TWI487729B - Method for manufacturing polyglycidyl ether - Google Patents

Description

Method for producing polyglycidyl ether

The present invention relates to a process for producing a polyglycidyl ether, and more particularly to a small amount of chlorine obtained by reacting a propylene oxide adduct of bisphenol, β-methylepichlorohydrin and a base in the presence of a phase transfer catalyst. A method for producing polyglycidyl ether.

The cured product obtained from the polyepoxide is widely used in various industrial fields, especially paints or the like because of its relatively good adhesion to various substrates, heat resistance, chemical resistance, electrical properties, mechanical properties and the like. In the field of adhesives.

Among these polyepoxides, a specific polyglycidyl ether obtained from a propylene oxide adduct of bisphenol and β-methylepichlorohydrin has been known to exhibit excellent curability in a cationic curing system. Useful for materials.

However, in the past, almost no investigation has been made on a method of producing a polyglycidyl ether using β-methylepichlorohydrin. For example, there is a method in which a polyol compound is reacted with β-methylepichlorohydrin and epichlorohydrin in the presence of an aqueous sodium hydroxide solution (Patent Document 1), but even if it is intended to be It is also difficult to produce the target product by producing the above specific polyglycidyl ether. Further, when a method for producing a general polyol or a diol is used, that is, an addition reaction using a Lewis acid catalyst or the like is carried out in the first step, and then a production method using a saponification reaction using a base is carried out in the second step, Inevitably, side reactions occur, and there is a disadvantage that the chlorine content becomes high.

Prior technical literature

Patent literature

Patent Document 1 Japanese Patent No. 3579959

Therefore, the inventors of the present invention conducted intensive studies to produce a polyglycidyl ether having a reduced overall chlorine content, and as a result, it was found that when a base is used to make a propylene oxide adduct of bisphenol and β-methylepichlorohydrin ring-closed. The method of using a phase transfer catalyst is effective, and thus the present invention has been completed.

Accordingly, it is an object of the present invention to provide a process for easily producing a polyglycidyl ether having a reduced overall chlorine content.

That is, the present invention is a process for producing a polyglycidyl ether which is produced by reacting a polyol represented by the following general formula (I), β-methylepichlorohydrin, and a base to produce the following general formula (II). A method of expressing a polyglycidyl ether characterized by carrying out the aforementioned reaction in the presence of a phase transfer catalyst.

General formula (I)

In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m and n each independently represent a number from 1 to 10;

General formula (II)

₂ are the same as those in (the I) the general formula R ₁ and R in the formula but R ₁ and R _2.

In the present invention, the phase transfer catalyst is preferably a quaternary ammonium base or a quaternary ammonium salt, particularly preferably a quaternary ammonium salt.

According to the present invention, it is possible to easily produce a polyglycidyl ether which is suitable for use in an electronic material or an electrically insulating material, has a very low chlorine content, and has a small epoxy equivalent, by a simple operation.

Hereinafter, a method for producing the polyglycidyl ether of the present invention will be described in detail.

In the production method of the present invention, the polyol represented by the above general formula (I) used as a starting material can be obtained by a general method of adding propylene oxide to bisphenol or the like, and is also easy to use. Obtained from commercial products.

The production method of the present invention is a method for producing the polyglycidyl ether represented by the above general formula (II) by reacting the above polyol, β-methylepichlorohydrin and a base. Here, the use ratio of the above-mentioned β-methylepichlorohydrin to the above-mentioned polyol is not particularly limited as long as it is equivalent to or more than the hydroxyl group of the polyol, but is usually 1.0 to 10.0 equivalents, preferably A range of 2.0 to 8.0 equivalents. When the ratio of the above β-methylepichlorohydrin is less than 1.0 equivalent (equivalent), a hydroxyl group which is not etherified with glycidol remains, and the purity is lowered. Further, when it exceeds 10.0 equivalents, it is not preferable because not only the β-methylepichlorohydrin is wasted, but also the reaction rate is lowered or the epoxy equivalent is increased by the side reaction.

Further, examples of the base include alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, and alkali metal carbonates such as sodium carbonate and potassium carbonate. Among the bases of the present invention, sodium hydroxide is particularly preferred. In the present invention, it is preferred to use these bases in an aqueous solution, but depending on the case, a powdery or solid base may be added simultaneously or separately with water.

The amount of the base to be used is not particularly limited as long as it is equal to or higher than the hydroxyl group of the polyol, and is usually 1.0 to 2.0 equivalents, particularly preferably 1.0 to 1.5 equivalents. When the amount of the base used is less than the equivalent amount of the hydroxyl group of the aliphatic polyol, the chlorohydrin ether group which is not etherified with glycidol remains, and the purity is lowered. Further, when it exceeds 2.0 equivalent, since it is not only wasteful, Moreover, the purity of the product may be lowered due to side reactions, which is not preferable.

The invention is characterized in that the reaction of the above polyol, β-methylepichlorohydrin and alkali is carried out in the presence of a phase transfer catalyst, and the phase transfer catalyst is used to make an organic compound insoluble to water and organic The solvent-insoluble reagent is known as a reagent used for the reaction.

The aforementioned phase transfer catalyst may be, for example, a tertiary amine of trimethylamine, trioctylamine or tridecylamine; for example, tetramethylammonium, methyltrioctylammonium, methyltriammonium ammonium, benzyl a quaternary ammonium salt of trimethylammonium; such as tetramethylammonium chloride, methyltrioctylammonium chloride, methyltriammonium chloride, and quaternary ammonium benzyltrimethylammonium chloride The salt is particularly preferably a quaternary ammonium salt in the present invention.

The amount of the phase transfer catalyst used can be appropriately used in consideration of the kind of the polyol, the excess ratio of β-methylepichlorohydrin, the amount of the reaction solvent used, the reaction temperature, and the like, and is used for 100 parts by mass of the polyol. It is usually in the range of 0.1 to 10.0 parts by mass, preferably 0.5 to 5.0 parts by mass. When the amount of the phase transfer catalyst used is less than 0.1 part by mass, the reaction rate is remarkably slowed, or the epoxy equivalent is lowered by the progress of the side reaction, so that it is not practical, and more than 10.0 equivalent is not only wasted. Phase transfer catalysts, even more depending on the situation, may even hinder the reaction, so it is not good.

Further, in the production method of the present invention, there is also an advantage that a polyglycidyl ether having a chlorine content which is remarkably low can be obtained in one reaction. Here, the term "a reaction" refers not only to a method in which all raw materials and catalysts are placed in one reaction, but also includes an aliphatic polyol, β-methylepichlorohydrin, and a catalyst, followed by addition of a base. The method of reaction. In the present invention, the latter method is preferable from the viewpoint of ease of reaction control.

The above reaction is carried out at a temperature of from about 30 ° C to about 100 ° C, preferably from about 40 ° C to about 80 ° C. Further, although a solvent which is inert to the reaction such as a hydrocarbon, an ether or a ketone may be used in the reaction, when β-methylepichlorohydrin is excessively used, since β-methylepichlorohydrin also has a solvent Function, so it is not necessary to use a solvent inert to the reaction as described above.

The separation of the polyglycidyl ether as a target after completion of the reaction can be carried out, for example, by the following general operation: that is, after the excess β-methylepichlorohydrin is distilled off, hydrocarbons may be added as necessary. The water-insoluble solvent is washed with water, and then the formed salt, catalyst, and unreacted or derivatized alcohol component are removed.

The polyglycidyl ether obtained by the production method of the present invention can be used for various purposes in addition to being used as an electronic/electric insulating material.

Hereinafter, the present invention will be described in more detail by way of examples and comparative examples, but the invention is not limited thereto. In the following examples and the like, the epoxy equivalent is a molecular weight of an epoxide (resin) per one epoxy group.

Example 1

a propylene oxide adduct of bisphenol A having a hydroxyl group of 314 (BPX-11 manufactured by ADEKA Co., Ltd.) 178.9 g (0.5 mol), β-methylepichlorohydrin 462.5 g (5.0 mol), 1.5 g of tetramethylammonium chloride (0.84 parts by mass based on 100 parts by mass of the polyol) was placed in a glass flask equipped with a thermometer, a stirrer, and a cooling tube, and the temperature inside the flask was raised to 60 ° C to maintain the internal pressure. At 11.3 kPa, reflux was carried out.

While maintaining the temperature and pressure of the reaction system, 108.3 g of a 48.5 mass% aqueous sodium hydroxide solution (1.3 mol of sodium hydroxide) was added dropwise over 90 minutes, and the mixture was aged at 60 ° C for 150 minutes, and the reaction system was filtered. The salt produced. After excess β-methylepichlorohydrin in the filtrate was distilled off at 120 ° C under reduced pressure, toluene was added and washed thoroughly, followed by distilling off toluene under reduced pressure, followed by filtration again to give a pale yellow liquid product. (MEP-1: bisphenol A-propylene oxide adduct bis-methyl glycidyl ether) 222 g.

As a result of the analysis, it was found that the overall chlorine content was significantly lower than 0.23% by mass (the saponifiable chlorine was 0.01% by mass), and the epoxy equivalent was 286 (calculated value 242), which was caused by the side reaction. There is very little polymer quantification. Further, the yield based on the bisphenol A-propylene oxide adduct was 90%.

Comparative example 1

A propylene oxide adduct of bisphenol A having a hydroxyl value of 314 (BPX-11 manufactured by Asahi Kasei Kogyo Co., Ltd.) 178.9 g (0.5 mol) and 2.0 g of tin tetrachloride hydrate were placed in a thermometer. A glass flask of a stirrer and a cooling tube was heated to 70 °C. While maintaining the temperature at 70 to 75 ° C, 127.8 g (1.2 mol) of β-methylepichlorohydrin was added dropwise over 2 hours, and after the completion of the dropwise addition, stirring was further carried out at 70 to 75 ° C for 1 hour to carry out β- Esterification by methyl epichlorohydrin. The rate of formation of the β-methylepichlorohydrin addition ester in this stage is 100% as indicated by the theoretical value (based on the propylene oxide adduct of bisphenol A).

Then, 60 g of toluene was added, and while stirring at 60 to 65 ° C for 1 hour, 91.6 g of a 48.5 mass% aqueous sodium hydroxide solution (1.1 mol of sodium hydroxide) was added dropwise, and the mixture was stirred at 60 to 65 ° C for 30 minutes. After further adding 100 g of toluene and sufficiently washing with water, toluene was distilled off under reduced pressure to obtain a product of a pale yellow liquid (MEP-2: β-methyl glycidyl ether of bisphenol A-propylene oxide adduct) ) 209g. The total chlorine content of the obtained product was 4.55% by mass (the saponifiable chlorine was 0.05% by mass), the epoxy equivalent was 365 (calculated value 263), and the high molecular weight due to the side reaction was remarkable.

The following tests were carried out using the compositions of the examples and the comparative examples prepared by the blending amounts shown in [Table 1].

(colloidal time)

The obtained composition was dropped into 0.5 g on a hot plate held at each measurement temperature, and mixed with a spatula or the like, and the time until the fluidity disappeared was measured.

(glass transition point, Tg)

A DSC chart was obtained by using a differential scanning calorimeter DSC6220 manufactured by SII Nanotechnologies Co., Ltd., setting a temperature increase rate of 10 ° C / min, and a scanning temperature range of 25 to 300 ° C. Then, the second temperature is further raised under the same conditions, and the glass transition point is obtained from the inflection point of the heat capacity.

(shear adhesion)

The shear adhesion of the hardened steel sheet/steel plate was determined by hardening at 100 ° C for 1 hour in accordance with the method of JIS K 6850.

From the above results, it can be seen that in the case of the present invention, that is, when an aliphatic polyol and β-methylepichlorohydrin are reacted in the presence of a phase transfer catalyst, it is verified that the production can be carried out at a high yield. An aliphatic polyglycidyl ether having a low chlorine content and a small epoxy equivalent, and the resulting resin has good reactivity and adhesion.

On the other hand, in the case where only a metal complex catalyst or a Lewis acid catalyst is used without using a phase transfer catalyst, not only the obtained aliphatic polyglycidyl ether has a high chlorine content ratio but also an epoxy equivalent. When the purity is lowered, the reactivity and the adhesion are lowered. Further, it was also confirmed that the aliphatic polyglycidyl ether obtained in the present invention has higher reactivity and adhesion than the epoxy resin having no methyl group at the β position (Comparative Examples 2 and 3).

Industrial applicability

According to the present invention, it is possible to easily produce a polyglycidyl ether which is suitable for use in an electronic/electric insulating material, has an extremely low chlorine content, and has a small epoxy equivalent, and is therefore highly industrially advantageous.

Claims (5)

A method for producing a polyglycidyl ether, which is carried out at a temperature of from 30 ° C to 100 ° C in the presence of a phase transfer catalyst having a mass of 100 to 100 parts by mass of the polyol represented by the following general formula (I) The bisphenol-propylene oxide addition represented by the following general formula (II) is obtained by reacting 1 to 10.0 equivalent of β-methylepichlorohydrin and 1.0 to 2.0 equivalent of a base of the polyol of the polyol. Ββ-methyl glycidyl ether; In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and m and n each independently represent a number from 1 to 10; ₂ are the same as those in (the I) the general formula R ₁ and R in the formula but R ₁ and R _2. The method for producing a polyglycidyl ether according to the first aspect of the invention, wherein the phase transfer catalyst is at least one compound selected from the group consisting of a quaternary ammonium base and a quaternary ammonium salt. The method for producing a polyglycidyl ether according to the second aspect of the invention, wherein the phase transfer catalyst is at least one compound selected from the group consisting of quaternary ammonium salts. The method for producing a polyglycidyl ether according to claim 2, wherein the phase transfer catalyst is selected from the group consisting of tetramethylammonium chloride, methyltrioctylammonium chloride, methyltriammonium chloride, And at least 1 of benzyltrimethylammonium chloride Kind of compound. The method for producing a polyglycidyl ether according to any one of claims 1 to 4, wherein the polyol, the phase transfer catalyst, and the β-methylepichlorohydrin are placed, and then the base is added.