-tetrachloro-1,2-difluoroethane and the like.

  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.

  As ketones, acetone, 2-butanone, 2-pentanone, 3-pentanone, 2-hexanone, methylisobutylketone, 2-heptanone, 4-heptanone, diisobutylketone, 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 the sulfur compound include carbon disulfide, dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, and sulfolane.

  Of the addition reaction solvents other than the 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 2,4′-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 2,4′-diaminodiphenyl ether, or epihalohydrin or epihalohydrin may be added to a solution containing 2,4′-diaminodiphenyl ether and protic solvent. A protic solvent may be added. Conversely, 2,4'-diaminodiphenyl ether and a protic solvent may be added to epihalohydrin, or 2,4'-diaminodiphenyl ether and a protic solvent may be added to a solvent containing epihalohydrin and protic solvent. .

  As temperature of the addition reaction process in this invention, 40-120 degreeC is preferable, More preferably, it is 50-100 degreeC. 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 it as 120 degrees C or less, the impureness resulting from cyclization of 3-halo-2-hydroxypropyl group can be suppressed.

  In the present invention, preferably, when the residual amount of N, N, N′-tris (3-halo-2-hydroxypropyl) -2,4′-diaminodiphenyl ether contained in the reaction mixture is minimized, It can be used as a measure of completion of the reaction.

  Further, after completion of the addition reaction step, 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) -2,4′-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 bicarbonate, potassium bicarbonate, 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, potassium Um 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.

  An alkali may be used independently and may mix and use two or more types. The amount of alkali used is preferably 4 to 16 mol times, more preferably 5 to 12 mol times the amount of 2,4'-diaminodiphenyl ether. By setting it to 4 mol times 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-sila Cloundecane, 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-3 -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, ben -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-butyldicyclohexyl No-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, bisnaphtho-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, dimethyldibenzo -24-crown-8 and the like.

  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 Bromide etc. , 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 Phosphonium 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, hydrogensulfate and hydroxide are more preferably used. Moreover, a phase transfer catalyst 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 2,4′-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 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.

  The reaction time is preferably 0.5 to 10 hours, more preferably 1 to 6 hours after completion of the addition of alkali. By setting it as 0.5 hours or more, the increase in easily saponifiable chlorine content resulting from 3-halo-2-hydroxypropyl group remaining without reacting can be prevented. 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 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, 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 mono Ethyl 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-n 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.

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

  Among 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 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 2,4′-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-2,4′-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 a solvent off, 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-2,4′-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 resin raw materials constituting composite materials such as insulating materials, adhesives, and glass fibers. Among them, it is preferably used for a composite material with a sealant for electric / electronic parts, an insulating material, an adhesive, glass fiber, and the like.

  A composition using the N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether of the present invention as a main ingredient is cured with a curing agent such as an amine, whereby high strength, high elastic modulus, A highly functional cured epoxy resin such as high adhesiveness, high toughness, heat resistance, weather resistance, solvent resistance and impact resistance can be obtained. In particular, the modulus of elasticity (tensile stress at 5% strain) is maintained while maintaining high strength and high heat resistance at almost the same level as conventional epoxy resin cured products made of N, N, N ', N'-tetraglycidyldiaminodiphenyl ethers. ) Can be made 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. The tensile stress (unit: MPa) is measured, and this is used as the elastic modulus.

  Further, when N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether of the present invention and a normal epoxy compound are blended 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 an Example demonstrates concretely, this invention is not restrict | limited only to an Example. In the following Examples, the description “XX weight times / diaminodiphenyl ether” means that each added amount is XX weight times the weight of 2,4′-diaminodiphenyl ether.

  In the present invention, the content of N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether in the epoxy compound, that is, N, N, N ′, N′-tetraglycidyl-2,4 ′ -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%).

Column: YMC-Pack ODS-AM303 4.6φ × 250mm
-Column temperature: 40 ° C
Mobile phase: Methanol: 0.1% (v / v) phosphoric acid aqueous solution = 55: 45 (v / v)
・ Flow rate: 1ml / min
・ Injection volume: 3μl
・ Detection: Ultraviolet (UV) detection, wavelength 254nm
Analysis time: 90 minutes Analysis sample preparation: 0.02 g of sample was weighed and dissolved in about 20 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 tube and a stirrer, epichlorohydrin 410.8 g (4.44 mol), toluene 185.2 g (2.5 times by weight / diaminodiphenyl ether), water 18.5 g ( 0.25 weight times / diaminodiphenyl ether) was added, and 74.1 g (0.37 mol) of 2,4'-diaminodiphenyl ether was added thereto. This mixture was stirred at a temperature of 80 ° C. for 15 hours to carry out an addition reaction. 3.8 g (0.01 mol) of tetrabutylammonium hydrogen sulfate was added to the reaction mixture, followed by dropwise addition of 185 g (2.22 mol) of a 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 formed salt was dissolved in 222.3 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 222.3 g (3.0 times by weight / diaminodiphenyl ether) of water, and the water layer and the oil layer were separated. The oil layer was filtered to remove insolubles, and toluene and epichlorohydrin were distilled off from the filtrate under reduced pressure. After adding 444.6 g of toluene (4.0 times by weight / diaminodiphenyl ether) to the concentrate, insolubles contained in the diluted solution were removed by filtration. When toluene was distilled off from the filtrate under reduced pressure, a brown viscous liquid mainly composed of N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether was obtained. The yield of this epoxy compound was 124.8 g (80% of the theoretical yield). Moreover, when the chemical purity of the epoxy compound was measured by the method mentioned above using HPLC, it was 84% (HPLC area%). The epoxy equivalent was 130 g / eq, and the viscosity was 21 Pa · s.

(Example 2)
10.0 g of the epoxy compound obtained in Example 1 was dissolved in 100.0 g of toluene, and 10.0 g of silica gel powder (manufactured by Wako Pure Chemical Industries, Ltd., Wakogel (registered trademark) FC-40) was filtered. It filtered using the Kiriyama funnel spread | overlaid in. When toluene was distilled off from the obtained filtrate under reduced pressure, 8.4 g of a brown viscous liquid mainly composed of N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether was obtained. When the chemical purity of this epoxy compound was measured by the method mentioned above using HPLC, it was 93% (HPLC area%). The epoxy equivalent was 117 g / eq, and the viscosity was 5 Pa · s.

Below, the hydrogen nuclear magnetic resonance (< ¹ > H-NMR) measurement result of the epoxy compound obtained in Example 2 is shown.

¹ H-NMR (CDCl ₃ , 400 MHz) δ 2.52 (m, 2H), 2.59 (dd, 2H), 2.71 (dd, 2H), 2.81 (dd, 2H), 3.10 ( m, 2H), 3.18 (m, 2H), 3.70 (m, 4H), 3.57 (m, 2H), 3.72 (m, 2H), 6.78 (d, 2H), 6.90 (m, 4H), 7.00 (t, 1H), 7.19 (d, 1H).

1, 2 and 3 show a hydrogen nuclear magnetic resonance ( ¹ H-NMR) spectrum chart of the epoxy compound obtained in Example 2, and FIG. 4 shows an infrared (IR) absorption spectrum chart.

  Based on the above results, the obtained compound was identified as N, N, N ′, N′-tetraglycidyl-2,4′-diaminodiphenyl ether.

(Reference Example 1)
The same procedure as in Example 1 was conducted except that 2,4′-diaminodiphenyl ether was changed to 4,4′-diaminodiphenyl ether in Example 1. N, N, N ′, N′-tetraglycidyl-4 A brown viscous liquid mainly composed of 4,4'-diaminodiphenyl ether was obtained. The yield of this epoxy compound was 157.0 g (100% of the theoretical yield). Moreover, when the chemical purity of the epoxy compound was measured by the method mentioned above using HPLC, it was 94% (HPLC area%). The epoxy equivalent was 115 g / eq, and the viscosity was 9 Pa · s.

(Reference Example 2)
The same procedure as in Example 1 was conducted except that 2,4′-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 157.1 g (100% of the theoretical yield). Moreover, when the chemical purity of the epoxy compound was measured by the method mentioned above using HPLC, it was 88% (HPLC area%). The epoxy equivalent was 118 g / eq, and the viscosity was 28 Pa · s.

(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 respect to 100 parts by weight of the epoxy compound obtained in Example 1. This liquid composition is defoamed by stirring under reduced pressure, poured into a Teflon (registered trademark) mold, cured at room temperature (0-10 ° C.) for 16 hours or more, and then heated at 60 ° C. for 2 hours. And cured to obtain a test piece. Using this test piece, a tensile test and a hardness measurement were performed. The test methods followed JIS K 6911-1995 thermosetting plastic general test method, 5.18 tensile strength, 5.16 hardness, respectively. Also, 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 test piece used for the tensile test had the shape described in 5.18.2 (2) FIG. 31 of JIS K6911-1955, and ASKER TYPE D (Polymer Keiki Co., Ltd.) was used as the hardness meter. .

  The cured product of Reference Example 1 had a tensile strength of 59.3 MPa, an elongation of 3.0 mm when the test piece broke, an elastic modulus (tensile stress at 5% strain) of 50.6 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 tetraglycidyl diaminodiphenylmethane (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 49.5 MPa, an elongation of 3.8 mm when the test piece broke, an elastic modulus (tensile stress at 5% strain) of 31.0 MPa, and a hardness of 83. .

  While the cured product of Reference Example 1 has the same hardness as Reference Example 2, the tensile strength is about 20% higher and the elongation when the test piece breaks is about 20% lower, but the elastic modulus (at 5% strain) The tensile stress was increased by about 63%.

(Reference Example 3)
A cured product in the same manner as in Reference Example 1 except that the epoxy compound in Reference Example 1 was changed to N, N, N ′, N′-tetraglycidyl-4,4′-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 55.8 MPa, an elongation when the test piece broke 3.3 mm, an elastic modulus (tensile stress at 5% strain) of 41.6 MPa, and a hardness of 85. .
While the cured product of Reference Example 1 has the same hardness as Reference Example 3, the tensile strength is about 6% higher and the elongation when the test piece breaks is about 9% lower, but the elastic modulus (at 5% strain) (Tensile stress) was increased by about 22%.

(Reference Example 4)
Cured product in the same manner 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 2. Were prepared and subjected to a tensile test and a hardness test.

The cured product of Reference Example 4 had a tensile strength of 59.9 MPa, an elongation of 3.8 mm when the test piece broke, an elastic modulus (tensile stress at 5% strain) of 38.9 MPa, and a hardness of 81. .
The cured product of Reference Example 1 has the same hardness and tensile strength as Reference Example 4, while the elongation when the specimen breaks is about 20% lower, but the elastic modulus (tensile stress at 5% strain) is about 30% higher.

Claims (8)

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

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 .

  The method for producing an epoxy compound according to claim 2, wherein the addition reaction step is performed at a temperature of 40 to 120 ° C.   In the said addition reaction process, the compound shown by Formula (2) and epihalohydrin are made to react in the solvent containing a protic solvent, The manufacturing method of the epoxy compound of Claim 2 or 3 characterized by the above-mentioned.   The method for producing an epoxy compound according to claim 4, wherein the protic solvent is a hydroxyl group-containing compound.   6. The method for producing an epoxy compound according to claim 5, wherein the hydroxyl group-containing compound is at least one compound selected from water, alcohols, and phenols.   The method for producing an epoxy compound according to any one of claims 2 to 6, wherein a phase transfer catalyst is used in the cyclization reaction step.   The said phase transfer catalyst is a quaternary ammonium salt and / or a quaternary phosphonium salt, The manufacturing method of the epoxy compound of Claim 7 characterized by the above-mentioned.

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