JPS58208282A - Preparation of polyglycidyl derivative - Google Patents

Abstract

PURPOSE:In the addition reaction of an aminophenol and an epihalohydrin, to obtain the titled compound in a short time, by reacting the amino group with the epihalohydrin in the absence of a catalyst, reacting the phenolic hydroxyl group with it in the presence of a phase transfer catalyst, followed by dehydrohalogenation. CONSTITUTION:In the reaction of a compound having a primary amino group and a phenolic hydroxyl group in the molecule, namely, an aminophenol (e.g., a condensate of o,m,p-aminophenol, m-aminophenol, and formaldehyde, etc.) and an epihalohydrin, the amino group of the aminophenol and the epihalohydrin are subjected to addition reaction in the absence of a catalyst, the phenolic hydroxyl group and the epihalohydrin are subjected to addition reaction in the presence of a phase transfer catalyst such as quaternary ammonium salt, quaternary phosphonium salt, or quaternary arsonium salt, and the reaction product is dehydrohalogenated with a caustic alkali, to give a polyglycidyl derivative. USE:A raw material for epoxy resins.

Description

Detailed Description of the Invention *The invention is directed to the production of polyaminophenols, which are compounds containing a primary ano group and one phenolic hydroxyl group in the molecule (hereinafter generally referred to as aminophenols), by reacting with toebino-10hydrin. 1ill of high purity glycidyl derivatives
It is about the method of building.

Polyglycidyl n5nu heat resistance of aminophenol (
It is useful as a raw material for epoxy 11M fat, which has been deprecated.

When polyglycidyl derivatives are produced by reacting aminophenols with epihalohydrin, unreacted amines easily undergo an addition reaction with the resulting glycidyl groups, resulting in a high molecular weight product.

For this reason, it is generally difficult to produce polyglycidyl derivatives with low molecular weight and high epoxy content. If the epoxy content is low, the heat resistance of the cured product will decrease when used as an epoxy resin. Furthermore, if unreacted amine remains, it will undergo a curing reaction by itself at room temperature, resulting in a significant decrease in storage stability as an epoxy resin. In order to avoid these drawbacks, the conventional method has been to react the aminophenol toepihalophytrine in the presence of a lithium salt at low temperature for a long period of time, and then dehydrogenate it. 37-17970). Although this method yields a low molecular weight polyglycidyl derivative, the first stage addition reaction requires a long time. For example, it takes 137 hours at 25°C, and even if the reaction is carried out at 45°C, which is the upper limit of the reaction temperature that can be used industrially, it still takes 10 to 12 hours or more.

In the present invention, the addition reaction between an amino group and epihalohydrin is carried out in the absence of a catalyst, and then the addition reaction between a phenolic hydroxyl group and epihalohydrin is carried out using a phase transfer catalyst. It is possible to significantly shorten the number of stage addition reactions. Furthermore, the obtained polyglycidyl derivative exhibits a high epoxy content and good storage stability, and the cured product exhibits a high heat distortion temperature.

As the starting material for the present invention, compounds containing both a primary amino group and a phenolic hydroxyl group in the molecule can generally be used. Specifically, monom-type aminophenols such as 0, m and p-aminophenol, polycyclic aminophenols such as 5-aminonaphthol, ', o, m,
Examples include condensates of p-aminophenol and formaldehyde. As the epihalohydrin, epichlorohydrin, epibromohydrin, and epiiodohydrin can be used.

In the first step of the present invention, aminophenols and epihalohydrin are reacted in the absence of a catalyst to simulate the addition reaction of an amino group to epi-lochtrin. It is desirable to use epihalohydrin in an amount of 3 times or more equivalent to the active hydrogen of the hydroxyl group and amino group of the aminophenol. The reaction temperature can be 70°C or higher to shorten the reaction time. The reaction time is, for example, 70°C to 8
One interval at 0°C is sufficient.

In the second step of the present invention, a phase transfer catalyst is added to the above reactants and a short reaction is carried out at 100°C to 11,0°C for 5 times.

Usually, 10 to 30 minutes is sufficient for this time. In this reaction, an addition reaction between a phenolic hydroxyl group and epihalohydrin occurs, and the resulting lohydrin is partially dehydrohalogenated by excess epihalohydrin to form glycidyl ether or glycidyl amine. Any amount of phase transfer catalyst can be used, but it is preferably 1 to 10 mol % based on the hydroxyl group of the aminophenol used.

, generally known phase transfer catalysts, such as quaternary ammonium salts such as tetrazo, tylammonium bromide, trioctylmethylammonium chloride, penciltriethylammonium chloride, benzyltrimethylammonium chloride, tetraphenylphosphonium chloride, tri- Quaternary phosphonium salts such as phenylmethylphosphonium chloride, and quaternary arsonium salts can be used.

In the third step of the present invention, the mixture of halohydrin amine, herohydrin ether, glycidyl amine, and glycidyl ether obtained in the second step is reacted with an aqueous caustic alkali solution to perform dehydrohalogenation. It is a polyglycidyl derivative. At this time, unreacted epihalohydrin can also be distilled off before reacting with the caustic aqueous solution. Alkali can be used in any concentration (preferably 10 to 50%). The amount of alkali to be used is preferably from equivalent to twice the active hydrogen of the hydroxyl group and amino group of the aminophenol used. The reaction temperature is preferably 40 to 60°C, and dehydrohalogenation is usually completed within one hour. After the dehydrohalogenation reaction is completed, the aqueous layer is removed from the reaction mixture, washed several times with water, and unreacted epihalohydrin is distilled off under reduced pressure to obtain a highly pure polyglycidyl derivative of aminephenols.

The yield is usually 95% or more.

A feature of the present invention is that in the addition reaction of aminophenols and shrimp lohydrin, the addition reaction of the amino group to epihalohydrin is carried out, and then the addition reaction of the phenolic hydroxyl group to epihalohydrin is carried out. On this occasion,
By conducting the former reaction in the absence of a catalyst and the latter reaction in the presence of a phase transfer catalyst, the total addition reaction time is significantly shorter than in conventional methods and can be completed in 1 to 1.5 hours.

Another feature of the present invention is that when dehydrohalogenating an addition product containing a halohydrin, it is reacted with an aqueous solution of caustic alkali in the presence of a phase transfer catalyst. The phase transfer catalyst added in the addition reaction is used as it is. The effect of the phase transfer catalyst in the dehydrohalogenation reaction is to promote the reaction to completion at low temperature and in a short time, which means that the residual chlorohydrin in the product is reduced compared to when the phase transfer catalyst is not used. This also suppresses the production of high molecular weight substances that may be produced by high-temperature reactions. Furthermore, since a phase transfer catalyst is used, an aqueous caustic alkali solution with a relatively low concentration can be used, and salts can be easily removed after the reaction. In the method of the present invention, the salt is completely dissolved in the aqueous layer and can be easily removed by liquid separation.

The polyglycidyl derivative obtained by the production method of the present invention is
It exhibits a high epoxy content and is virtually free of polymers. For example, polyglycidyl derivatives produced from m- and p-aminophenols have an epoxy content of 83% or more and are low-viscosity liquids. The polyglycidyl derivative obtained by the method of the present invention can be hardened using a known hardening agent.

The obtained cured product generally exhibits a high heat distortion temperature and has excellent properties as an epoxy resin.

Next, the present invention will be explained using specific examples, but the present invention is not limited only to these examples.

Example 1 A mixture of 1.09 f (10 mmol) of m-aminophenol and 11 g (120 mmol) of epichlorohydrin was heated to 70°C and reacted with stirring for 1 hour, and then 0.1 jl of benzyltriethylammonium chloride was added.
(0.5 mmol) was added, heated to ioooC, and reacted for 20 minutes with stirring. The reaction mixture was cooled to 50°C, 12f (60 mmol) of a 20% aqueous sodium hydroxide solution was added, and the mixture was vigorously stirred at 50°C for 50 minutes. This reaction mixture was allowed to stand, and after removing the aqueous layer, it was washed twice with water.

Unreacted epichlorohydrin was distilled off at 110°C under reduced pressure (3 mavHp) to obtain a pale yellow liquid of 2.64f (95% yield as triglycidyl derivative of m-aminophenol). The epoxy equivalent measured by the hydrochloric acid-dioxane method was 108, and the epoxy content was 86% of the theoretical amount.
Met.

To 100 parts of this polyglycidyl derivative, 136 parts of methylhimic anhydride and 2 parts of dimethylbenzylamine were added.
After curing at 00°C for 3 hours and then at 150°C for 15 hours, a pale brown cured product was obtained. The heat distortion temperature of this product was 168°C.

Example 2 A mixture of 1.09 f (10 mmol) of p-aminophenol and 1 lf (120 mmol) of epichlorohydrin was heated to 80°C and stirred for 1 hour. 0,5
mmol) was added, heated to 100°C, and stirred for 20 minutes. The reaction mixture was cooled to 50°C and 121% of a 20% aqueous solution of caustic soda was added. ' (60 mmol) was added and vigorously stirred at 50°C for 1 hour. This reaction mixture was allowed to stand, and after removing the aqueous layer, it was washed twice with water. Unreacted epichlorohydrin was distilled off at 110° C. under reduced pressure (3 Hf) to obtain a pale yellowish brown liquid of 2.68 f (yield 95% as a p-ruaminophenol triglycidyl derivative). The epoxy equivalent weight was 111 and the epoxy content was 83% of theory.

To 100 parts of this polyglycidyl derivative, 136 parts of methylhimic anhydride and 2 parts of dimethylbenzylamine were added,
Heat deformation temperature 17 for curing under the same conditions as Example 1
A cured product at 5°C was obtained.

Example 3 m-Aminophenol (100 mmol) and formalin aqueous solution (501 mol) were reacted under the catalyst of hydrochloric acid to obtain a condensate with a melting point of 160 to 180°C. This condensate 115y and epichlorohydrin 11f (12
When the reaction was carried out in the same manner as in Example 1 using 2.39 g of a brown solid, 2.39 g of a brown solid was obtained. This one is 7
Softens between 0 and 80°C. Ephoxy equivalent weight was 121.

When 136 parts of methylhimic anhydride and 2 parts of dimethylbenzylamine were added to 100 parts of this polyglycidyl derivative and cured under the same conditions as in Example 1, the heat distortion temperature was 210.
A cured product was obtained at a temperature of at least °C.

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Claims (5)

[Claims] (1) A compound containing a primary amino group and a phenolic hydroxyl group in the molecule is reacted with epihalohydrin to form an adduct of the amino group and epihalohydrin, and then an addition reaction of the phenolic hydroxyl group and epihalohydrin is performed in the presence of a phase transfer catalyst, A method for producing a polyglycidyl derivative, which comprises dehydrogenating the thus obtained mixture of halohydrin ether, halohydrin amine, glycidyl ether, and glycidyl amine with a caustic alkali. (2) The production method according to claim 1, wherein a mixture containing a halohydrin ether and a halohydrin amine is dehydrogenated using an aqueous caustic alkali solution in the presence of a phase transfer catalyst. (3) The manufacturing method according to claim 1 or 2, wherein the phase transfer catalyst is a quaternary ammonium salt, a quaternary phosphonium salt, or a quaternary arsonium 1. (4) The compound containing a primary aino group and a 7-enolic hydroxyl group in the 5+-preliminary meat is o, mgL and p-aminophenol! lf Claims The manufacturing method described in the first volume. (5) The manufacturing method according to claim 4fJ1, wherein the compound containing a primary amino group and a phenolic hydroxyl group in the molecule is a condensate of m-7 minophenol and formaldehyde.