[go: up one dir, main page]

WO2013089006A1 - Procédé de production d'un composé de glycidylamine époxy - Google Patents

Procédé de production d'un composé de glycidylamine époxy Download PDF

Info

Publication number
WO2013089006A1
WO2013089006A1 PCT/JP2012/081557 JP2012081557W WO2013089006A1 WO 2013089006 A1 WO2013089006 A1 WO 2013089006A1 JP 2012081557 W JP2012081557 W JP 2012081557W WO 2013089006 A1 WO2013089006 A1 WO 2013089006A1
Authority
WO
WIPO (PCT)
Prior art keywords
epoxy compound
acid
phenoxyaniline
glycidylamine
reaction
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2012/081557
Other languages
English (en)
Japanese (ja)
Inventor
秀利 加藤
学哉 石川
仁郎 中谷
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toray Fine Chemicals Co Ltd
Original Assignee
Toray Fine Chemicals Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Toray Fine Chemicals Co Ltd filed Critical Toray Fine Chemicals Co Ltd
Publication of WO2013089006A1 publication Critical patent/WO2013089006A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D301/00—Preparation of oxiranes
    • C07D301/27—Condensation of epihalohydrins or halohydrins with compounds containing active hydrogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
    • C07D303/02—Compounds containing oxirane rings
    • C07D303/36—Compounds containing oxirane rings with hydrocarbon radicals, substituted by nitrogen atoms

Definitions

  • the present invention relates to a method for producing an industrially useful glycidylamine epoxy compound.
  • 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 is 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.
  • 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.
  • glycidylamine epoxy compounds have low viscosity and high heat resistance, so they are used for space / aircraft composite materials, heat resistant adhesives, semiconductor encapsulants, and the like.
  • Patent Document 1 a novel glycidylamine-based epoxy compound that is excellent in mechanical properties, chemical resistance, heat resistance, and electrical properties by curing with various curing agents and a method for producing the same.
  • the obtained glycidylamine epoxy compound had low chemical purity, that is, contained a large amount of impurities. For this reason, oligomerization caused by impurities progressed with time, and there was a problem that storage stability was poor.
  • the glycidylamine-based epoxy compound undergoes thermal decomposition due to heating during distillation. It was difficult to purify efficiently.
  • An object of the present invention is to provide a method for efficiently producing an industrially useful glycidylamine-based epoxy compound.
  • the glycidylamine-based epoxy compound preferably has a chemical purity of 95% or higher, and a viscosity at 40 ° C. measured using an E-type viscometer is preferably 0.30 Pa ⁇ s or lower.
  • the compound selected from the phenols, organic acids, inorganic acids and water is preferably used in an amount of 0.01 to 20 times by weight with respect to phenoxyaniline.
  • the method for producing a glycidylamine epoxy compound of the present invention since the addition reaction of phenoxyaniline and epichlorohydrin is performed at a lower temperature than in the conventional method, the time required for production is reached in a short time. Can be shortened. Further, the amount of solvent used can be saved, which is economically advantageous.
  • the glycidylamine epoxy compound obtained by the production method of the present invention has high chemical purity and excellent storage stability.
  • a curing agent By curing the resin composition containing this high-purity glycidylamine epoxy compound and a curing agent, high strength, high elastic modulus, high adhesion, high toughness, heat resistance, weather resistance, solvent resistance and resistance
  • group epoxy compound and a normal epoxy resin are mixed and hardened with an amine, the hardened
  • the glycidylamine epoxy compound obtained by the production method of the present invention has a high chemical purity, preferably 95% or more, and thus does not need to be purified. Therefore, the yield is good because there is no loss that occurs during purification.
  • the glycidylamine-based epoxy compound obtained by the present invention has a viscosity of 40 ° C. measured using an E-type viscometer, preferably 0.30 Pa ⁇ s or less, and the viscosity is low. Can be economically advantageous.
  • the glycidylamine 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.
  • the method for producing a glycidylamine-based epoxy compound of the present invention comprises an addition reaction step in which phenoxyaniline and epichlorohydrin are reacted to obtain phenoxy-N, N-bis (2-hydroxy-3-chloropropyl) aniline; This comprises a cyclization reaction step in which the obtained phenoxy-N, N-bis (2-hydroxy-3-chloropropyl) aniline is reacted with an alkali to obtain a glycidylamine epoxy compound.
  • the production method of the present invention converts phenoxyaniline represented by the following general formula (1) and epichlorohydrin to 0 in the presence of a compound selected from phenols, organic acids, inorganic acids, and water.
  • the reaction is performed at ⁇ 60 ° C.
  • Examples of the phenoxyaniline represented by the general formula (1) include 2-phenoxyaniline, 3-phenoxyaniline, and 4-phenoxyaniline. Of these, 4-phenoxyaniline is preferred.
  • At least one polar compound selected from phenols, organic acids, inorganic acids, and water is used as a solvent for the addition reaction.
  • the solvent may be a combination of two or more of these compounds.
  • phenols examples include phenol, cresol, o-cresol, m-cresol, p-cresol, 2,3-dimethylphenol, 2,4-dimethylphenol, 2,5-dimethylphenol, 2,6-dimethylphenol, Examples include 3,4-dimethylphenol, 3,5-dimethylphenol, bisphenol A, alkylphenols, and the like.
  • organic acids include formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, pivalic acid, valeric acid, isovaleric acid, caproic acid, 2-ethylbutyric acid, caprylic acid, 2-ethylhexanoic acid, oleic acid, acetic anhydride , Propionic anhydride, butyric anhydride, citric acid, lactic acid, oxalic acid, octylic acid, naphthenic acid, neodecanoic acid, caprylic acid, capric acid, lauric acid, myristic acid, palmitic acid, stearic acid, arachidic acid, behenic acid , Ligrinoceric acid, cerotic acid, montanic acid, mellic acid, succinic acid, lindelic acid, tuzuic acid, succinic acid, myristoleic acid, zomarinic acid, petroceric acid, oleic
  • inorganic acids examples include hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid, hydrofluoric acid, and the like.
  • hydrochloric acid is preferred.
  • General industrial water can be used. That is, it is water purified by precipitation, coagulation, filtration, distillation, ion exchange, ultrafiltration, reverse osmosis, etc., using river water, groundwater, lake water, seawater, brine, etc. as the water source.
  • the polar compound selected from phenols, organic acids, inorganic acids, and water is preferably 0.01 to 20 times by weight, more preferably 0.05 to 10 times by weight, and still more preferably 0.0 to 10 times the weight of the phenoxyaniline. It is recommended to use 1 to 5 times by weight.
  • the amount of the polar solvent comprising a compound selected from phenols, organic acids, inorganic acids and water is 0.01 weight times or more with respect to phenoxyaniline, the addition reaction is completed quickly, which is preferable.
  • the compound chosen from phenols, an organic acid, an inorganic acid, and water can be easily remove
  • a compound other than a compound selected from phenols, organic acids, inorganic acids, and water may be added as long as the reaction between phenoxyaniline and epichlorohydrin is not inhibited.
  • examples of other types of compounds include hydrocarbons, halogenated hydrocarbons, ethers, esters, ketones, nitrogen compounds, and sulfur compounds.
  • hydrocarbon examples include hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, isooctane, nonane, trimethylhexane, decane, dodecane, benzene, toluene, xylene, ethylbenzene, Examples include cumene, mesitylene, cyclohexylbenzene, diethylbenzene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane.
  • halogenated hydrocarbon examples 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, Butyl chloride, sec-butyl chloride, isobutyl chloride, tert-butyl chloride, 1-chloropentane, chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, 1,2,4-trichlor
  • 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. And 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,
  • 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, ⁇ -tolunitrile, pyridine.
  • ⁇ -picoline, ⁇ -picoline, ⁇ -picoline, 2,4-lutidine, 2,6-lutidine, quinoline isoquinoline, N, N-dimethylformamide, N, N-diethylformamide, N, N-dimethylacetamide, etc. Can be mentioned.
  • sulfur compounds include carbon disulfide, dimethyl sulfide, diethyl sulfide, thiophene, tetrahydrothiophene, dimethyl sulfoxide, and sulfolane.
  • cyclohexane, toluene, xylene, ethylbenzene, cumene, mesitylene and diethylbenzene are particularly preferably used.
  • These other compounds can be used alone or in combination of two or more.
  • the other compound can be used in an amount of preferably 10 times by weight or less, more preferably 5 times by weight or less with respect to phenoxyaniline.
  • epichlorohydrin or a solution containing epichlorohydrin may be added to a solution containing phenoxyaniline or phenoxyaniline, or conversely epichlorohydrin or epichlorohydrin.
  • a solution containing phenoxyaniline or a solution containing phenoxyaniline may be added.
  • it is preferable to control the addition rate in accordance with the reaction rate such as adding the raw material to be added continuously or dividedly over time.
  • the time required for the addition is preferably selected from 0.5 to 6 hours.
  • the reaction time in the addition reaction step in the present invention is usually 0.5 to 60 hours under stirring after the addition of the raw materials.
  • the content of phenoxy-N- (2-hydroxy-3-chloropropyl) aniline contained in the reaction solution is preferably 5% (HPLC area%) or less, more preferably 2% or less ( HPLC area%).
  • the amount of phenoxy-N- (2-hydroxy-3-chloropropyl) aniline is 5% or less, formation of a dimer is suppressed, and a glycidylamine epoxy compound having high purity and low viscosity can be obtained.
  • the amount of phenoxy-N, N-bis (2-hydroxy-3-chloropropyl) aniline is preferably 80% (HPLC area%) or more, more preferably 85% (HPLC area%).
  • phenoxy-N- (2-hydroxy-3-chloropropyl) aniline and phenoxy-N, N-bis (2-hydroxy-3-chloropropyl) aniline depends on the chemistry of the glycidylamine epoxy compound described later. It can be measured by the same analytical method as purity.
  • the addition reaction temperature is 0 to 60 ° C., preferably 10 to 50 ° C., more preferably 20 to 40 ° C. If the addition reaction temperature is less than 0 ° C., it takes a long time to complete the reaction, and if it exceeds 60 ° C., the chemical purity of the resulting glycidylamine-based epoxy compound decreases and the viscosity increases.
  • the phenoxy-N, N-bis (2-hydroxy-3-chloropropyl) aniline obtained by the addition reaction is cyclized with an alkali to give the following general formula (2): Prepare the glycidylamine-based epoxy compound shown.
  • Examples of the alkali used in the cyclization reaction step 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, lithium hydrogen carbonate, 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 te t- amylate, potassium tert- amylate, sodium n- Hekishirato, potassium n- Hekishirato and tetramethylammonium hydroxide is exemplified. Of these, sodium hydro
  • the alkali itself may be added to the solution obtained by the addition reaction, but may be added dropwise as a water or alcohol solution.
  • the amount of alkali used is preferably 1 to 10 mole times that of phenoxy-N, N-bis (2-hydroxy-3-chloropropyl) aniline, ie, dichlorohydrin.
  • the cyclization reaction is preferably performed in the presence of a quaternary ammonium salt and / or a quaternary phosphonium salt. By adding these salts together, the reaction is accelerated and the yield of the glycidylamine epoxy compound is improved.
  • Quaternary ammonium salts include tetramethylammonium, trimethyl-ethylammonium, dimethyldiethylammonium, triethyl-methylammonium, tripropyl-methylammonium, tributyl-methylammonium, trioctyl-methylammonium, tetraethylammonium, trimethyl-propylammonium, Trimethylphenylammonium, benzyltrimethylammonium, benzyltriethylammonium, diallyldimethylammonium, n-octyltrimethylammonium, stearyltrimethylammonium, cetyldimethylethylammonium, tetrapropylammonium, tetran-butylammonium, ⁇ -methylcholine, phenyltrimethylammonium, etc.
  • Bromide, salt Salt, iodine Casio may be mentioned hydrogen sulfate and hydroxide, and the like. Particularly preferred are trioctyl-methylammonium, tetraethylammonium, benzyltrimethylammonium, benzyltriethylammonium, tetra-n-butylammonium bromide, chloride, hydrogensulfate and hydroxide.
  • the quaternary phosphonium salts include tetramethylphosphonium, trimethyl-ethylphosphonium, dimethyldiethylphosphonium, triethyl-methylphosphonium, tripropyl-methylphosphonium, tributyl-methylphosphonium, trioctyl-methylphosphonium, tetraethylphosphonium, trimethyl-propylphosphonium.
  • the amount of quaternary ammonium salt and / or quaternary phosphonium salt to be added may be a catalytic amount, and is preferably 0.001 to 0.5 mol times with respect to phenoxyaniline.
  • the reaction temperature is preferably 0 to 90 ° C, more preferably 10 to 70 ° C.
  • the reaction time is preferably 0.5 to 10 hours after the addition of the alkali compound is completed.
  • alkali, quaternary ammonium salt and / or quaternary phosphonium salt may be added to the solution obtained in the addition reaction step, or a new solvent may be added.
  • a new solvent may be added.
  • solvent added in the cyclization reaction step alcohol solvents, hydrocarbon solvents, ether solvents and ester solvents are preferably used.
  • alcohol solvents include primary alcohols such as methanol, ethanol, 1-propanol, 1-butanol, 1-pentanol and 1-hexanol, isopropanol, 2-butanol, 2-pentanol, 3-pentanol, Secondary alcohols such as 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 mono
  • hydrocarbon solvent examples include hexane, 2-methylpentane, 2,2-dimethylbutane, 2,3-dimethylbutane, heptane, octane, isooctane, nonane, trimethylhexane, decane, dodecane, benzene, toluene, xylene, Examples include ethylbenzene, cumene, mesitylene, cyclohexylbenzene, diethylbenzene, cyclopentane, methylcyclopentane, cyclohexane, methylcyclohexane, and ethylcyclohexane.
  • ether solvents include diisopyr ether, dibutyl ether, dihexyl ether, anisole, phenetole, diphenyl ether, tetrahydrofuran, tetrahydropyran, ethylene glycol dibutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, and diethylene glycol dibutyl ether.
  • ester solvents include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate.
  • preferred solvents are methanol, ethanol, 1-propanol, 1-butanol, isopropanol, 2-butanol, tert-butanol, cyclohexane, toluene, xylene, ethylbenzene, cumene, mesitylene and diethylbenzene.
  • the amount of the solvent used in the cyclization reaction step is preferably 0.1 to 20 times by weight, more preferably 1 to 10 times by weight with respect to phenoxyaniline.
  • the target glycidylamine epoxy compound is isolated by (1) distillation of the reaction solvent, (2) extraction with a hydrophobic solvent, (3) distillation of the extraction solvent, (4) distillation and ( 5) It can be achieved by a combination of general unit operations such as crystallization.
  • an organic solvent such as toluene is added to the liquid after the cyclization reaction, the target product of the present invention is extracted into the oil layer, and the aqueous layer is separated and removed. Furthermore, it is preferable to completely remove the salt dissolved in the oil layer by washing the obtained oil layer with water.
  • the amount of the organic solvent used is preferably 0.2 to 50 times by weight, more preferably 1 to 20 times by weight with respect to the object of the present invention.
  • the glycidylamine epoxy compound as the target product is isolated by crystallization from the obtained oil layer, it is easy to obtain a high purity.
  • the crystallization method include cooling crystallization, concentrated crystallization, and poor solvent crystallization.
  • a thin film distillation apparatus In the distillation and distillation of the extraction solvent, a thin film distillation apparatus may be used. Examples of the thin film distillation apparatus include a centrifugal molecular distillation apparatus and a falling film molecular distillation apparatus. The distilled solvent or the like may be reused.
  • the chemical purity of the glycidylamine epoxy compound obtained by using the production method of the present invention is preferably 95% or more, more preferably 97% or more. If the chemical purity of the glycidylamine-based epoxy compound is less than 95%, the storage stability is lowered, and the cured resin cured by the curing agent may not have the desired performance.
  • the chemical purity of the glycidylamine-based epoxy compound is a fraction (HPLC area%) of the peak area of the glycidylamine-based epoxy compound as measured by a method described later using high performance liquid chromatography.
  • the content of the dimer in the glycidylamine-based epoxy compound is preferably 2.2% or less.
  • the dimer in this specification refers to a compound represented by the following general formula (4) or general formula (5).
  • the content of the dimer By setting the content of the dimer within the above-described range, a glycidylamine epoxy compound having high purity and low viscosity can be obtained.
  • the content of the dimer represented by the general formula (4) and the general formula (5) contained in the glycidylamine-based epoxy compound is determined by the high performance liquid chromatography method for measuring the chemical purity of the glycidylamine-based epoxy compound. The amount of the compound detected in an elution time of 53 to 57 minutes (HPLC area%).
  • the glycidylamine epoxy compound obtained by using the production method of the present invention has a viscosity at 40 ° C. measured using an E-type viscometer, preferably 0.30 Pa ⁇ s or less, more preferably 0.28 Pa ⁇ s. It is as follows. When the viscosity of the glycidylamine-based epoxy compound exceeds 0.30 Pa ⁇ s, it is economically disadvantageous because the filler cannot be highly filled. In the present specification, the viscosity of the glycidylamine-based epoxy compound is a viscosity when measured at 40 ° C. by a method described later using an E-type viscometer.
  • the fraction (HPLC area%) of the peak area of the glycidylamine-based epoxy compound was measured by liquid chromatography under the following conditions (CLASS-VP, manufactured by Shimadzu Corporation) and used as the chemical purity.
  • the content of the dimer of phenoxy-N- (2-hydroxy-3-chloropropyl) aniline and glycidylamine epoxy compound was also measured under the same analytical conditions.
  • the dimer content of the glycidylamine epoxy compound was measured by the fraction (HPLC area%) of the peak area of the compound detected at an elution time of 53 to 57 minutes.
  • viscosity The viscosity at 40 ° C. was measured using an E-type viscometer of a glycidylamine epoxy compound under the following conditions. Viscometer: RE80U (manufactured by Toki Sangyo Co., Ltd.), rotor code No. 1 ⁇ Temperature: 40 °C ⁇ Rotation speed: 20rpm 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.
  • Epoxy equivalent The epoxy equivalent of the glycidylamine epoxy compound was measured by the hydrochloric acid-dioxane method. Specifically, a dioxane solution of methanol and 0.2N hydrochloric acid was added to a glycidylamine epoxy compound, and the mixture was stirred for 30 minutes to be reacted. A phenolphthalein solution was added as an indicator to the resulting reaction solution and neutralized with a 0.1N aqueous sodium hydroxide solution.
  • XX weight times / 4-phenoxyaniline means that the added amount is XX weight times the weight of 4-phenoxyaniline.
  • XX mole times / 4-phenoxyaniline means that the amount added is XX mole times the mole amount of 4-phenoxyaniline.
  • Example 1 In a four-necked flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, 210.3 g of epichlorohydrin (6.0 mol times / 4-phenoxyaniline) and 70.12 g of 4-phenoxyaniline (0. 38 mol) was charged. Acetic acid 17.4 g (0.25 weight times / 4-phenoxyaniline) was added dropwise over 30 minutes while purging with nitrogen. The addition reaction was carried out by raising the temperature to 40 ° C. and aging with stirring for 9 hours to produce 4-phenoxy-N, N-bis (2-hydroxy-3-chloropropyl) aniline.
  • Phenoxy-N- (2-hydroxy-3-chloropropyl) aniline was not detected in the reaction solution at the end of the addition reaction. Subsequently, 3.91 g of tetrabutylammonium hydrogen sulfate (0.03 mol times / 4-phenoxyaniline) was added, and then 126.7 g of a 48% aqueous sodium hydroxide solution (3.0 mol times / 4-phenoxyaniline) was added. The ripening reaction was carried out by adding dropwise over 1 hour and further aging with stirring for 4 hours.
  • Example 2 In the same manner as in Example 1, except that acetic acid was changed to 17.4 g of 35% hydrochloric acid (0.25 times by weight / 4-phenoxyaniline) and the addition reaction time was changed from 9 hours to 21 hours. did. As a result, 111.7 g (weight yield (based on 4-phenoxyaniline): 98.7%) of a brown viscous liquid mainly composed of 4-phenoxy-N, N-diglycidylaniline was obtained. The amount of phenoxy-N- (2-hydroxy-3-chloropropyl) aniline contained in the reaction solution at the end of the addition reaction was 0.3% (HPLC area%).
  • Example 3 In a four-necked flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer, 210.2 g of epichlorohydrin (6.0 mole times / 4-phenoxyaniline) and 17.6 g of ion-exchanged water (0.25) Weight times / 4-phenoxyaniline) and 70.61 g (0.38 mol) of 4-phenoxyaniline were charged. The addition reaction was carried out by raising the temperature to 40 ° C. and aging with stirring for 46 hours to produce 4-phenoxy-N, N-bis (2-hydroxy-3-chloropropyl) aniline.
  • Phenoxy-N- (2-hydroxy-3-chloropropyl) aniline was not detected in the reaction solution at the end of the addition reaction. Subsequently, 3.91 g of tetrabutylammonium hydrogen sulfate (0.03 mol times / 4-phenoxyaniline) was added, and then 95.9 g of a 48% aqueous sodium hydroxide solution (3.0 mol times / 4-phenoxyaniline) was added. The ripening reaction was carried out by adding dropwise over 1 hour and further aging with stirring for 4 hours.
  • Example 4 In Example 3, it implemented like Example 3 except having changed the reaction temperature in an addition reaction process from 40 degreeC to 60 degreeC, and changing reaction time from 46 hours to 12 hours. As a result, 111.0 g (weight yield (based on 4-phenoxyaniline): 99.2%) of a brown viscous liquid mainly composed of 4-phenoxy-N, N-diglycidylaniline was obtained. Phenoxy-N- (2-hydroxy-3-chloropropyl) aniline was not detected in the reaction solution at the end of the addition reaction. When the chemical purity of this epoxy compound was measured by the method mentioned above using HPLC, it was 96% (HPLC area%).
  • the dimer detected at an elution time of 53 to 57 minutes was 2.0% (HPLC area%), the epoxy equivalent was 160 g / eq, and the viscosity measured at 40 ° C. using an E-type viscometer was 0.29 Pa. ⁇ It was s.
  • Example 5 In Example 4, except that the amount of ion-exchanged water was changed from 17.6 g (0.25 times by weight / 4-phenoxyaniline) to 70.1 g (1.0 times by weight / 4-phenoxyaniline). The same experiment as in Example 4 was performed. As a result, 111.8 g (weight yield (based on 4-phenoxyaniline): 99.8%) of a brown viscous liquid mainly composed of 4-phenoxy-N, N-diglycidylaniline was obtained. The amount of phenoxy-N- (2-hydroxy-3-chloropropyl) aniline contained in the reaction solution at the end of the addition reaction was 0.1% (HPLC area%).
  • the amount of phenoxy-N- (2-hydroxy-3-chloropropyl) aniline contained in the reaction mixture at the end of the addition reaction was 8.0% (HPLC area%).
  • a portion of 247.4 g of 2-propanol and residual epichlorohydrin was distilled off from the addition reaction solution under reduced pressure.
  • To the concentrate were added 140.3 g of toluene (2.0 weight times / 4-phenoxyaniline) and 3.86 g of tetrabutylammonium hydrogen sulfate (0.03 mole times / 4-phenoxyaniline), followed by 48% hydroxylation.
  • the chemical purity of the obtained epoxy compound was measured by the method described above using HPLC and found to be 92% (HPLC area%).
  • the dimer detected at an elution time of 53 to 57 minutes was 1.3% (HPLC area%), the epoxy equivalent was 167 g / eq, and the viscosity measured at 40 ° C. using an E-type viscometer was 0.24 Pa. ⁇ It was s.
  • Comparative Example 2 In Comparative Example 1, the experiment was performed in the same manner as Comparative Example 1 except that the addition reaction temperature was changed from 60 ° C to 80 ° C. 111.4 g of 4-phenoxy-N, N-diglycidylaniline (weight yield (based on 4-phenoxyaniline): 99.3%) was obtained. The phenoxy-N- (2-hydroxy-3-chloropropyl) aniline contained in the reaction solution at the end of the addition reaction was 0.2% (HPLC area%). When the chemical purity of the obtained epoxy compound was measured by the method mentioned above using HPLC, it was 95% (HPLC area%).
  • the dimer detected at an elution time of 53 to 57 minutes was 2.4% (HPLC area%), the epoxy equivalent was 162 g / eq, and the viscosity measured at 40 ° C. using an E-type viscometer was 0.31 Pa. ⁇ It was s.
  • the amount of phenoxy-N- (2-hydroxy-3-chloropropyl) aniline contained in the reaction solution at the end of the addition reaction was 0.2% (HPLC area%).
  • 3.92 g of tetrabutylammonium hydrogen sulfate (0.03 mol times / 4-phenoxyaniline) was added, followed by 96.6 g of 48% sodium hydroxide (3.0 mol times / 4- Phenoxyaniline) was added dropwise at a temperature of 30 ° C. over 30 minutes, and further aged at 30 ° C. with stirring for 4 hours to carry out a cyclization reaction.
  • Comparative Example 4 In Comparative Example 3, an experiment was performed in the same manner as Comparative Example 3 except that ion-exchanged water was not added in the addition reaction step and the reaction time was changed from 6 hours to 9 hours. As a result, 111.7 g of a brown viscous liquid mainly composed of 4-phenoxy-N, N-diglycidylaniline was obtained (weight yield (based on 4-phenoxyaniline): 98.4%). Phenoxy-N- (2-hydroxy-3-chloropropyl) aniline was not detected in the reaction solution at the end of the addition reaction. When the chemical purity of this epoxy compound was measured by the method mentioned above using HPLC, it was 93% (HPLC area%).
  • the dimer detected at an elution time of 53 to 57 minutes was 4.6% (HPLC area%), the epoxy equivalent was 168 g / eq, and the viscosity measured at 40 ° C. using an E-type viscometer was 0.37 Pa. ⁇ It was s.
  • the amount of phenoxy-N- (2-hydroxy-3-chloropropyl) aniline contained in the reaction mixture at the end of the addition reaction was 15.8% (HPLC area%).
  • 3.87 g of tetrabutylammonium hydrogen sulfate (0.03 mol times / 4-phenoxyaniline) was added, and then 97.0 g of a 48% sodium hydroxide aqueous solution (3.0 mol times / 4-phenoxyaniline) was added.
  • the solution was added dropwise over 1 hour, and further aged with stirring for 4 hours to carry out a cyclization reaction.
  • Table 1 shows a list of experimental conditions and quality of Examples and Comparative Examples.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Epoxy Compounds (AREA)

Abstract

La présente invention a pour objet un procédé efficace de production d'un composé de glycidylamine époxy utile au niveau industriel. La présente invention produit un composé de glycidylamine époxy représenté par la formule générale (2) en faisant réagir une phénoxyaniline représentée par la formule générale (1) avec une épichlorohydrine à 0 à 60 °C en présence d'un composé choisi parmi des phénols, un acide organique, un acide inorganique et l'eau.
PCT/JP2012/081557 2011-12-15 2012-12-05 Procédé de production d'un composé de glycidylamine époxy Ceased WO2013089006A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2011274526 2011-12-15
JP2011-274526 2011-12-15

Publications (1)

Publication Number Publication Date
WO2013089006A1 true WO2013089006A1 (fr) 2013-06-20

Family

ID=48612460

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2012/081557 Ceased WO2013089006A1 (fr) 2011-12-15 2012-12-05 Procédé de production d'un composé de glycidylamine époxy

Country Status (2)

Country Link
JP (1) JPWO2013089006A1 (fr)
WO (1) WO2013089006A1 (fr)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014162947A1 (fr) * 2013-04-01 2014-10-09 東レ・ファインケミカル株式会社 Procédé de production d'un composé époxy de type diglycidylamine
WO2016129561A1 (fr) * 2015-02-13 2016-08-18 東レ・ファインケミカル株式会社 Procédé de production de composé comprenant un groupe n,n-bis(2-hydroxy-3-chloropropyl)amino
JP2020033320A (ja) * 2018-08-31 2020-03-05 東レ・ファインケミカル株式会社 ジグリシジルアミン系エポキシ化合物の精製方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3723361A (en) * 1970-09-24 1973-03-27 Shell Oil Co Cyano-substituted polyepoxides
JPS62246563A (ja) * 1986-04-17 1987-10-27 Kanegafuchi Chem Ind Co Ltd 新規エポキシ樹脂及びその製造方法
WO2010047244A1 (fr) * 2008-10-20 2010-04-29 東レ・ファインケミカル株式会社 Composé époxy et procédé de préparation de celui-ci

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3723361A (en) * 1970-09-24 1973-03-27 Shell Oil Co Cyano-substituted polyepoxides
JPS62246563A (ja) * 1986-04-17 1987-10-27 Kanegafuchi Chem Ind Co Ltd 新規エポキシ樹脂及びその製造方法
WO2010047244A1 (fr) * 2008-10-20 2010-04-29 東レ・ファインケミカル株式会社 Composé époxy et procédé de préparation de celui-ci

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
CHUNG H. LAU ET AL.: "Structure and Properties Relationships of Epoxy Resins Part 1:Crosslink Density of Cured Resin:(I)Model Resins Synthesis", BRITISH POLYMER JOURNAL, vol. 17, no. 1, 1985, pages 19 - 21 *

Cited By (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2014162947A1 (fr) * 2013-04-01 2014-10-09 東レ・ファインケミカル株式会社 Procédé de production d'un composé époxy de type diglycidylamine
WO2016129561A1 (fr) * 2015-02-13 2016-08-18 東レ・ファインケミカル株式会社 Procédé de production de composé comprenant un groupe n,n-bis(2-hydroxy-3-chloropropyl)amino
JPWO2016129561A1 (ja) * 2015-02-13 2017-04-27 東レ・ファインケミカル株式会社 Ｎ，ｎ−ビス（２−ヒドロキシ−３−クロロプロピル）アミノ基を有する化合物の製造方法
CN107207408A (zh) * 2015-02-13 2017-09-26 东丽精细化工株式会社 具有n,n‑双(2‑羟基‑3‑氯丙基)氨基的化合物的制造方法
US10017485B2 (en) 2015-02-13 2018-07-10 Toray Fine Chemicals Co., Ltd. Manufacturing method for compound having N,N-bis(2-hydroxy-3-chloropropyl)amino group
CN107207408B (zh) * 2015-02-13 2019-06-07 东丽精细化工株式会社 具有n,n-双(2-羟基-3-氯丙基)氨基的化合物的制造方法
JP2020033320A (ja) * 2018-08-31 2020-03-05 東レ・ファインケミカル株式会社 ジグリシジルアミン系エポキシ化合物の精製方法
JP7061538B2 (ja) 2018-08-31 2022-04-28 東レ・ファインケミカル株式会社 ジグリシジルアミン系エポキシ化合物の精製方法

Also Published As

Publication number Publication date
JPWO2013089006A1 (ja) 2015-04-27

Similar Documents

Publication Publication Date Title
US8415490B2 (en) Epoxy compound and manufacturing method thereof
WO2013021851A1 (fr) Composé époxy de haute pureté et son procédé de fabrication
WO2013089006A1 (fr) Procédé de production d'un composé de glycidylamine époxy
JP6147422B2 (ja) Ｎ，ｎ−ビス（２−ヒドロキシ−３−クロロプロピル）アミノ基を有する化合物の製造方法
JP2013193980A (ja) 低粘度エポキシ化合物およびその製造方法
WO2011034114A1 (fr) Composé diépoxy, procédé de production de celui-ci et composition contenant ledit composé diépoxy
US8664413B2 (en) High-purity epoxy compound and method of producing thereof
JP6095620B2 (ja) ビナフタレン骨格を有するエポキシ樹脂
JP2012219081A (ja) 高純度ジグリシジルアミン系エポキシ化合物およびその製造方法
WO2014162947A1 (fr) Procédé de production d'un composé époxy de type diglycidylamine
JP2013075889A (ja) 高純度エポキシ化合物およびその製造方法
JP6432791B2 (ja) ２−グリシジルオキシ−ｎ，ｎ−ジグリシジルアニリンの製造方法
JP2013185134A (ja) エポキシ化合物およびその製造方法
JP7061538B2 (ja) ジグリシジルアミン系エポキシ化合物の精製方法
JP2013184954A (ja) エポキシ化合物およびその製造方法
JP2013184955A (ja) エポキシ化合物およびその製造方法
JP2011213683A (ja) フタルイミド構造含有グリシジルエーテル化合物およびその製造方法
WO2011135925A1 (fr) Composé diépoxyde, procédé pour le préparer et compositions le contenant
JP2016155891A (ja) ビナフタレン骨格を有する精製エポキシ樹脂の製造方法
JP2015232093A (ja) 多官能グリシジルアニリン系エポキシ化合物の製造方法
JP2011195526A (ja) 高純度アニリド構造含有グリシジルエーテル化合物の製造方法
JP2010180148A (ja) Ｎ−グリシジルフタルイミドの製造方法

Legal Events

Date Code Title Description
ENP Entry into the national phase

Ref document number: 2013505222

Country of ref document: JP

Kind code of ref document: A

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 12856654

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 12856654

Country of ref document: EP

Kind code of ref document: A1