JPH01168679A - Production of glycidyl ethers - Google Patents

Abstract

PURPOSE:To easily obtain the title compound having low content of hardly hydrolyzable halogen, in high yield, by reacting monohydric alcohols, etc., with a 1-halo-2,3-epoxyalkane using a specific solvent in combination with an alkali metal hydroxide. CONSTITUTION:The objective compound useful as a raw material for electronic part such as a sealant of semiconductor, etc., an electrically conductive paste or adhesive for light-emitting diode, etc., especially electronic parts in electronic field can be produced by reacting (A) monohydric or polyhydric alcohols (e.g., benzyl alcohol or hydrogenated bisphenol) with (B) 1-20mol (based on 1mol of OH of the component A) of a 1-halo-2,3-epoxyalkane using (C) 0.1-10 pts.wt. (based on 1 pt.wt. of the component B) of a sulfoxide compound such as dimethyl sulfoxide as a solvent in the presence of (D) 0.9-1.3mol (based on 1mol of the OH of the component A) of an alkali metal hydroxide such as NaOH at 20-140 deg.C.

Description

DETAILED DESCRIPTION OF THE INVENTION Field of Industrial Application The present invention relates to an improvement in a method for producing glycidyl ethers. More specifically, the present invention particularly includes:
This invention relates to a method for producing in high yield glycidyl ethers with a low content of hardly hydrolyzable nitrogen, which are useful as raw materials for electronic component materials such as encapsulating materials for semiconductor devices, conductive paste materials, and adhesives for light emitting diodes. It is something.

Conventional technology In the past, glycidyl ethers had highly reactive epoxy groups, and their cured products had excellent properties, so they were widely used as raw materials for making various molds, but in recent years, the electronics field has rapidly developed. As a result, there has been an increasing demand for it as a raw material for electronic component materials such as encapsulating materials for semiconductor devices and conductive paste materials.

By the way, as the degree of integration of electronic parts increases, glycidyl ethers used as raw materials are required to have a higher quality when used as materials for electronic parts. It is required that the total amount of chlorine contained in the ethers, that is, the total amount of easily hydrolyzable chlorine and hardly hydrolyzable chlorine, is 11,000 pp or less.

Generally, residual chlorine in glycidyl ethers includes easily hydrolyzable chlorine represented by the following formula (I), formula (n),
Refractory chlorine represented by @) and (Foundation) are known.

HC2 H20H''H The easily hydrolyzable chlorine can be quickly dehydrochlorinated by treating the product glycidyl ether with an alkali metal hydroxide. On the other hand, dehydrochlorination of water-decomposable chlorine is possible by carrying out the dehydrochlorination reaction under harsh conditions; however, in this case, the cleavage of the epoxy ring is promoted, resulting in an intermolecular reaction between glycidyl ethers. Polymerization occurs, making it impossible to use it as a raw material for electronic component materials. Therefore, in the production of glycidyl ethers, it is an important issue how to suppress the production of this separation water-decomposable chlorine during the addition reaction.

Up to now, as a method for producing glycidyl ethers using phenols as raw materials, for example, one method has been to add sodium hydroxide to a solution in which bisphenol A and epichlorohydrin are dissolved.

Although methods for producing epoxy resins are known, the glycidyl ethers obtained in this way usually contain about 1200 to 4500 ppm of hydrolyzable chlorine.

In general, commercially available epoxy resins also include
Contains about 1000 to 20001) pm of water-decomposable chlorine.

In order to reduce the chlorine content in the epoxy resin obtained by such glycidyl etherification of phenols, a method has been proposed in which, for example, the glycidylation reaction of phenols is carried out in an aprotic solvent (Japanese Patent Application Laid-Open No. 60-31517), it was difficult to reduce the water-decomposable chlorine content to 400 ppm or less even by this method.

On the other hand, in the method of producing glycidyl ethers by reacting alcohols and epichlorohydrin in the presence of an alkali metal hydroxide, the production rate of beglycidyl ethers is extremely low compared to the glycidylation of phenols. It is not used as an industrial manufacturing method.

In glycidyl etherification of alcohols, a method for improving the production rate of the desired glycidyl ethers is to first convert the adduct of alcohols and epichlorohydrin using a Lewis acid catalyst such as boron trifluoride ether complex. A method has been proposed for producing glycidyl ethers by adding an aqueous sodium hydroxide solution to the solution and carrying out a dehydrochlorination reaction (Japanese Patent Publication No. 1983-
24149), and a method of reacting alcohols with epichlorohydrin in the presence of an alkali metal hydroxide using a phase transfer catalyst such as a quaternary ammonium salt has also been reported ["Synthesis"].
s) J No. 649 (1985)].

However, in the former method using a Lewis acid catalyst, although the yield of glycidyl ether is as high as 96-98%, the total amount of chlorine in the purified glycidyl ether is as high as 2-8% by weight. Most of the chlorine is separated water-decomposable chlorine, and the epoxy value of the glycidyl ether is as low as 70 to 90% of the theoretical epoxy value. In addition, in the latter method using a phase transfer catalyst, the content of separated water-decomposable chlorine is approximately 2000 p.
pm, and although it is reduced in intensity compared to the above method, it has the disadvantage that the 1 reaction rate is as low as 54 to 89%.

Problems to be Solved by the Invention The present invention overcomes the drawbacks of the conventional method of producing glycidyl ethyl compounds with low chlorine ffff1 through the glycidylation reaction of alcohols, and is particularly useful for electronic component materials in the electronics field. The purpose of this invention is to provide a method for producing glycidyl ethers in good yield using alcohols with a low content of separation water-decomposable halogens, which are suitable as raw materials for alcohols such as alcohols.

Means for Solving the Problems The present inventors have conducted intensive research on a method for producing glycidyl ether with a low chlorine content, particularly a low water-decomposable chlorine content. It was discovered that the objective could be achieved by using a specific solvent together with a metal hydroxide, and based on this knowledge, the present invention was completed.

That is, the present invention provides, in the presence of an alkali metal hydroxide,
Production of glycidyl ethers, characterized in that a sulfoxide compound is used as a solvent in producing glycidyl ethers by reacting monohydric or polyhydric alcohols with 1-no-2,3-epoxyalkanes. The present invention provides a method.

The present invention will be explained in detail below.

In the method of the present invention, examples of monohydric or polyhydric alcohols used as raw materials include methyl alcohol, ethyl alcohol, flobyl alcohol, methyl alcohol, and pentyl alcohol.

Hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl alcohol, tesyl alcohol, lauryl alcohol, ethynyl alcohol, flobenyl alcohol, futhynyl alcohol, pentenyl alcohol,
Hexenyl alcohol, heftenyl alcohol, octenyl alcohol.

Nonenyl alcohol, tesenyl alcohol, ethynyl alcohol, flovinyl alcohol, futhynyl alcohol, pentynyl alcohol, hexynyl alcohol, octyl alcohol, nonyl alcohol, tesynyl alcohol, cyclopropyl alcohol, cyclopentyl alcohol, cyclohexyl alcohol, allyl alcohol,
Benzyl alcohol, substituted benzyl alcohol, sorbitol, ethylene glycol, phlopylene gelicol,
polyethylene glycol, polypropylene glycol,
Examples include, but are not limited to, polytetramethylene glycol, phythanediol, bentanediol, hexanediol, neopentyl glycol, trimethylolpropane, glycerin, polyglycerol, pentaerythritol hydrogenated bisphenol A, hydrogenated bisphenol F, etc. isn't it.

l/% claw used in the method of the present invention, 3-
As the epoxyalkane, for example, 1-chloro-2,3
-Epoxypropane, 1-promo2,3-epoxypropane, l-chloro-2-methyl-2,3-epoxypropane, 1-7'romo2-methyl-2,3-epoxypropane, 1-chloro-2 , 3-epoxybutane, 1-
Examples include, but are not limited to, chloro-2,3-epoxypenkune.

In the method of the present invention, these 1-no, 2.3-
The epoxy alkane is generally used in an amount of 1 to 20 mol, preferably 2 to 10 mol, per 1 mol of hydroxyl group of the alcohol. If this amount is less than 1 mole, the glycidyl ethers produced in the reaction tend to polymerize due to intermolecular reaction, and if it exceeds 20 moles, productivity decreases, which is not preferable.

Examples of the alkali metal hydroxide used in the method of the present invention include sodium hydroxide, potassium hydroxide, and lithium hydroxide.

It is not limited to these. The amount of these alkali metal hydroxides used is usually 0.9 to 1.3 mol, preferably 1.0 to 1.3 mol, per mol of hydroxyl group of the alcohol.
It is selected within the range of 1.2 moles. If the amount used is less than 9 moles, there will be a large amount of easily hydrolyzable chloride, and the amount of alkali metal hydroxide used in the dehydrogenation step after product recovery will be large, which is undesirable. If it exceeds .3 mole, side reactions such as hydrolysis of 1-halo-2,3-epoxyalkane occur, which is not preferable.

Sulfoxide compounds used in the method of the present invention include dimethyl sulfoxide, diethyl sulfoxide, ethyl methyl sulfoxide, etc.
Among these, dimethyl sulfoxide is particularly preferred.

These sulfoxide compounds may be used alone or in combination of two or more, and the amount used is 1-halo-2,3-epoxyalkaf 1
It is usually selected in the range of 0.1 to 10 parts by weight, preferably 2 to 2 parts by weight, based on the weight of the sail. If the amount used is less than 0.1 part by weight, the amount of hardly hydrolyzable halogen will be large and the effect of the present invention will not be fully exhibited, and if it exceeds 10 parts by weight, it will take time and effort to recover the product. However, it is disadvantageous from an industrial standpoint.

Next, to explain one example of a preferred embodiment of the method of the present invention, first, monohydric or polyhydric alcohol and 1-halo-2
. This reaction is usually carried out at 20-140°C.
, preferably at a temperature in the range of 40 to 120°C.

If this temperature is less than 20°C, the reaction takes a long time and is not practical, and if it exceeds 140°C, the reaction may run out of control, which is not preferable.

Furthermore, in order to accelerate the reaction, 1-halo-2
．． It is preferable to remove the reaction product water from the system by azeotroping the reaction product water with the 3-epoxyalkane. In addition, it is recommended to add the alkali metal hydroxide in small portions over a period of about 1 to 5 hours, or to add it continuously. This is not preferred because it accelerates the hydrolysis of the epoxy alkane.

After the completion of the reaction, if the target product has a low boiling point, it can be recovered as is by distillation, but if it has a high boiling point, the 1-no-10-2,3-epoxyalkane and the reaction product water are first distilled. After thoroughly removing the residue, a poorly water-soluble solvent such as ketones such as methyl isobutyl ketone or aromatic hydrocarbons such as toluene is added to the residual liquid, and the disulfoxide compound is removed by washing with water, followed by distillation. It is sufficient to obtain glycidyl ethers.

The glycidyl ethers thus obtained contain about 100 ppm to 1 weight of easily hydrolyzable halogen, but the amount of separated water-degradable halogen is already 11.
000pp or less.

The glycidyl ethers are dissolved as they are or in an inert solvent such as methyl isobutyl ketone or toluene, and then an alkali metal hydroxide, preferably equivalent to the mole of the easily hydrolyzable halogen, is added to the solution. The reaction is carried out at a temperature in the range of 40 to 120° C. for about 2 hours, and then the reaction solution is washed with water or filtered, and then distilled to obtain glycidyl ethers made from desired alcohols. Easily hydrolyzable halogens and hardly hydrolyzable halogens contained in these glycidyl ethers are usually 50 ppm or less and 11,000 ppm or less, respectively.
pp or less.

Effects of the Invention According to the method of the present invention, monohydric or polyhydric alcohols and 1-
Halo-2,3-epoxyalkane tocara and glycidyl ethers with a low content of persistent halogen can be produced in high yield.

Since the glycidyl ethers obtained by the method of the present invention have a low chlorine content, they are suitable as raw materials for, for example, sealing materials for semiconductor devices in the electronics field, electronic component materials such as conductive paste materials, and light-emitting diode adhesives. used.

EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples in any way.

In addition, each characteristic in one example was measured according to the method shown below.

(1) Easily hydrolyzable chlorine glycidyl ether 507! 1), 20 g of IN-KOH methanol solution was added thereto, boiled for 15 minutes, titrated with silver nitrate, and the chlorine atoms in the compound were expressed as a weight fraction.

(2) Dissolve water-degradable chlorine glycidyl ether in 25-ethylene glycol monobutyl ether, add IN-KOH propylene glycol solution 25-L, boil for 20 minutes, titrate with silver nitrate, and dissolve the compound. The weight fraction of the total amount of chlorine in the sample is determined, and the weight fraction of the easily hydrolyzable chlorine amount is subtracted from this value.

(3) Epoxy equivalent This was carried out in accordance with the method of J Engineering S K-7236.

(4) Yield By capillary gas chromatography.

The amount of unreacted alcohol was determined.

Examples 1 to 5 Thermometer, dropping funnel for continuous addition of alkali metal hydroxide, stirring blade, and moisture evaporating from the reaction system;
- Chloro 2.3 - Capacity 2 with a separation tube equipped with a cooling tube to cool and liquefy dipoquin chloropane, separate the organic layer and aqueous layer based on the difference in specific gravity, return the organic layer to the reaction system, and remove the aqueous layer.
Using a separable flask with a baffle, use the containers shown in the attached table.

amount of alcohol and 1-chloro-2,3-epoxypropane were reacted. The reaction was carried out by continuously dropping an aqueous sodium hydroxide solution in the amount shown in the table for 2 hours in the presence of the sulfoxide compound of the type and amount shown in the table, and during this period the reaction temperature was kept at 6.
The temperature was maintained at 0°C, and after one drop of addition was completed, the same temperature was maintained for 1 hour to complete the reaction.

After the reaction is completed, unreacted 1-chloro-2,3-epoxypropane is removed by vacuum distillation, and the resulting crude glycidyl ether containing the by-product salt and sulfoxide compound is obtained. -Til was dissolved in toluene, and by-product salts and sulfoxide compounds were removed by washing with water. At this point, a portion of the sample was taken, and after removing toluene by distillation, easily hydrolyzable chlorine, separated hydrolyzable chlorine, and yield of the crude glycidyl ether were determined. The results are shown in the line table.

Next, 200 f of toluene was added to the crude glycidyl ether.
was added, and then an aqueous sodium hydroxide solution equivalent to the easily hydrolyzable chlorine of the crude glycidyl ether was added.
After reacting at 0° C. for 2 hours and washing with water nine times, toluene was removed by distillation.

Easily hydrolyzable chlorine, separated hydrolyzable chlorine, and epoxy equivalent of the glycidyl ether thus obtained were determined. The results are shown in the line table.

Comparative Examples 1 to 3 The same reaction equipment as that used in Example 1 was used, and the same procedure as in Example 1 was used, except that a quaternary ammonium salt shown in the attached table was used as a catalyst instead of using a sulfoxide compound. carried out. The results are shown in a line table.

As can be seen from this table, the reaction rate in Examples 1 to 5 was 98% or more, while the reaction rate in Comparative Examples 1 to 3 was about 92%, and the effect of using the sulfoxide compound was Remarkable.

Furthermore, the separation water-decomposable chlorine in Comparative Examples 1 to 3 was 16
00 ppm or more, whereas those of Examples 1 to 5 all have values of 400 ppm or less.

Claims (1)

[Claims] 1. In the production of glycidyl ethers by reacting monohydric or polyhydric alcohols with 1-halo-2,3-epoxy alkanes in the presence of an alkali metal hydroxide, as a solvent A method for producing glycidyl ethers, characterized by using a sulfoxide compound. 2. The manufacturing method according to claim 1, wherein the sulfoxide compound is dimethyl sulfoxide.