KR19980071938A - Preparation method of biphenyl epoxy compound - Google Patents

Abstract

The present invention relates to a biphenyl epoxy compound. In particular, the present invention relates to a method for producing a high purity tetramethyl biphenyl epoxy compound, which is a high purity epoxy compound usable as a semiconductor encapsulant and an electronic material, having a hydrolyzable chlorine content of less than 400 ppm and an epoxy equivalent of 195 or less. A method for producing a phenyl epoxy compound.

Description

Preparation method of biphenyl epoxy compound

The present invention relates to a biphenyl epoxy compound. In particular, the present invention relates to a method for producing a high purity tetramethyl biphenyl epoxy compound, which is a high purity epoxy compound usable as a semiconductor encapsulant and an electronic material, having a hydrolyzable chlorine content of less than 400 ppm and an epoxy equivalent of 195 or less. A method for producing a phenyl epoxy compound.

The method for preparing the tetramethyl biphenyl epoxy compound is based on 3,3 ', 5,5'-tetramethyl 4,4'-biphenol (hereinafter referred to as TBP) and epichlorohydrin (hereinafter referred to as ECH) at the terminal of TBP. The hydroxy group is subjected to epoxidation to prepare 3,3 ', 5,5'-tetramethyl 4,4'-biphenyl diglycidyl ether (hereinafter tetramethyl biphenyl epoxy).

In order to use this tetramethyl biphenyl epoxy compound as an electronic material, it is preferable to prepare an epoxy compound having an epoxy equivalent of 200 or less, hydrolyzable chlorine of less than 400 ppm, and a content of chlorine and sodium ions of 2 ppm or less. In addition, when the epoxy cured product is manufactured using a curing agent, the mechanical strength, chemical resistance, shrinkage resistance and water absorption should be excellent. Looking at the tetramethyl biphenyl epoxy compound, Japanese Unexamined Patent Publication No. 60-67475, Japanese Unexamined Patent Publication No. Hei 2-187420, Japanese Unexamined Patent Publication No. Hei 2-1225, EP 0579301A2, and US 4,072,656, etc. The preparation of epoxy compounds using a phase transfer catalyst (or solvent) in a biphenol / tetramethyl biphenol mixture is disclosed.

The alkaline base used in the epoxidation reaction is a lot of sodium hydroxide and sodium hydroxide aqueous solution. When the sodium hydroxide and sodium hydroxide aqueous solution mentioned in the above prior art is used, the yield is not only lowered but also unreacted end groups are generated. There is a drawback that many ring-opened epoxy groups are present during the reaction. When the ring-opened epoxy group is present in the epoxy compound, many gel-like side reactants are generated by the ring-opened compound, which is attached to the reactor wall or is present in the solution. Gel by-products that cling to the substrate have a problem that they are not easily removed by organic solvents. Sodium hydroxide reacts with epichlorohydrin to produce side reactants such as glycidol, glycerol, 3-chloro 1,2-propanediol and 2-chloro 1,3-propanediol. The water produced during the reaction and water used as other solvents have an azeotropic distillation ratio with epichlorohydrin, so that distilled epichlorohydrin is not always present in the water, and pure epichlorohydrin is not obtained due to other impurities.

By using the method of the present invention to compensate for the above disadvantages and increase the yield to minimize the generation of unreacted epoxy groups, to ensure that the gel-like by-products do not stick to the reactor base wall and to produce a minimum of gel-like by-products Yield could be increased.

In addition, an epoxidation reaction of tetramethyl biphenol and tepichlorohydrin in anhydrous state (or a small amount of water) was carried out to prepare a high purity tetramethyl biphenyl epoxy compound having an epoxy equivalent of 195 or less and hydrolyzable chlorine of less than 400 ppm. It was. In the present invention, the terminal of the TBP is prevented from generating side reactions such as glycidol, glycerol, 3-chloro 1,2-propanediol and 2-chloro 1,3-propanediol, which are generated when using an alkaline base and an alkaline aqueous solution. Distilled ECH has the advantage that it can be reused without refining because it reacts with ECH by converting hydroxy group to hydroxide.

Referring to the present invention in detail, all of the hydroxy groups of 3,3 ', 5,5'-tetramethyl 4,4'-biphenol (hereinafter TBP) are reacted with sodium methoxylated base to give TBP 3,3', 5,5 Convert to '-tetramethyl 4,4'-biphenoxide. A tetrabiphenyl epoxy compound was prepared by subjecting 3,3 ', 5,5'-tetramethyl 4,4'-biphenoxide to the ECH by a continuous addition method and a batch addition method. More specifically, the biphenol oxide methanol solution is prepared by converting the phenol group of TBP to phenoxide using a methanol solution of 1.01 to 1.05 moles of sodium methoxide at 100 parts by weight of TBP at a reaction temperature of 50 to 65 ° C. The biphenoxide methanol solution is added to 380 to 770 parts by weight of ECH, preferably 460 to 640 parts by weight, by continuous feeding method, batch feeding method, or the like for epoxidation reaction. The reaction temperature at this time is 50-65 degreeC. After the epoxidation reaction, methanol and ECH are distilled off by simple distillation and vacuum distillation. After distillation, 250 to 440 parts by weight of toluene is added at about 110 ° C. and kneaded for about 30 minutes.

After cooling the temperature to 90-95 ℃, add 100-200 parts by weight of distilled water and stir for about 30 minutes, and then remove the water by layer separation, 100 parts by weight of distilled water is further put into the reactor to remove impurities and filtered to separate the water. After kneading at 85 ° C. for 1 hour using 25-50 parts by weight of a 3% sodium hydroxide aqueous solution, water is removed. Then, 75-100 parts by weight of 1% aqueous sodium hydroxide aqueous solution is stirred for 1 hour, and water is removed by layer separation. Wash with 50-100 parts by weight of distilled water to remove residual basicity. Toluene is removed by simple distillation and vacuum distillation to give a pale brown epoxy compound. At this time, the equivalent weight of the epoxy compound was 198 or less and the hydrolyzable chlorine was less than 400 ppm, yielding a tetramethyl biphenyl epoxy compound having a yield of 96% or more. The light brown epoxy compound was decolorized using methanol or acetone solvent to obtain a white crystalline epoxy compound. Prepared.

In addition to toluene, xylene, methyl isobutyl ketone, and the like may be used as a solvent of the pale brown epoxy compound obtained after the removal of ECH in the above reaction.

In addition to the advantages of the present invention mentioned above, distilled methanol and ECH can be easily separated and distilled ECH and methanol can be reused without refining. This is due to the fact that the present invention proceeds to the epoxidation reaction in almost anhydrous state, so that little water is generated during the reaction. Methanol is produced when the TBP is converted to biphenoxide using sodium methoxide, and methanol is produced when the TBP is converted to biphenoxide with an alkaline base, and TBP is converted to biphenoxide with an alkaline base. In this case, even a small amount of water may be produced, but this small amount of water is less likely to generate other side reactions.

On the other hand, when the alkaline base is added to the mixture of TBP and ECH and the epoxidation reaction is carried out, since the water and other side reactants are relatively generated according to the present invention, the distilled ECH contains many impurities, so that the distilled ECH is reused. In order to get a financial system.

In addition to using the above-mentioned sodium methoxylated base, TBP is converted to biphenoxide using an aqueous solution of 1.01 to 1.05 moles of alkaline base (sodium hydroxide and potassium hydroxide) for use in the epoxidation reaction. It is also possible to prepare tetramethyl biphenylepoxy compounds having a% or more equivalent, 195 or less and a hydrolyzable chlorine content of 400 ppm or less.

On the other hand, when the methoxide or sodium methoxide methanol solution is added to the mixture of ECH and TBP or the mixture of ECH, TBP and methanol, the epoxy equivalent increases and the yield decreases. This is because the reaction between ECH and sodium methoxide proceeds rapidly, and much of ECH and sodium methoxide are exhausted. Sodium methoxylatide is shorter than the initial number of moles, there are many unreacted groups in which the hydroxyl group of the TBP does not participate in the epoxidation reaction.

The present invention describes the following examples to specifically illustrate the preparation of the tetramethyl biphenyl epoxy compound, but the present invention is not limited thereto.

The physical property measuring method used in the present invention is as follows.

1) Epoxy equivalent (g / eq): JIS K7236

2) Hydrolyzable Chlorine (ppm): NIPPON KAYAKU Method B

(30 min reflux in 1 normal potassium ethanol / dioxane)

3) Sodium ion (ppm): measured by atomic absorption photometer

4) Chlorine ion (ppm): Silver chloride precipitation titration method

[Production Example 1]

1.0 parts of sodium methoxide and 200 parts by weight of methanol were sequentially added to 100 parts by weight of 3,3 ', 5,5'-tetramethyl 4,4'-biphenol (hereinafter referred to as TBP) to obtain a hydroxyl group of biphenol of TBP. All conversion to phenoxide gave 3,3 ', 5,5'-tetramethyl 4,4'-biphenoxide. The reaction temperature was 65 ℃ and the reaction was carried out in a nitrogen atmosphere.

[Production Example 2]

The preparation was carried out in the same manner as in Preparation Example 1, except that 1.02 mol of sodium hydroxide was used instead of 1.02 mol of sodium methoxide in Preparation Example 1.

Example 1

With respect to 100 parts by weight of 3,3 ', 5,5'-tetramethyl 4,4'-biphenol of Preparation Example 1, all of the epichlorohydrin methanol solution was continuously added under a reaction temperature of 65 deg. When the epoxidation reaction is completed, methanol and ECH are simply distilled and distilled under reduced pressure, and then, 370 parts by weight of toluene is added at 110 ° C., cooled to 95 ° C. with stirring for 30 minutes, 100 parts by weight of distilled water is added to the reactor and stirred for 1 hour. Separated by separation. 100 parts by weight of distilled water was added to the reactor again, impurities were removed while passing through a filter, and water was separated. After performing this process once more, water was separated after stirring for 1 hour with 75 parts by weight of 1% aqueous sodium hydroxide solution. To remove residual basicity, the mixture was washed with 75 parts by weight of distilled water. Toluene was removed by simple distillation and distillation under reduced pressure to obtain a light brown epoxy compound. This pale brown compound was decolorized using methanol and acetone solution to obtain a white epoxy compound. Physical properties of this compound are shown in Table 1.

Example 2

3,3 ', 5,5'-tetra prepared in Preparation Example 2 instead of 3,3', 5,5'-tetramethyl 4,4'-biphenoxide methanol solution prepared in Preparation Example 1 in Example 1 It carried out similarly to Example 1 except having used the methyl 4,4'-biphenoxide methanol solution.

Physical properties thereof are shown in Table 1.

Comparative Example 1

To 100 parts by weight of 3,3 ', 5,5'-tetramethyl 4,4'-biphenol, 420 parts by weight of ECH, and 140 parts by weight of methanol, 1.05 mol of sodium methoxide was sequentially added at a reaction temperature of 65 deg. The reaction was carried out. After the epoxidation reaction was completed, methanol and ECH were removed, and 370 parts by weight of toluene at 110 ° C. were placed in a reactor and stirred for 30 minutes. 100 parts by weight of distilled water was added to the reactor at 95 ° C. and stirred for 30 minutes to remove water by layer separation. Thereafter, the process was performed in the same manner as in Example 1 to perform 3,3 ′, 5,5′-tetramethyl 4, 4'-biphenyl epoxy compound was prepared. Physical properties thereof are shown in Table 1.

Fertilizer Example 2

A 3,3 ', 5,5'-tetramethyl 4,4'-biphenyl epoxy compound was prepared in the same manner as in Comparative Example 1 except that 1.05 mol of sodium hydroxide was used instead of sodium methoxide in Comparative Example 1. Physical properties thereof are shown in Table 1.

Comparative Example 3

In Example 1, 420 parts by weight of ECH was sequentially added to 3,3 ', 5,5'-tetramethyl 4,4'-biphenoxide methanol solution prepared in Preparation Example 1, in the same manner as in Example 1. Carried out. Physical properties thereof are shown in Table 1.

[Comparative Example 4]

In Example 2, 420 parts by weight of ECH was sequentially added to 3,3 ', 5,5'-tetramethyl 4,4'-biphenoxide methanol solution prepared in Preparation Example 1, in the same manner as in Example 2. Carried out. Physical properties thereof are shown in Table 1.

TABLE 1

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Decolorization After bleaching Decolorization After bleaching Decolorization After bleaching Decolorization After bleaching Decolorization After bleaching Decolorization After bleaching Equivalent (g / eq) 198 190 197 191 220 209 230 211 210 198 215 197 Hydrolyzable Chlorine (ppm) 320 180 370 220 400 190 480 320 360 210 410 220 Sodium ions (ppm) 15 1.0 2.0 1.0 2.1 1.0 3.5 1.0 2.5 1.0 1.5 1.0 Chlorine Ion (ppm) 15 1.0 1.5 1.0 3.2 1.0 3.0 1.0 3.0 1.0 3.0 1.0 yield(%) 96 95 95.7 94 85 78 86 81 87 85 86 84

Claims (5)

3,3 ', 5,5 by adding 1.01 to 1.05 moles of a basic compound to 100 parts by weight of 3,3', 5,5'-tetramethyl-4,4'-biphenol and 380 to 770 parts by weight of epichlorohydrin A process for producing a biphenyl epoxy, comprising producing a '-tetramethyl-4,4'-biphenyl epoxy compound. a) 3,3 ', 5,5'-tetramethyl using a basic compound in 100 parts by weight of 3,3', 5,5'-tetramethyl-4,4'-biphenol at a reaction temperature of 50 to 65 ° C. Preparing a 4,4'-biphenoxide methanol solution, b) adding 380 to 770 parts by weight of epichlorohydrin to the biphenoxide methanol solution, and c) epoxidation reaction. And distilling epichlorohydrin. The method of claim 2, further comprising d) dissolving the reaction product in an organic solvent and washing with distilled water, e) washing with water after adding an aqueous sodium hydroxide solution, and f) distilling toluene off. Epoxy Resin Manufacturing Method. The method for producing a biphenyl epoxy resin according to claim 2, wherein the basic compound is sodium methoxide, sodium methoxide methanol solution, sodium hydroxide, or sodium hydroxide. The method for producing a biphenyl epoxy resin according to claim 3, wherein the organic solvent is toluene, xylene, or methyl isobutyl ketone.