JP2018159053A - Method for producing polyfunctional glycidylamine type epoxy compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a polyfunctional glycidylamine type epoxy compound having high production efficiency on an industrial scale. SOLUTION: In a cyclization reaction in which a liquid containing a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group and an aqueous solution containing an alkali are mixed to produce a polyfunctional glycidylamine type epoxy compound. , The cyclization reaction is carried out in an emulsified state having a dispersed phase of a liquid containing the compound having the N, N-bis (2-hydroxy-3-chloropropyl) amino group in the continuous phase of the aqueous solution containing the alkali. It is characterized by that. [Selection diagram] Fig. 1

Description

  The present invention relates to a process for producing a polyfunctional glycidylamine type epoxy compound that is industrially useful, that is, has high production efficiency.

  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.

  As a method for producing a polyfunctional glycidylamine type epoxy compound, as described in Patent Documents 1 and 2, N, N-bis (2-hydroxy-) produced by addition reaction of epichlorohydrin to an amine compound. An aqueous solution containing an alkali is mixed with a liquid containing a compound having a 3-chloropropyl) amino group with a stirrer equipped with a stirring blade, and a polyfunctional glycidylamine type epoxy compound is produced by a cyclization reaction by dehydrochlorination.

  However, as in the production methods described in Patent Documents 1 and 2, a liquid containing a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group and an aqueous solution containing an alkali are mixed with a stirrer equipped with a stirring blade. When they are mixed, a long reaction time is required, and in order to secure an industrial production amount, a large facility is required and the production efficiency is low.

  That is, an industrial production method with high production efficiency has been desired in the production of a polyfunctional glycidylamine type epoxy compound.

  Accordingly, there has been a demand for a production method for efficiently producing a polyfunctional glycidylamine type epoxy compound obtained by reacting an alkali with a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group. .

JP 2003-119244 A International Publication No. 2010/047244

  The objective of this invention is providing the manufacturing method of a polyfunctional glycidyl amine type epoxy compound with high production efficiency on an industrial scale.

  As a result of intensive studies in view of the above problems, the present inventors mixed a liquid containing a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group with an aqueous solution containing an alkali to obtain glycidyl. In a cyclization reaction for producing an amine-type epoxy compound, a dispersed phase of a liquid containing a compound having the N, N-bis (2-hydroxy-3-chloropropyl) amino group in a continuous phase of the aqueous solution containing the alkali The present inventors have found a method for producing a polyfunctional glycidylamine type epoxy compound characterized in that the cyclization reaction is carried out in an emulsified state.

  According to the method for producing a polyfunctional glycidylamine type epoxy compound of the present invention, a liquid containing a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group in an aqueous continuous phase containing an alkali. Since the polyfunctional glycidylamine type epoxy compound can be generated in a short time by cyclization reaction in an emulsified state in which oil droplets are formed, productivity is greatly improved compared to conventional methods. be able to.

It is explanatory drawing which shows typically an example of the circulating reaction apparatus with a static mixer. It is explanatory drawing which shows typically an example of the reaction apparatus with an emulsifier. 2 is an explanatory diagram schematically showing a reaction apparatus described in Synthesis Example 1. FIG. (A) is a line drawing which shows an example of the dispersion state of the reaction liquid obtained by the manufacture example of Example 2, (b) is a reference drawing which reduced the line drawing of (a) to the same magnification as FIG. It is. 5 is a line drawing showing an example of a dispersion state of a reaction solution obtained in a production example of Comparative Example 1. FIG. It is a graph which compares the progress of reaction in the manufacture example of an Example and a comparative example.

Below, it describes in detail about the manufacturing method of the polyfunctional glycidyl amine type epoxy compound of this invention.
The method for producing a polyfunctional glycidylamine-type epoxy compound of the present invention comprises a cyclization reaction in which a liquid containing a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group and an aqueous solution containing an alkali are mixed. The cyclization reaction is carried out in an emulsified state in which a dispersed phase composed of a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group is formed in a continuous phase composed of an aqueous solution containing an alkali. This is a cyclization reaction method for efficiently obtaining a functional glycidylamine type epoxy compound.

  In the present specification, “a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group” means that the N, N-bis (2-hydroxy-3-chloropropyl) amino group is 1 An amine compound having two or more, such as N, N-bis (2-hydroxy-3-chloropropyl) amine compound, N, N, N ′, N′-tetra (2-hydroxy-3-chloropropyl) diamine compound Etc.

  In the production method of the present invention, a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group can be produced by subjecting an amine compound to an addition reaction of epichlorohydrin.

  As the amine compound, a monoamine compound or a diamine compound can be used. Examples of monoamine compounds include aniline, o-toluidine, m-toluidine, p-toluidine, 2-phenoxyaniline, 3-phenoxyaniline, 4-phenoxyaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol and the like. Illustrated. By adding epichlorohydrin to the monoamine compound, an N, N-bis (2-hydroxy-3-chloropropyl) amine compound is obtained. As the monoamine compound, aniline, toluidine, phenoxyaniline, and aminophenol are preferable, and aniline, o-toluidine, m-toluidine, 4-phenoxyaniline, 3-aminophenol, and 4-aminophenol are particularly preferable.

  On the other hand, when a diamine compound is used as the amine compound and epichlorohydrin is subjected to an addition reaction, an N, N, N ′, N′-tetra (2-hydroxy-3-chloropropyl) diamine compound is obtained. Examples of the diamine compound include 4,4′-diaminodiphenylmethane, 3,3′-diaminodiphenylmethane, 3,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,3′-diaminodiphenyl ether, and 3,4 ′. -Diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone and the like. As the diamine compound, diaminodiphenyl ether, diaminodiphenylmethane, and diaminodiphenylsulfone are preferable. Among them, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, and 4,4′-diaminodiphenyl. Sulphone, 3,3′-diaminodiphenyl sulfone is preferred.

  In the production method of the present invention, the compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group is preferably aniline, o-toluidine, m-toluidine, p-toluidine, 2-phenoxyaniline, 3-phenoxyaniline, 4-phenoxyaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4 A compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group derived from an amine compound selected from 3,4′-diaminodiphenylsulfone and 3,3′-diaminodiphenylsulfone may be used.

Examples of the alkali used in the cyclization reaction 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 tert Amylate, potassium tert- amylate, sodium n- Hekishirato, potassium n- Hekishirato and tetramethylammonium hydroxide is exemplified. Of these, sodium hydroxide and potassium hydroxide are preferably used. These alkalis can be used alone or in combination of two or more.
The alkali is dissolved in a solution containing water and used as an aqueous solution.

  In this invention, the usage-amount of an alkali is 2-30 mol times with respect to the amine-type compound which is a raw material of the compound which has a N, N-bis (2-hydroxy-3-chloropropyl) amino group. preferable.

  The cyclization reaction is preferably performed in the presence of a quaternary ammonium salt and / or a quaternary phosphonium salt. By adding and coexisting these salts, the reaction is promoted and the yield of the polyfunctional 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, β-methylcholine, phenyltrimethylammonium, etc. Bromide, chloride , May be mentioned iodine Casio, hydrogencarbonates and hydroxides such as sulfuric acid. 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. , Trimethylphenylphosphonium, benzyltrimethylphosphonium, diallyldimethylphosphonium, n-octyltrimethylphosphonium, stearyltrimethylphosphonium, cetyldimethylethylphosphonium, tetrapropylphosphonium, tetran-butylphosphonium, phenyltrimethylphosphonium, methyltriphenylphosphonium, ethyltriphenyl Phosphonium Bromide salts such as finely tetraphenylphosphonium, chloride salt, iodine Casio, may be mentioned hydrogen sulfate and hydroxide, and the like.

  The addition amount of the quaternary ammonium salt and / or quaternary phosphonium salt may be a catalytic amount, and is 0.001 to 0 with respect to the N, N-bis (2-hydroxy-3-chloropropyl) amino group-containing compound. .5 mole times is preferred.

  In the cyclization reaction of the present invention, the reaction temperature is preferably 0 to 90 ° C, more preferably 10 to 70 ° C. Moreover, reaction time becomes like this. Preferably it is 0.2 to 60 minutes, More preferably, it is 0.5 to 40 minutes.

  As a liquid containing a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group used in the cyclization reaction of the present invention, an epichlorohydrin is added to an amine compound and reacted. You may use the reaction liquid containing the compound which has the N, N-bis (2-hydroxy-3-chloropropyl) amino group to produce | generate as it is, or distill off the solvent and epichlorohydrin which coexist in the reaction liquid. Alternatively, a new solvent may be added.

  As the solvent added in the cyclization reaction, an alcohol solvent, a hydrocarbon solvent, an ether solvent and an ester solvent are preferably used.

  Examples of 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 Recall 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- Chirueteru, tripropylene glycol, tripropylene glycol monomethyl ether and tripropylene glycol mono -n- butyl ether.

  Examples of the hydrocarbon solvent 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.

  Examples of ether solvents include diisopropyl 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.

  Examples of the ester solvent include methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, and isobutyl acetate.

  Among them, 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 is preferably 0.1 to 20 times by weight with respect to the compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group, more preferably 1 10 times by weight.

  In the present invention, a liquid containing a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group and an aqueous solution containing an alkali are mixed, and an aqueous continuous phase comprising an aqueous solution containing an alkali contains N , N-bis (2-hydroxy-3-chloropropyl) amino group is formed into an emulsified state in which an oil droplet-like dispersed phase comprising a liquid containing the compound is formed. As a result, mass transfer between the aqueous phase and the oil phase occurs very quickly, and the cyclization reaction can be completed in a short time. In the present specification, the “emulsified state” means that the oil phase is dispersed in droplets in the aqueous phase. The diameter of the oil droplet-like dispersed phase in the emulsified state is preferably 500 μm or less, and more preferably 200 μm or less. There are dynamic light scattering method, centrifugal sedimentation light transmission method, laser diffraction method, Field Flow Fractionation method, electrical zone detection method, microscopy method, etc. .

  In the production method of the present invention, a liquid containing a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group and an aqueous solution containing an alkali are mixed and emulsified using a static mixer and / or an emulsifier. Can be in a state.

  A static mixer is a static mixer that does not use power, and has a special mixing element (element) installed in the pipe. The liquid that passes through the pipe uses its own velocity energy. , A device for continuous mixing.

  FIG. 1 schematically shows an example of a reaction apparatus using a static mixer. A liquid mixture of a liquid containing a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group and an aqueous solution containing an alkali in the reaction tank 1 (hereinafter sometimes referred to as “reaction liquid”). It is strong because it is sent to the static mixer 3 by the liquid feed pump 2 and these reaction liquids are repeatedly subjected to division, conversion, enlargement, reduction, unity, etc. and moving when passing through the elements in the static mixer 3. A shearing force can be applied to form an emulsified state. The cyclization reaction proceeds in this emulsified state, and the reaction solution becomes a mixed solution of the raw material compound and the cyclization reaction product.

In order to make the flow rate sent to the static mixer in the present invention into an emulsified state of a liquid containing a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group and an aqueous solution containing an alkali, the larger one is required. Although effective, it is preferably adjusted so that the linear velocity in the tube is 20 to 500 cm / second.
Moreover, although there exist a one-pass system and an outside tank circulation line system as an operation form, it is not limited to either.

  Emulsifiers are classified into high-speed rotation methods (turbine / stator type, thin-film swirl type), colloid mill method, high-pressure jet method, and ultrasonic method, all of which apply strong shearing force to the reaction solution to emulsify. It forms a state and is not limited to any one. For example, in the case of a high-speed rotating turbine-stator type emulsifier, faster rotation of the turbine and smaller clearance are effective for forming the emulsion. The rotational speed of the turbine is preferably 2000 to 60000 rpm, and the clearance between the turbine and the stator is preferably 0.1 to 5 mm.

In addition, as operation modes, there are a batch method, a one-pass method, an external circulation line method, an internal circulation one-through method, and a thin film swirl method, but it is not limited to any one.
FIG. 2 is an explanatory view schematically showing an example of a batch-type reaction apparatus having an emulsifier. In a batch-type reaction vessel 4, a mixed solution (reaction solution) of a solution containing a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group and an aqueous solution containing an alkali is introduced, and the reaction vessel By operating the homogenizer 5 arranged in 4, a strong shearing force is applied to the reaction solution, and an emulsified state is formed. By operating the homogenizer 5, the reaction liquid in the reaction tank 4 becomes emulsified in a short time, and the cyclization reaction proceeds rapidly.

  In the present invention, the polyfunctional glycidylamine type epoxy compound which is the target product is isolated by (1) removing unreacted raw materials, (2) distilling off the reaction solvent, (3) extraction with a hydrophobic solvent, (4) extraction. This can be achieved by a combination of general unit operations such as solvent distillation, (5) distillation and (6) crystallization.

  For example, an organic solvent such as toluene is added to the liquid after the cyclization reaction, the polyfunctional glycidylamine type epoxy compound is extracted into the oil phase, and the aqueous phase is separated and removed. Furthermore, it is preferable to completely remove the salt dissolved in the oil phase by washing the obtained oil phase with water. The amount of the organic solvent used is preferably 0.2 to 50 times by weight and more preferably 1 to 20 times by weight with respect to the object of the present invention.

  A polyfunctional glycidylamine type epoxy compound is obtained by distilling low boiling components such as an extraction solvent and unreacted epichlorohydrin from the obtained oil phase. When distilling off the low boiling point components, 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 extracted solvent, unreacted epichlorohydrin and the like may be reused.

  The polyfunctional glycidylamine type epoxy compound obtained by the production method of the present invention has a chemical purity of 80% or more, preferably 90 or more. When the chemical purity of the polyfunctional glycidylamine type epoxy compound is less than 80%, the storage stability is lowered, and the cured resin cured by the curing agent may not have the desired physical properties. In this specification, the chemical purity of the polyfunctional glycidylamine type epoxy compound is determined by the fraction of the peak area of the polyfunctional glycidylamine type epoxy compound (HPLC area%) as measured by the method described later using high performance liquid chromatography. ).

  Hereinafter, although an Example demonstrates concretely, this invention is not restrict | limited only to an Example. In addition, the analytical value of the polyfunctional glycidylamine type | mold epoxy compound obtained in this specification was measured with the following method. Whether or not an emulsified state was formed was determined by the following measurement.

(Chemical purity)
The fraction (HPLC area%) of the peak area of the polyfunctional glycidylamine type epoxy compound was measured by liquid chromatography under the following conditions (CLASS-VP manufactured by Shimadzu Corporation), and used as the chemical purity.
Column: YMC-Pack ODS-AM303 4.6φ × 250mm
-Column temperature: 40 ° C
-Mobile phase: 0.1% (v / v) phosphoric acid aqueous solution as composition (A), methanol as composition (B), and a mixture of volume ratio (A) :( B) = 40: 60 as mobile phase It was.
・ Flow rate: 1 ml / min ・ Injection volume: 3 μl
・ Detection: UV 254nm
・ Analysis time: 80 minutes ・ Analysis sample preparation: 0.02 g of sample is weighed and diluted to about 50 ml of methanol. However, as long as the same result as the analysis result based on the above analysis conditions is obtained, it is limited to this analysis condition. is not.

(Confirmation of emulsification state)
The aluminum plate was placed on dry ice, and the aluminum plate was sufficiently cooled. The sampled reaction solution was quickly spread thinly on the plate, allowed to stand for a while, and frozen. The reaction liquid frozen with an optical microscope VH-5000 manufactured by KEYENCE was observed, and it was observed whether or not an emulsified state in which an oil droplet-like dispersed phase was formed in an aqueous continuous phase was observed. 4 and 5 are schematic diagrams illustrating the interface between the water phase and the oil phase in imaging obtained by an optical microscope.

  In the following Examples and Comparative Examples, the description “XX weight times / amine compound” means that the amount added is XX weight times the weight of the amine compound. In addition, the description “XX mole times / amine compound” means that the amount added is XX mole times the mole amount of the amine compound.

(Synthesis Example 1) 4-phenoxy-N, N-bis (2-hydroxy-3-chloropropyl) aniline 25 wt% (4-phenoxyaniline) in the reaction raw material liquid tank 6 using the apparatus shown in FIG. / Epichlorohydrin solution (4-phenoxyaniline: epichlorohydrin = 1: 6 (molar ratio)) and acetic acid in the acidic compound solution tank 7 are fed by a feed pumps 8 and 9, respectively, at a feed rate of 1.10 g. 5/8 inch SUS304 tubular reactor 11 (inner diameter: 13.4 mm, length: 400 mm, space volume: 48 ml (min./min) and 0.13 g / min. (Shibata Chemical Co., Ltd., SUS316L Helipack No. 1 filling)) (liquid space velocity in the reaction tube of the reaction solution was 1.4 h ⁻¹ ). 150 g of addition reaction liquid transferred from the outlet of the tubular reactor 11 to the reaction liquid receiver 12 was obtained. When purity analysis of 4-phenoxy-N, N-bis (2-hydroxy-3-chloropropyl) aniline in the obtained reaction solution was performed, the purity was 96.5% (HPLC area%). .

(Synthesis Example 2) N, N, N ′, N′-tetrakis (2-hydroxy-3-chloropropyl) 3,4′-diaminodiphenyl ether 15 in the reaction raw material liquid tank 6 using the apparatus shown in FIG. 3 wt% (3,4′-diaminodiphenyl ether) / epichlorohydrin solution (3,4′-diaminodiphenyl ether: epichlorohydrin = 1: 12 (molar ratio)), and acidic compound solution tank 7 Acetic acid was fed into a 5 / 8-inch SUS304 tubular reactor 11 (with a feed rate of 1.16 g / min and 0.08 g / min, respectively, in a constant temperature bath 10 at 80 ° C. by means of liquid feed pumps 8 and 9. Inner diameter: 13.4 mm, length: 800 mm, space volume: 96 ml (Shibata Chemical Co., Ltd., SUS316L Helipack No. 1 filling)) (Reaction of the reaction solution at this time) Internal solution space velocity was 0.7 h ^-1). 200 g of additional reaction liquid transferred from the outlet of the tubular reactor 11 to the reaction liquid receiver 12 was obtained. A purity analysis of N, N, N ′, N′-tetrakis (2-hydroxy-3-chloropropyl) 3,4′-diaminodiphenyl ether in the obtained reaction solution was conducted, and the purity was 93.5%. (HPLC area%).

Synthesis Example 3 N, N-bis (2-hydroxy-3-chloropropyl) -m-aminophenol Using the apparatus shown in FIG. 3, 11.6 wt% (m-amino) in the reaction raw material liquid tank 6 Phenol) / epichlorohydrin solution (m-aminophenol: epichlorohydrin = 1: 9 (molar ratio)) and acetic acid in the acidic compound solution tank 7 are fed by a feed pump 8 and 9, respectively, at a feed rate of 1 5/8 inch SUS304 tubular reactor 11 (inner diameter: 13.4 mm, length: 400 mm, space volume) installed in a constant temperature bath 10 at 70 ° C. at 0.13 g / min and 0.11 g / min. 48 ml (manufactured by Shibata Chemical Co., Ltd., SUS316L Helipack No. 1 filling) was fed (the liquid space velocity in the reaction tube of the reaction solution at this time was 1.4 h ⁻¹ ). 200 g of additional reaction liquid transferred from the outlet of the tubular reactor 11 to the reaction liquid receiver 12 was obtained. When purity analysis of N, N-bis (2-hydroxy-3-chloropropyl) -m-aminophenol in the obtained reaction solution was performed, the purity was 98.1% (HPLC area%). .

(Synthesis Example 4) N, N, N ′, N′-tetrakis (2-hydroxy-3-chloropropyl) 4,4′-diaminodiphenylmethane 15 in the reaction raw material liquid tank 6 using the apparatus shown in FIG. 2 wt% (4,4′-diaminodiphenylmethane) / epichlorohydrin solution (4,4′-diaminodiphenylmethane: epichlorohydrin = 1: 12 (molar ratio)), and acidic compound solution tank 7 Acetic acid was fed into a 5 / 8-inch SUS304 tubular reactor 11 (with a feed rate of 1.16 g / min and 0.08 g / min, respectively, in a constant temperature bath 10 at 70 ° C. by a feed pump 8 and 9). Inner diameter: 13.4 mm, length: 400 mm, space volume: 48 ml (Shibata Chemical Co., Ltd., SUS316L made Helipack No.1 filling)) (liquid in reaction tube of reaction liquid at this time) During rate was 1.4H ^-1). 200 g of additional reaction liquid transferred from the outlet of the tubular reactor 11 to the reaction liquid receiver 12 was obtained. When purity analysis of N, N, N ′, N′-tetrakis (2-hydroxy-3-chloropropyl) 4,4′-diaminodiphenylmethane in the obtained reaction solution was performed, the purity was 93.9%. (HPLC area%).

Example 1
To 150 g of the reaction solution containing 4-phenoxy-N, N-bis (2-hydroxy-3-chloropropyl) aniline obtained in Synthesis Example 1, 1.8 g of tetra n-butylammonium hydrogen sulfate (0.03 mol times / 4-phenoxyaniline) and 164.2 g of a 22% aqueous sodium hydroxide solution (5.0 mole times / 4-phenoxyaniline) were added, and a circulating reaction apparatus with a static mixer shown in FIG. 1 (static mixer: manufactured by Noritake Limited) Using T4-21R-2PT (inner diameter: 5 mm, number of elements: 21, length: 16.5 cm)), the mixture is circulated at a flow rate of 1.0 L / min (in-tube linear velocity: 85 cm / sec) to form an emulsified state and cyclize Reaction was performed. The cyclization reaction was completed in a treatment time of 20 minutes. In the cyclization reaction, an amino group having 2-hydroxy-3-chloropropyl [that is, 4-phenoxy-N- (2-hydroxy-3-chloropropyl) -N-glycidylaniline] is detected in the reaction solution. When gone, the reaction was considered complete. When the state of the reaction liquid was observed with an optical microscope, it was confirmed that an emulsified state in which an oil droplet-like dispersed phase was formed in an aqueous continuous phase was confirmed.

  After completion of the cyclization reaction, stationary liquid separation was performed. The standing liquid separation was performed by adding 50.2 g of water and 16.7 g of methanol to the obtained organic layer and washing it. Epichlorohydrin, water and methanol were removed from the obtained organic layer under reduced pressure to obtain 53.2 g of 4-phenoxy-N, N-diglycidylaniline (weight yield (based on 4-phenoxyaniline): 99%). It was. The chemical purity of the obtained 4-phenoxy-N, N-diglycidylaniline was 94.9% (HPLC area%).

(Example 2)
To 150 g of the reaction solution containing 4-phenoxy-N, N-bis (2-hydroxy-3-chloropropyl) aniline obtained in Synthesis Example 1, 1.8 g of tetra n-butylammonium hydrogen sulfate (0.03 mol times / 4-phenoxyaniline) and 164.2 g of a 22% aqueous sodium hydroxide solution (5.0 mole times / 4-phenoxyaniline) were added, and the reactor with an emulsifier shown in FIG. 2 (homogenizer: Turbine Stator manufactured by Primix Co., Ltd.) A high-speed rotation method using ROBOMICS, a clearance between the turbine and the stator of 0.5 mm) was processed at a turbine rotational speed of 16000 rpm to form an emulsified state, and a cyclization reaction was performed. The cyclization reaction was completed in a treatment time of 3 minutes. The completion of the cyclization reaction was the same as in Example 1.

  When the state of the reaction liquid in the production example of Example 2 was observed with an optical microscope, as shown in the line drawing of FIG. 4 (a), a dispersed phase (hatched portion) composed of small oil droplets was present in the aqueous continuous phase. It was confirmed that the emulsion was formed. FIG. 4B is a reference diagram showing the scale of FIG. 4A substantially the same as the scale of FIG. 5 described later for comparison.

  After completion of the cyclization reaction, stationary liquid separation was performed. The standing liquid separation was performed by adding 50.2 g of water and 16.7 g of methanol to the obtained organic layer and washing it. Epichlorohydrin, water, and methanol are removed from the obtained organic layer under reduced pressure to obtain 52.2 g of 4-phenoxy-N, N-diglycidylaniline (weight yield (4-phenoxyaniline standard): 97%). It was. The chemical purity of the obtained 4-phenoxy-N, N-diglycidylaniline was 93.7% (HPLC area%).

(Comparative Example 1)
To 150 g of the reaction solution containing 4-phenoxy-N, N-bis (2-hydroxy-3-chloropropyl) aniline obtained in Synthesis Example 1, 1.8 g of tetra n-butylammonium hydrogen sulfate (0.03 mol times / 4-phenoxyaniline), 164.2 g of a 22% aqueous sodium hydroxide solution (5.0 mole times / 4-phenoxyaniline) were charged, and a four-necked flask reactor with a meniscus type stirring blade (flask: 500 ml of glass, Meniscus type stirring blade: made of PTFE, width 75 mm, height 22 mm, thickness 4 mm) was stirred at a stirrer rotational speed of 350 rpm.

  The cyclization reaction was completed in a processing time of 120 minutes. The completion of the cyclization reaction was the same as in Example 1. When the state of the reaction solution was observed with an optical microscope, it was confirmed that both the aqueous phase and the oil phase (hatched portion) were in a continuous phase-like form and not in an emulsified state as shown in the line drawing of FIG. .

  After completion of the cyclization reaction, stationary liquid separation was performed. The standing liquid separation was performed by adding 50.2 g of water and 16.7 g of methanol to the obtained organic layer and washing it. Epichlorohydrin, water, and methanol were removed from the obtained organic layer under reduced pressure to obtain 52.2 g of 4-phenoxy-N, N-diglycidylaniline (weight yield (based on 4-phenoxyaniline): 97%). It was. The chemical purity of the obtained 4-phenoxy-N, N-diglycidylaniline was 93.0% (HPLC area%).

FIG. 6 shows the reaction time of the residual ratio of 4-phenoxy-N- (2-hydroxy-3-chloropropyl) -N-glycidylaniline as an intermediate product in the production examples of Examples 1 and 2 and Comparative Example 1. Is a graph plotted against. As shown in the production examples of Examples 1 and 2, it is clear that the reaction proceeds rapidly by carrying out the cyclization reaction in an emulsified state.
The results of the production examples of Examples 1 and 2 and Comparative Example 1 are collectively shown in Table 1.

(Example 3)
In the production example of Example 1, sulfuric acid was added to 200 g of the reaction solution containing N, N, N ′, N′-tetrakis (2-hydroxy-3-chloropropyl) 3,4′-diaminodiphenyl ether obtained in Synthesis Example 2. 1.45 g of tetra n-butylammonium hydrogen (0.03 mol / 3,4′-diaminodiphenyl ether), 181.7 g of 22% sodium hydroxide aqueous solution (7.0 mol / 3,4′-diaminodiphenyl ether) The cyclization reaction was carried out in the same manner as in the production example of Example 1 except that it was added. The cyclization reaction was completed in a treatment time of 20 minutes. The completion of the cyclization reaction was confirmed by the reaction of an amino group having 2-hydroxy-3-chloropropyl [that is, 4-phenoxy-N- (2-hydroxy-3-chloropropyl) -N-glycidylaniline] in the reaction solution. The reaction was considered complete when no longer detected. When the state of the reaction solution was observed with an optical microscope, it was confirmed that the reaction solution was in an emulsified state in which oil droplets were formed in the aqueous continuous phase.

  After completion of the cyclization reaction, stationary liquid separation was performed. The standing liquid separation was performed by adding 85.8 g of water and 28.5 g of methanol to the obtained organic layer and washing it. Epichlorohydrin, water and methanol were removed from the obtained organic layer under reduced pressure, and 57.5 g of N, N, N ′, N′-tetraglycidyl 3,4′-diaminodiphenyl ether (weight yield (3,4 ′) -Based on diaminodiphenyl ether): 95%). The chemical purity of the obtained N, N, N ′, N′-tetraglycidyl 3,4′-diaminodiphenyl ether was 92.0% (HPLC area%).

Example 4
In the production example of Example 2, sulfuric acid was added to 200 g of the reaction solution containing N, N, N ′, N′-tetrakis (2-hydroxy-3-chloropropyl) 3,4′-diaminodiphenyl ether obtained in Synthesis Example 2. 1.45 g of tetra n-butylammonium hydrogen (0.03 mol / 3,4′-diaminodiphenyl ether), 181.7 g of 22% sodium hydroxide aqueous solution (7.0 mol / 3,4′-diaminodiphenyl ether) The cyclization reaction was carried out in the same manner as in the production example of Example 2 except that it was added. The cyclization reaction was completed in a treatment time of 3 minutes. The completion of the cyclization reaction was the same as in Example 3. When the state of the reaction solution was observed with an optical microscope, it was confirmed that the reaction solution was in an emulsified state in which oil droplets were formed in the aqueous continuous phase.

  After completion of the cyclization reaction, stationary liquid separation was performed. The standing liquid separation was performed by adding 85.8 g of water and 28.5 g of methanol to the obtained organic layer and washing it. Epichlorohydrin, water and methanol were removed from the obtained organic layer under reduced pressure, and 56.2 g of N, N, N ′, N′-tetraglycidyl 3,4′-diaminodiphenyl ether (weight yield (3,4 ′) -Based on diaminodiphenyl ether): 93%). The chemical purity of the obtained N, N, N ′, N′-tetraglycidyl 3,4′-diaminodiphenyl ether was 91.5% (HPLC area%).

(Comparative Example 2)
In the production example of Comparative Example 1, sulfuric acid was added to 200 g of the reaction solution containing N, N, N ′, N′-tetrakis (2-hydroxy-3-chloropropyl) 3,4′-diaminodiphenyl ether obtained in Synthesis Example 2. Hydrogen tetra-n-butylumonium 1.45 g (0.03 mol times / 3,4′-diaminodiphenyl ether), 221.7% aqueous sodium hydroxide solution 181.7 g (7.0 mol times / 3,4′-diaminodiphenyl ether) The cyclization reaction was carried out in the same manner as in the production example of Comparative Example 1 except that it was added. The cyclization reaction was completed in a processing time of 150 minutes. The completion of the cyclization reaction was the same as in Example 3. When the state of the reaction solution was observed with an optical microscope, it was confirmed that the reaction solution was not in an emulsified state.

  After completion of the cyclization reaction, stationary liquid separation was performed. The standing liquid separation was performed by adding 85.8 g of water and 28.5 g of methanol to the obtained organic layer and washing it. Epichlorohydrin, water, and methanol were removed from the obtained organic layer under reduced pressure, and 57.3 g of N, N, N ′, N′-tetraglycidyl 3,4′-diaminodiphenyl ether (weight yield (3,4 ′) -Based on diaminodiphenyl ether): 95%). The chemical purity of the obtained N, N, N ′, N′-tetraglycidyl 3,4′-diaminodiphenyl ether was 91.8% (HPLC area%).

(Example 5)
In the production example of Example 1, 52.9 g (4. 4) of isopropyl alcohol was added to 200 g of the reaction liquid containing N, N-bis (2-hydroxy-3-chloropropyl) -m-aminophenol obtained in Synthesis Example 3. 5 mol times / m-aminophenol) and 226.8% aqueous sodium hydroxide solution 186.8 g (5.3 mol times / m-aminophenol) were added. went. The cyclization reaction was completed in a processing time of 15 minutes. The completion of the cyclization reaction was defined as completion of the reaction when no amino group having 2-hydroxy-3-chloropropyl was detected in the reaction solution. When the state of the reaction solution was observed with an optical microscope, it was confirmed that the reaction solution was in an emulsified state in which oil droplets were formed in the aqueous continuous phase.

  After completion of the cyclization reaction, stationary liquid separation was performed. The standing liquid separation was performed by adding 63.5 g of water and 21.1 g of methanol to the obtained organic layer and washing it. Epichlorohydrin, water and methanol were removed from the obtained organic layer under reduced pressure to obtain 45.8 g of triglycidyl-m-aminophenol (weight yield (m-aminophenol standard): 85%). The chemical purity of the obtained triglycidyl-m-aminophenol was 74.5% (HPLC area%).

(Example 6)
In the production example of Example 2, 52.9 g (4. 4) of isopropyl alcohol was added to 200 g of the reaction liquid containing N, N-bis (2-hydroxy-3-chloropropyl) -m-aminophenol obtained in Synthesis Example 3. 5 mol times / m-aminophenol) and 226.8% aqueous sodium hydroxide solution 186.8 g (5.3 mol times / m-aminophenol) were added, and the cyclization reaction was carried out in the same manner as in the production example of Example 2. went. The cyclization reaction was completed in a treatment time of 3 minutes. The completion of the cyclization reaction was the same as in Example 5. When the state of the reaction solution was observed with an optical microscope, it was confirmed that the reaction solution was in an emulsified state in which oil droplets were formed in the aqueous continuous phase.

  After completion of the cyclization reaction, stationary liquid separation was performed. The standing liquid separation was performed by adding 63.5 g of water and 21.1 g of methanol to the obtained organic layer and washing it. Epichlorohydrin, water and methanol were removed from the obtained organic layer under reduced pressure to obtain 44.2 g of triglycidyl-m-aminophenol (weight yield (m-aminophenol standard): 82%). The chemical purity of the obtained triglycidyl-m-aminophenol was 73.2% (HPLC area%).

(Comparative Example 3)
In the production example of Comparative Example 1, 52.9 g of isopropyl alcohol was added to 200 g of the reaction liquid containing N, N-bis (2-hydroxy-3-chloropropyl) -m-aminophenol obtained in Synthesis Example 3 (4. 5 mol times / m-aminophenol) and 226.8% aqueous sodium hydroxide solution 186.8 g (5.3 mol times / m-aminophenol) were added, and the cyclization reaction was carried out in the same manner as in Production Example of Comparative Example 1. went. The cyclization reaction was completed in a processing time of 120 minutes. The completion of the cyclization reaction was the same as in Example 5. When the state of the reaction solution was observed with an optical microscope, it was confirmed that the reaction solution was not in an emulsified state.

  After completion of the cyclization reaction, stationary liquid separation was performed. The standing liquid separation was performed by adding 63.5 g of water and 21.1 g of methanol to the obtained organic layer and washing it. Epichlorohydrin, water and methanol were removed from the obtained organic layer under reduced pressure to obtain 45.3 g of triglycidyl-m-aminophenol (weight yield (standard): 84%). The chemical purity of the obtained triglycidyl-m-aminophenol was 72.0% (HPLC area%).

(Example 7)
In the production example of Example 1, hydrogen sulfate was added to 200 g of the reaction solution of N, N, N ′, N′-tetrakis (2-hydroxy-3-chloropropyl) 4,4′-diaminodiphenylmethane obtained in Synthesis Example 4. Charged 1.46 g of tetra n-butylammonium (0.03 mol times / 4,4′-diaminodiphenylmethane) and 182.0 g of 22% aqueous sodium hydroxide (7.0 mol times / 4,4′-diaminodiphenylmethane). A cyclization reaction was performed in the same manner as in the production example of Example 1 except that. The cyclization reaction was completed in a treatment time of 20 minutes. The completion of the cyclization reaction was defined as completion of the reaction when no amino group having 2-hydroxy-3-chloropropyl was detected in the reaction solution. When the state of the reaction solution was observed with an optical microscope, it was confirmed that the reaction solution was in an emulsified state in which oil droplets were formed in the aqueous continuous phase.

  After completion of the cyclization reaction, stationary liquid separation was performed. To the obtained organic layer, 85.1 g of water and 28.3 g of methanol were added and washed, followed by standing liquid separation. Epichlorohydrin, water, and methanol were removed from the obtained organic layer under reduced pressure to obtain 55.0 g (weight yield (4,4′-diaminodiphenylmethane reference): 91%). The chemical purity of the obtained N, N, N ′, N′-tetraglycidyl 4,4′-diaminodiphenylmethane was 92.3% (HPLC area%).

(Example 8)
In the production example of Example 2, 200 g of the reaction solution obtained in Synthesis Example 4 was added to 1.46 g of tetra n-butylammonium hydrogen sulfate (0.03 mol times / 4,4′-diaminodiphenylmethane), 22% sodium hydroxide. The cyclization reaction was carried out in the same manner as in the production example of Example 2 except that 182.0 g of the aqueous solution (7.0 mole times / 4,4′-diaminodiphenylmethane) was added. The cyclization reaction was completed in a treatment time of 3 minutes. The completion of the cyclization reaction was the same as in Example 7. When the state of the reaction solution was observed with an optical microscope, it was confirmed that the reaction solution was in an emulsified state in which oil droplets were formed in the aqueous continuous phase.

  After completion of the cyclization reaction, stationary liquid separation was performed. To the obtained organic layer, 85.1 g of water and 28.3 g of methanol were added and washed, followed by standing liquid separation. Epichlorohydrin, water, and methanol were removed from the obtained organic layer under reduced pressure to obtain 54.4 g (weight yield (4,4′-diaminodiphenylmethane reference): 90%). The chemical purity of the obtained N, N, N ′, N′-tetraglycidyl 4,4′-diaminodiphenylmethane was 91.5% (HPLC area%).

(Comparative Example 4)
In the production example of Comparative Example 1, 200 g of the reaction solution obtained in Synthesis Example 4 was added to 1.46 g of tetra n-butylammonium hydrogen sulfate (0.03 mol times / 4,4′-diaminodiphenylmethane), 22% sodium hydroxide. The cyclization reaction was carried out in the same manner as in the production example of Comparative Example 1 except that 182.0 g (7.0 mol times / 4,4′-diaminodiphenylmethane) of the aqueous solution was added. The cyclization reaction was completed in a processing time of 120 minutes. The completion of the cyclization reaction was the same as in Example 7. When the state of the reaction solution was observed with an optical microscope, it was confirmed that the reaction solution was not in an emulsified state.

  After completion of the cyclization reaction, stationary liquid separation was performed. To the obtained organic layer, 85.1 g of water and 28.3 g of methanol were added and washed, followed by standing liquid separation. Epichlorohydrin, water, and methanol were removed from the obtained organic layer under reduced pressure to obtain 53.4 g (weight yield (4,4′-diaminodiphenylmethane reference): 88%). The chemical purity of the obtained N, N, N ′, N′-tetraglycidyl 4,4′-diaminodiphenylmethane was 90.0% (HPLC area%).

DESCRIPTION OF SYMBOLS 1 Reaction tank 2 Liquid feed pump 3 Static mixer 4 Reaction tank 5 Homogenizer 6 Reaction raw material liquid tank 7 Acidic compound solution tank 8 Liquid feed pump 9 Liquid feed pump 10 Constant temperature tank 11 Tubular reactor 12 Reaction liquid receiver

Claims (4)

  In a cyclization reaction in which a liquid containing a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group and an aqueous solution containing an alkali are mixed to produce a polyfunctional glycidylamine type epoxy compound, the alkali is removed. Performing the cyclization reaction in an emulsified state having a dispersed phase of a liquid containing the compound having the N, N-bis (2-hydroxy-3-chloropropyl) amino group in a continuous phase of the aqueous solution containing the aqueous solution. A method for producing a polyfunctional glycidylamine type epoxy compound.   A liquid containing a compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group and an aqueous solution containing an alkali are mixed to obtain an emulsified state using a static mixer and / or an emulsifier. The method for producing a polyfunctional glycidylamine type epoxy compound according to claim 1.   3. The compound having an N, N-bis (2-hydroxy-3-chloropropyl) amino group is prepared by an addition reaction between an amine compound and epichlorohydrin. A method for producing a polyfunctional glycidylamine type epoxy compound.   Aniline, o-toluidine, m-toluidine, p-toluidine, 2-phenoxyaniline, 3-phenoxyaniline, 4-phenoxyaniline, 2-aminophenol, 3-aminophenol, 4-aminophenol, 4,4′-diamino N, N-bis derived from an amine compound selected from diphenylmethane, 4,4′-diaminodiphenyl ether, 3,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, and 3,3′-diaminodiphenyl sulfone ( The method for producing a polyfunctional glycidylamine type epoxy compound according to any one of claims 1 to 3, wherein a compound having a 2-hydroxy-3-chloropropyl) amino group is used.

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