JPS6147474A - Preparation of brominated oxirane derivative - Google Patents

Abstract

PURPOSE:To produce the titled compound useful as an electronic material, etc., in high yield and purity and low hydrolyzable chlorine content, by reacting a brominated alkylphenol with epichlorohydrin, and carrying out dehydrochlorination reaction with an alkali in two steps. CONSTITUTION:A brominated alkylphenol of formula I (R is >=1C alkyl; n is 1-3) is subjected to the addition reaction with epichlorohydrin in the presence of a catalyst such as tetraethyl ammonium bromide, and the obtained brominated alkylphenyl chlorohydrin ether is subjected to the dehydrochlorination reaction with excess epichlorohydrin using an aqueous solution of an alkaline compound while removing the water together with epichlorohydrin by azeotropic distillation under reduced pressure. After removing the excess epichlorohydrin, the resultant brominated oxirane derivative is dissolved in an organic solvent, and the second dehydrochlorination reaction of the residual hydrolyzable chlorine is carried out with an alkaline compound to obtain the objective compound of formula II.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Application Field] The present invention relates to a method for producing brominated oxirane derivatives, and particularly to a method for producing high purity brominated oxirane derivatives in an efficient manner.

High purity brominated oxirane derivatives obtained by carrying out the present invention are useful as electrical/electronic materials and paint resins.

[Conventional technology]

Conventionally known methods for producing oxirane derivatives from aromatic hydroxy compounds include a one-stage method and a two-stage method. The one-stage method is a method for producing oxirane derivatives in which an alkali or alkaline earth metal hydroxide is added, a hydroxy compound and epichlorohydrin are reacted, and etherification and dehydrochlorination are carried out simultaneously.

The two-step method is a method in which epichlorohydrin is added to an aromatic hydroxy compound, a small amount of an alkali compound, a catalyst, etc. is added, and a reaction is first carried out, and then an alkali compound is added to carry out dehydrochlorination.

The latter two-stage method is common in terms of yield and product purity.

These reactions can be explained using the following reaction formula.

``臥(1) (2) <3) ■Purchase [Problem that the invention aims to solve] However, these have a yield of 70-85% and low purity, which is not satisfactory for the field of electrical and electronic materials. .

The object of the present invention is to produce brominated oxirane derivatives from brominated alkylphenols in high yield and at high efficiency.

The purpose is to provide a method for manufacturing with high purity. Brominated oxirane derivatives used in electrical and electronic materials etc. have the drawback of prolonging the curing time and corroding metals etc. when the amount of hydrolyzable chlorine is high. Therefore, the reality is that consumers demand brominated oxirane derivatives with a low content of hydrolyzable chlorine.

[Means for solving problems]

As a result of extensive investigation, the present inventors found that the combination of brominated alkylphenol represented by the following general formula (II) (wherein R represents an alkyl group having 1 or more carbon atoms, and n represents an integer of 1 to 3) and epichlorohydrin A method for producing a brominated oxirane derivative represented by the following general formula (I) (wherein R and n are the same as above) by reaction has been found.

Specifically, the present invention provides a method for producing a brominated oxirane derivative comprising the following first to third steps.

1st step: Brominated nofurgilf Jnol and epichlorohydrin are reacted with f=I in the presence of a catalyst to obtain brominated alkylphenyl chlorohydrin ether. 2nd step: Brominated alkylphenyl chlorohydrin ether is reacted with excess epichlorohydrin. In the presence of an aqueous solution of an alkaline compound, water is subjected to a dehydrochlorination reaction under reduced pressure with epichlorohydrin while being azeotropically distilled, and excess epichlorohydrin is distilled off.Third step Brominated A obtained in the above step The xylan derivative is dissolved in an organic solvent, and the hydrolyzable chlorine remaining in the xylan derivative is subjected to a second dehydrochlorination reaction using an alkali compound to obtain high 1Iii1'! A highly brominated oxirane derivative is obtained.

[For production]

The brominated alkylphenol used in the present invention includes 4
, 6-dipromo 〇-cresol, 4,6-dipromo 2-isopropylphenol, 2,4.6-dibromo 3-isopropylphenol, 2,6-dipromo 4
-tert-butylphenol, 2,6-dipromo4
-3eC-butylphenol, 2-bromo-4-isopropylphenol, 2.6-siglomo-Actylphenol, 2.6-dipromo-4-tert-dodecylphenol, 4-promo-O-cresol, and the like.

Next, examples of the catalyst used in the addition reaction of brominated alkylphenol and epichlorohydrin in the first step include quaternary amine salts, basic anion exchange resins, and alkali metal halides. Specifically, examples of the quaternary amine salt include te-1-laethylammonium bromide, trimethylbenzylammonium bromide, trimethylzetylammonium chloride, and tribudylammonium bromide. As the basic anion exchange resin, commercially available basic anion exchange resins can be used.

The amount of the catalyst is approximately 5.0 parts by weight based on 100 parts by weight of brominated alkylphenol as a raw material. A single catalyst or a mixture of catalysts can be used.

The addition reaction temperature varies depending on the raw materials, but is usually 30 to 12
The temperature is 0°C, preferably 40 to 80°C. The reaction time is until the addition reaction is substantially completed, and varies depending on the reaction temperature and the amount of catalyst, but is usually 0.5-16 hours, preferably 2-10 hours.

Examples of the alkali used in the second step and the third step include hydroxide, chlorium hydroxide, hydroxide, calcium hydroxide, and the like. The amount of alkali used in the second step is 75 to 0.99 mol of U2O per 1 mol of brominated alkylphenol used as the raw material, and the dehydrochlorination reaction is carried out in the presence of this alkali compound. In this dehydrochlorination, water is azeotropically distilled off with epichlorohydrin while maintaining the reaction system under reduced pressure conditions of 50 to 300 Torr.
The alkali addition rate and distillation rate are adjusted while maintaining the water content in the reaction system at 0.1 to 5.0% by weight. If the alkali addition rate is too fast, the pH in the reaction system will increase, causing polymerization, which is not preferable. It is preferable to maintain pl-(7 to 9.5) in the reaction system, usually for about 0.5 to 8 hours.

It is also possible to carry out the reaction without removing water from the reaction system, but this is industrially disadvantageous because epichlorohydrin is decomposed by the water in the reaction system.

The reaction temperature is 30-130°C, preferably 50-90°C. Next, excess epichlorohydrin is removed by distillation under reduced pressure, and the by-produced alkali halide salt is removed by filtration or washing with water to obtain a brominated oxirane derivative.

In the third step, the brominated oxirane derivative obtained in the second step is dissolved in a 1M solvent, and an alkali of o, oi = 0.15 mole is added to 1 mole of brominated alkylphenol as a raw material to dissolve bromine. By removing the chlorohydrin ether remaining in the oxirane derivative,
A highly purified brominated A xylan derivative can be obtained in high yield and purity.

The above-mentioned solvent is a solvent that does not react with the oxirane group, such as methyl ethyl ketone, toluene, dioxane, etc., and can be used singly or in combination.

The concentration of the alkaline aqueous solution is usually 1 to 50% by weight, preferably 10. to 20% by weight.

Reaction temperature is 30-120°C, preferably 50-90°C
It is. The reaction time is usually 0.5 to 10 hours until the chlorohydrin needles remaining in the brominated oxirane derivative disappear.

〔Effect of the invention〕

As shown in Table 2 below, the high purity brominated oxirane derivative prepared in this manner contains 0.1% by weight or less of hydrolyzable chlorine, especially 0.01 to 0.05% by weight.
It has an extremely low weight Φ%, making it extremely useful as a resin for the electronic and electrical industries.

〔Example〕

The present invention will be described in more detail with reference to Examples below, but these Examples are merely illustrative and the present invention is not limited by the Examples. Note that the term ``section'' hereinafter simply refers to the ff1fi section.

Example 1 4.6-dipromo 2-isopropylphenol 1.0
Mol (294 parts), 370 parts of epichlorohydrin, 1st
The catalyst listed in the table was charged into a four-way flask equipped with a thermometer, a condenser, and a stirrer, and reacted at 75±5° C. for 4 hours.

Next, the reaction solution was cooled to 60° C., a water separator was attached, and a 50% aqueous sodium hydroxide solution was added dropwise over about 3 hours. At this time, the reaction system was 150±50To
The reaction temperature was maintained at an azeotropic temperature with 1 pic] corhydrin, the water produced was removed, and the epichlorohydrin was returned to the reaction system to carry out the reaction. hydroxide 1
After dropping the aqueous helium solution, the remaining epichlorohydrin was distilled off from the system under reduced pressure, and the by-product salt was removed by filtration or washing with water. The obtained brominated oxirane derivative was dissolved in methyl ethyl ketone, and after adding 20% aqueous sodium hydroxide solution in the amount shown in Table 1 for 1 to 3 hours, the organic layer was washed 6 times with 500 ml of pure water. Finally, methyl ethyl ketone was distilled off from the organic layer under reduced pressure to obtain a highly pure brominated oxirane derivative.

The analytical values of the highly purified brominated oxirane derivative thus obtained are shown in Table 2.

Examples 2 to 6 In Example 1, 4,6-dipromo-2-isobutylphenol was replaced with other brominated alkylphenol.
The production method using moles is shown in Table 1 together with Example 1. Furthermore, the analysis results of the obtained target compound are shown in Table 2.

Comparative Examples 1 to 2 Examples will be shown in which the third step, the purification step, is not performed using the same reaction apparatus as used in Examples 1 to 6. The results are shown in Table 2.

Table 1 shows the types of catalysts and amounts of alkali in Examples and Comparative Examples.

Claims (2)

[Claims] (1) Brominated alkylphenol represented by the following general formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [II] (where R is an alkyl group with 1 or more carbon atoms, and n is an integer from 1 to 3. ) and epichlorohydrin are reacted using the following general formula [I
] ▲There are mathematical formulas, chemical formulas, tables, etc.▼ [I] (However, in the formula, R and n are the same as above.) A method for producing a brominated oxirane derivative. (2) Brominated alkylphenol represented by the following general formula [II] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [II] (where R is an alkyl group with 1 or more carbon atoms, and n is an integer from 1 to 3. ) and epichlorohydrin to form the following general formula [I
] There are brominated oxirane derivatives represented by ▲ mathematical formulas, chemical formulas, tables, etc. ▼ In the production method of [I] (where R and n are the same as above), in the first step, brominated alkylphenol and epichlorohydrin are combined in the presence of a catalyst. Sub-addition reaction to obtain brominated alkyl phenyl chlorohydrin ether Second step Brominated alkyl phenyl chlorohydrin ether is reacted with an aqueous solution of an alkali compound in the presence of excess epichlorohydrin, and water is depressurized together with epichlorohydrin. Step 3: Perform dehydrochlorination reaction with azeotropic distillation to distill off excess epichlorohydrin. Third step: Dissolve the brominated oxirane derivative obtained in the above step in an organic solvent, and dissolve the remaining hydration in the oxirane derivative. A method for producing a brominated oxirane derivative, which comprises obtaining a highly purified brominated oxirane derivative through a second dehydrochlorination reaction of decomposable chlorine using an alkali compound.