TWI458717B - Production method of epoxypropyl ether compound and mono allyl monocyclopropyl ether compound - Google Patents

Description

Method for producing glycidyl propyl ether compound and monoallyl monoepoxypropyl ether compound

The present invention relates to a process for producing a glycidyl propyl ether compound and a monoallyl monoepoxypropyl ether compound. More specifically, the present invention relates to the efficient oxidation of a carbon-carbon double bond of the allyl group of a compound having an allyl ether bond by hydrogen peroxide using a predetermined catalyst. A method for producing a epoxidized propyl ether compound characterized by epoxidation, and a method for oxidizing hydrogen peroxide by oxidizing the allyl carbon-carbon double bond of a compound having an allyl ether bond Monoallyl monoepoxypropyl ether compound.

The epoxy propyl ether, which is known as a raw material of an epoxy resin, is industrially produced on a large scale and is widely used in various fields.

The conventional method for producing a glycidyl propyl ether is obtained by reacting an alcohol or a phenol with an epichlorohydrin under alkaline conditions in the presence or absence of a catalyst. Method of propyl ether. In this method, the organochlorine compound is inevitably left, and in some applications, for example, in the use of an electronic motor, there is a disadvantage that the insulating property is lowered.

Therefore, it has also been reviewed that the allyl ether is directly epoxidized by using an oxidizing agent to bond the carbon-carbon double bond of the allyl group. In the following Patent Document 1 (Japanese Patent Publication No. Hei 10-511722) and Patent Document 2 (JP-A-60-60123), it is disclosed that bisphenol-A is a diallyl ether or a novolac type phenol. The polyallyl ether of the resin is epoxidized by hydrogen peroxide in the presence of a quaternary ammonium salt in the organic solvent of toluene or the like using sodium tungstate and a phosphoric acid catalyst. In this method, the amount of the tungsten compound used must be very large, and the epoxidation rate is not sufficient, and it cannot be implemented as an industrial production method.

In the following Patent Document 3 (U.S. Patent No. 5,633,391), it is disclosed that an olefin is brought into contact with bis(trimethyldecyl) peroxide as an oxidizing agent in the presence of a cerium oxide catalyst in an organic solvent. A method of epoxidizing an olefin, but it requires a high-priced catalyst and an oxidizing agent, and when the phenyl allyl ether is produced, the yield is also insufficient.

In the following, the phenol novolak resin is subjected to allyl etherification by halogenated allyl group, as disclosed in Japanese Patent Laid-Open Publication No. Hei. No. Hei. No. Hei. It is a method of epoxidation with a peracid in an organic solvent, and it is necessary to use a high-risk peracid.

Further, the following Patent Document 6 (Japanese Patent Publication No. 2002-526483) discloses that in the presence of a titanium-containing zeolite catalyst, a tertiary amine, a tertiary amine oxide or a mixture thereof, A method in which hydrogen peroxide is epoxidized. This method is useful when a olefin compound having a small molecular weight is used as a matrix. However, when a matrix having a large molecular weight like a phenyl ether has a poor catalyst efficiency, it is not applicable.

[Previous Technical Literature]

[Patent Literature]

[Patent Document 1] Japanese Patent Publication No. 10-511722

[Patent Document 2] Japanese Laid-Open Patent Publication No. 60-60123

[Patent Document 3] US Patent No. 5633391

[Patent Document 4] Japanese Patent Laid-Open No. 7-145221

[Patent Document 5] Japanese Patent Laid-Open Publication No. SHO 58-173118

[Patent Document 6] Japanese Patent Publication No. 2002-526483

The problem to be solved by the present invention is to provide a method for efficiently producing a glycidyl ether compound from a compound having an allyl ether bond using hydrogen peroxide as an oxidizing agent under mild conditions.

There have been no reports of the synthesis of monoallyl monoepoxypropyl ether compounds having a biphenyl skeleton. The monoallyl monoepoxypropyl ether compound can be hydrogenated by reacting with a compound having a Si-H group by having an allyl group, and further can introduce a biphenyl epoxy group to a compound having various Si-H groups. Propyl ether group. For example, in the case of synthesizing an epoxy resin used in a resist or a sealing material, it is hydrogenated by a hydrazine compound having various Si-H groups, and it is considered that the reaction can be simultaneously performed by the first-order reaction. It is extremely useful to introduce a biphenyl skeleton having high heat resistance and high etching resistance and an epoxy group necessary for curing. Therefore, the object of the present invention is to provide a novel monoallyl monoepoxypropyl ether compound having a biphenyl skeleton having high heat resistance and high etching resistance.

The inventors of the present invention have conducted intensive studies and experiments to solve the above problems, and found that by using a tungsten compound, a tertiary organic amine, and a phenylphosphonic acid as a catalyst, an aqueous hydrogen peroxide solution is reacted with an allyl ether compound. Further, the present invention can be completed by efficiently producing a correspondingly epoxidized propyl ether compound.

That is, the present invention is as follows.

[1] A method for producing a glycidyl propyl ether compound, which comprises reacting a compound having an allyl ether bond with hydrogen peroxide, and oxidizing the carbon-carbon double bond of the allyl group to produce a corresponding A method of a glycidyl propyl ether compound characterized by using a tungsten compound, a tertiary amine, and a phenylphosphonic acid as a reaction catalyst.

[2] The method for producing a glycidyl ether compound according to the above [1], wherein the tungsten compound is a partially neutralized salt of tungstic acid.

[3] The method for producing a glycidyl ether compound according to the above [1] or [2] wherein the tungsten compound is a mixture of sodium tungstate and tungstic acid, a mixture of sodium tungstate and mineral acid, or tungstic acid and a mixture of base compounds.

[4] The method for producing a glycidyl ether compound according to any one of the above [1] to [3] wherein the tertiary amine is a trialkylamine, and the carbon number of the alkyl group bonded to the nitrogen atom thereof The total is 6 or more and 50 or less.

[5] The method for producing a glycidyl ether compound according to any one of the above [1] to [4] wherein the compound having an allyl ether bond is a compound having a complex allyl ether bond .

[6] The method for producing a glycidyl ether compound according to any one of the above [1] to [4] wherein the compound having an allyl ether bond is a compound having two allyl ether bonds. Further, there is a step of separating the monoallyl monoepoxypropyl ether compound from which only one of the allyl ether bonds is epoxidized from the reaction product.

[7] The method for producing a glycidyl propyl ether compound according to any one of the above [1] to [6], wherein an organic solvent is not used as a reaction solvent.

[8] The method for producing a glycidyl ether compound according to any one of the above [1] to [7] wherein the compound having an allyl ether bond has the following formula (1):

【化1】

In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a carbon number of 6 to 10 The aryl group or R ¹ and R ² together may form an alkylene group having 2 to 6 carbon atoms or a cycloalkylene group having 3 to 12 carbon atoms. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a carbon number of 6 to An aryl group of 10, and n represents a structure represented by an integer of 0 or 1.

[9] The method for producing a glycidyl ether compound according to any one of the above [1] to [8] wherein the compound having an allyl ether bond is selected from a diallyl group derived from bisphenol-A At least one of a group of ether, bisphenol-F diallyl ether, and 3,3',5,5'-tetramethylbiphenyl-4,4'-diallyl ether.

[10] The method for producing a glycidyl ether compound according to any one of the above [1] to [7] wherein the compound having an allyl ether bond is selected from α, ω having a carbon number of 2 to 20. - a mixture of polyolefin diol diallyl ether, 1,4-cyclohexane dimethanol diallyl ether, and tricyclo [5.2.1.0 ^2,6 ]decane dimethanol diallyl ether At least one.

[11] The method for producing a glycidyl ether compound according to any one of [1] to [7] wherein the compound having an allyl ether bond is a phenol-formaldehyde ‧ allyl alcohol polycondensate or Cresol-formaldehyde ‧ allyl alcohol polycondensate.

[12] A monoallyl monoepoxypropyl ether compound having a biphenyl skeleton, which is represented by the following general formula (2):

[Chemical 2]

In the formula, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or The aryl group having 6 to 10 carbon atoms is represented by.

[13] The monoallyl monoepoxypropyl ether compound having a biphenyl skeleton according to the above [12], wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the formula are a methyl group.

According to the method for producing a glycidyl ether compound of the present invention, by using a tungsten compound, a tertiary organic amine, and a phenylphosphonic acid as a catalyst, hydrogen peroxide can be reacted with an allyl ether compound to produce a corresponding one. A epoxidized propyl ether compound, which is highly resistant to the incorporation of impurities such as organic chlorine, can be manufactured in the field of electronic materials safely and in good yield with low yield, and is widely used in various industrial fields including the chemical industry. An epoxy resin which is a useful material of a raw material of various polymers of an adhesive or a coating resin. Therefore, the production method of the epoxypropyl ether compound of the present invention can produce a huge effect industrially. Further, since the monoallyl monoepoxypropyl ether compound of the present invention has an allyl group, it can be subjected to a hydrazine hydrogenation reaction with a compound having a Si-H group, since a compound having various Si-H groups can be introduced. It is a biphenyl epoxypropyl ether group which is extremely useful as an epoxy resin raw material used for a resist or a sealing material or the like.

Hereinafter, the present invention will be described in detail.

In the method for producing a glycidyl ether compound of the present invention, hydrogen peroxide is used as the oxidizing agent. Hydrogen peroxide can be used as an aqueous hydrogen peroxide solution. The concentration of hydrogen peroxide is not particularly limited, and is usually selected from the range of 1 to 80%, preferably 5 to 80%, more preferably 10 to 60%. From the viewpoint of industrial productivity, and from the viewpoint of energy cost at the time of separation, hydrogen peroxide is preferably at a high concentration, and on the other hand, from the viewpoints of economy, safety, etc., without excessively high concentration and/or Excess amount of hydrogen peroxide is preferred. If the concentration of hydrogen peroxide is less than 1%, the reactivity is low. The amount of hydrogen peroxide used is also not particularly limited, and is preferably from 0.5 to 10 equivalents, preferably from 0.8 to 10 equivalents, based on the allylic carbon-carbon double bond of the allylic ether-bonded compound to be subjected to epoxidation. ~ 2 equivalent range. If it is outside this range, the raw materials of one of them become excessive and uneconomical.

In the method for producing a glycidyl ether compound of the present invention, a tungsten compound used as a catalyst is preferably a compound which forms a tungstate anion in water, and examples thereof include tungstic acid, tungsten trisulfide, and tungsten trisulfide. Hexachlorochloride, phosphotungstic acid, ammonium tungstate, potassium tungstate dihydrate, sodium tungstate dihydrate, etc., and tungstic acid, tungsten trioxide, phosphotungstic acid, sodium tungstate dihydrate, etc. . These tungsten compounds may be used singly or in combination of two or more.

The catalytic activity of such a compound which forms a tungstic anion in water is higher than the relative cation of 0.2 to 0.8 with respect to the tungstic anion 1.0. For the preparation method of the tungsten composition, for example, an alkali metal salt of tungstic acid and tungstic acid can be mixed at the above ratio, and tungstic acid and an alkali compound (hydroxide, carbonate, etc. of an alkali metal or an alkaline earth metal) can be used. Mixing, or by combining an alkali metal salt or an alkaline earth metal salt of tungstic acid with a mineral acid-like acidic compound such as phosphoric acid or sulfuric acid, a partial neutralizing salt of tungstic acid can be formed by the above-mentioned preparation method. Preferred examples of such a compound include a mixture of sodium tungstate and tungstic acid, a mixture of sodium tungstate and mineral acid, or a mixture of tungstic acid and an alkali compound.

The tungsten compound is used as a catalyst. The tungsten element is selected from the group consisting of 0.0001 to 20 mol% based on the number of carbon-carbon double bonds of the allyl group of the compound having an allyl ether bond. Preferably, it is in the range of 0.01 to 20 mol%. If it is less than 0.0001% by mole, the reactivity is low, and if it is more than 20% by mole, it is disadvantageous to cost.

The tertiary amine used as a catalyst has a total carbon number of 6 or more, preferably 10 or more organic amines (trialkylamine), which is bonded to the nitrogen atom of the nitrogen atom, due to epoxidation reaction. The activity is high and is preferred.

Examples of the tertiary organic amines include triethylamine, tributylamine, tri-n-octylamine, tris-(2-ethylhexyl)amine, N,N-dimethyloctylamine, N,N-Dimethyl laurylamine, N,N-dimethyltetradecylamine, N,N-dimethylhexadecanylamine, N,N-dimethyloctadecylamine, N , N-dimethyl behenylamine, N,N-dimethylcocoalkylamine, N,N-dimethyltallow alkylamine, N,N-dimethyl hardened tallow alkylamine, N , N-dimethyloctadecylamine, N,N-diisopropyl-2-ethylhexylamine, N,N-dibutyl-2-ethylhexylamine, N-methyldioctyl Amine, N-methyldidecylamine, N-methyldicocoalkylamine, N-methyl hardened tallow alkylamine, N-methyldecyl octadecylamine, and the like. The total number of alkyl carbon atoms bonded to the nitrogen atom of the tertiary amine is preferably 50 or less, more preferably 30 or less, in consideration of the solubility of the compound having an allyl ether bond as a reaction substrate.

These tertiary amines may be used singly or in combination of two or more. The amount thereof is based on the number of carbon-carbon double bonds of the allyl group of the compound having an allyl ether bond, preferably from 0.0001 to 10 mol%, more preferably 0.01 to 10 mol. The range of ear %. If it is less than 0.0001% by mole, the reactivity is low, and if it is more than 10% by mole, it is disadvantageous in cost.

In the method for producing a glycidyl ether compound of the present invention, phenylphosphonic acid is further used as a (helper) catalyst. It is used in an amount of from 0.0001 to 10 mol%, more preferably from 0.01 to 10 mol%, based on the number of allyl carbon-carbon double bonds of the allyl ether-bonded compound of the matrix. The range of %. If it is less than 0.0001% by mole, the reactivity is low, and if it is more than 10% by mole, it is disadvantageous in cost.

In the method for producing a glycidyl ether compound of the present invention, the substrate to be subjected to epoxidation is not particularly limited as long as it is a compound having an allyl ether bond, and the number of allyl ether bonds contained in the compound may be It can be one or two or more. a compound having one allylic ether linkage number, which may be exemplified by phenyl allyl ether, o-, m-, p-cresol monoallyl ether, biphenyl-2-ol monoallyl ether And biphenyl-4-ol monoallyl ether, butyl allyl ether, cyclohexyl allyl ether, cyclohexane methanol monoallyl ether and the like.

The compound having two groups of allyl ether linkages may, for example, 1,5-pentanediol diallyl ether, 1,6-hexanediol diallyl ether, 1,9-nonanediol II α,ω-alkylene glycol diallyl ether having a carbon number of 2 to 20, such as allyl ether, 1,10-nonanediol diallyl ether, neopentyl glycol diallyl ether α,ω-polyolefin diol diallyl ether, 1,4-cyclohexanedimethanol diallyl ether, tricyclo[5.2.1.0 ^2,6 ]decane II Methanol diallyl ether, or the general formula (1) below:

[化3]

In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, or a carbon number of 6 to 10 The aryl group, or R ¹ and R ² together may form an alkylene group having 2 to 6 carbon atoms or a cycloalkylene group having 3 to 12 carbon atoms. R ³ , R ⁴ , R ⁵ and R ⁶ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a carbon number of 6 to An aryl group of 10, and n represents a compound represented by an integer of 0 or 1. Here, when n is 0, it means that two benzene rings are directly bonded (biphenyl skeleton). Among these, R ¹ to R ⁶ are each independently a hydrogen atom or a methyl group, and n is preferably 1 or 0.

Specific examples of the compound include diallyl ether of bisphenol-A, diallyl ether of bisphenol-F, and 2,6,2',6'-tetramethylbisphenol-A diene. Propyl ether, 2,2'-diallyl bisphenol-A diallyl ether, 2,2'-di-t-butyl bisphenol-A diallyl ether, 4,4'-linked Phenolic diallyl ether, 2,2'-diisopropylbiphenol diallyl ether, 4,4'-ethylene bisphenol diallyl ether, 4,4'-cyclohexylene bisphenol Diallyl ether, 4,4'-(1-α-methylbenzylidene) bisphenol diallyl ether, 4,4'-(3,3,5-trimethylcyclohexylene) double Phenolic diallyl ether, 4,4'-(1-methyl-benzylidene) bisphenol diallyl ether, 3,3',5,5'-tetramethylbiphenyl-4,4 '-Diallyl ether and the like.

Further, the compound having three or more allyl ether linkages may, for example, be a phenol-formaldehyde ‧ allyl alcohol polycondensate or a cresol-formaldehyde ‧ allyl alcohol polycondensate.

These substrates may be used without using an organic solvent, or an organic solvent may be used as needed, and an aqueous solution of hydrogen peroxide may be mixed with the above-mentioned catalyst to carry out an epoxidation reaction, and an epoxidation reaction may be carried out without using an organic solvent, thereby reducing production cost and manufacturing. It is advantageous to simplify the equipment (for example, omission of explosion-proof equipment, etc.), waste disposal, and improvement of the working environment. When a solvent is used, since the reaction rate is slow and the unsatisfactory reaction such as a hydrolysis reaction depending on the solvent is easily carried out, it is necessary to be appropriately selected. When the viscosity of the compound having an allyl ether bond as a reaction substrate is too high, or when it is a solid, the necessary minimum organic solvent can be used. The organic solvent which can be used is preferably an aromatic hydrocarbon, an aliphatic hydrocarbon or an alicyclic hydrocarbon, and examples thereof include toluene, hydrazine, hexane, octane, and cyclohexane. The amount of use thereof is preferably from the viewpoint of the production cost and the like, and is preferably 50 parts by mass or less, more preferably 30 parts, per 100 parts by mass of the compound having an allyl ether bond. Below the mass. When the amount of the organic solvent used is more than 50 parts by mass based on 100 parts by mass of the compound having an allyl ether bond, the substrate concentration is lowered and the reactivity is lowered.

Further, as a method of performing epoxidation, in consideration of industrially stable production, the catalyst and the substrate can be placed in the reactor first, and the reaction temperature is kept at a fixed temperature as much as possible, and it is confirmed that hydrogen peroxide is reacted by the reaction. The situation of consumption, while slowly joining. According to this method, even if hydrogen peroxide is abnormally decomposed in the reactor to generate oxygen gas, the amount of hydrogen peroxide stored is small, and the pressure can be increased to a minimum.

When the reaction temperature is too high, there are many side reactions, and hydrogen peroxide is also easily decomposed. When the temperature is too low, the consumption rate of hydrogen peroxide is slow and accumulated in the reaction system. It is preferably in the range of -10 to 120 ° C, more preferably in the range of 20 ° C to 100 ° C.

After the completion of the reaction, there is almost no difference in the difference in specific gravity between the water layer and the organic layer. At this time, by mixing the aqueous layer with a saturated aqueous solution of the inorganic compound, the specific gravity difference is caused to the organic layer, even if the organic extraction solvent is not used. Two layers of separation are possible. In particular, since the specific gravity of the tungsten compound is heavy, in order to sink the water layer to the lower layer, a tungsten compound exceeding the aforementioned usage amount required for the original catalyst can be used. At this time, it is preferable to further increase the efficiency of the tungsten compound by using the tungsten compound derived from the water layer.

On the other hand, depending on the substrate, the specific gravity of the organic layer may become close to 1.2. At this time, water is further added, and by making the specific gravity of the water layer close to 1, the upper layer may be a water layer, and the lower layer may be organic. Floor. Further, the extraction of the reaction liquid may be carried out by extraction with an organic solvent such as toluene, cyclohexane, hexane or dichloromethane, and the most suitable separation method may be selected depending on the conditions.

After the organic layer separated from the aqueous layer is concentrated in this manner, the obtained epoxy propyl ether compound can be taken out by a usual method such as distillation, chromatography separation, recrystallization or sublimation. When the compound having an allyl ether bond is a compound having two allyl ether bonds, by performing the above separation and purification operation, only one of the allyl ether bonds can be epoxidized from the reaction product. The monoallyl monoepoxypropyl ether compound is isolated. For example, when a diallyl ether compound having a biphenyl skeleton is used as a substrate, the organic layer contains monoallyl monoepoxypropyl ether, diepoxypropyl ether, and unreacted diallyl ether. The compound can be purified from the column chromatography method described in Example 16 to be described later, for example, to obtain the following general formula (2):

【化4】

In the formula, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or Monoallyl monoepoxypropyl ether represented by an aryl group having 6 to 10 carbon atoms. R ⁷ , R ⁸ , R ⁹ and R ¹⁰ may also be a methyl group.

[Examples]

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited by the following examples.

[Example 1]

For a 300 mL three-necked beaker equipped with a dropping funnel and a Dairy condenser, put sodium tungstate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) at 0.950 g (2.88 mmol) and tungstic acid (manufactured by Nippon Inorganic Chemicals Co., Ltd.) 0.720 g (2.88 mmol), trioctylamine (manufactured by Kyoei Chemical Co., Ltd.), 2.04 g (5.76 mmol), phenylphosphonic acid (manufactured by Nissan Chemical Co., Ltd.), 0.911 g (5.76 mmol), allyl phenyl 80 g (0.576 mol) of an ether was stirred with a magnetic stirrer, and after heating to 70 ° C in an oil bath, the reaction temperature was not more than 75 ° C, and 84.0 g (0.864 mol) of a 35% aqueous hydrogen peroxide solution was added dropwise. After the completion of the dropwise addition, stirring was continued for 2 hours, and the reaction liquid was allowed to cool to room temperature. Thereafter, 40 g of ethyl acetate was added to make the upper layer an organic layer and the lower layer a water layer, and the organic layer was separated.

As a result of analyzing the organic layer, the conversion of allyl phenyl ether was 55.8%, and the selectivity to p- propyl propyl ether was 66.3%.

Further, the conversion rate and the selectivity are based on the results of analysis by gas chromatography, and are calculated based on the following calculation formula.

Conversion rate (%) = (1 - residual raw material moles / used raw material moles) × 100

Selection rate (%) = {(mole of target compound / number of raw materials used) × 10000} / conversion rate (%)

[Comparative Example 1]

The reaction was carried out under the same conditions as in Example 1 except that phenylphosphonic acid was not added. As a result, the conversion ratio of allyl phenyl ether was 3.6%, and only a very small amount of epoxypropyl phenyl ether was detected by gas chromatography.

[Comparative Example 2]

The reaction was carried out under the same conditions as in Example 1 except that trioctylamine was not added. As a result, the conversion ratio of allyl phenyl ether was 5.3%, and only a very small amount of epoxypropyl phenyl ether was detected by gas chromatography.

[Examples 2 to 10]

The epoxidation reaction was carried out in the same manner as in Example 1 except that the catalyst components shown in Table 1 below were placed and the molar ratio was placed. The results are shown in Table 1 below.

[Synthesis Example 1]: Synthesis of diallyl ether of bisphenol-F

In a 2000 ml eggplant type beaker, 200 g (0.999 mol) of bisphenol-F-ST (manufactured by Mitsui Chemicals Co., Ltd.) and 50% aqueous 5%-Pd/C-STD type (manufactured by NECHEMCAT Co., Ltd.) of 2.13 g were placed. (0.499 mmol), triphenylphosphine (Beixing Chemical Co., Ltd.) 2.62 g (9.99 mmol), potassium carbonate (made by Asahi Glass Co., Ltd.) 276 g (2.00 mol), allyl acetate (Showa Denko) 220 g (2.20 mol) and 200 g of isopropyl alcohol were reacted at 85 ° C for 8 hours in a nitrogen atmosphere. After the reaction, a part was sampled, diluted with ethyl acetate, and analyzed by gas chromatography to confirm that the ratio of bisphenol-F diallyl ether to monoallyl ether was changed to 99:1.

Thereafter, 400 g of toluene was added to the reaction liquid, and Pd/C and the precipitated solid were removed by filtration, and isopropyl alcohol and toluene were distilled off by an evaporator. After repeating this reaction and the post-treatment operation four times, a distillate of 748 g (66% yield, bisphenol-F diallyl ether) was obtained by a molecular distillation apparatus (manufactured by Daikoku Co., Ltd.). 98.7%, the remaining is monoallyl ether), 368 g of non-distillate (bisphenol-F diallyl ether 88%). These analyses were carried out by gas chromatography. The viscosity of the distillate at 25 ° C was 25 mPa ‧ (measured by a B-type viscometer (DV-E (type: LVDV-E) manufactured by BROOKFIELD). Further, the isomer ratio was o, o'-: o, p'-: p, p'- = 17: 52: 31 (analytical value obtained by gas chromatography).

[Synthesis Example 2]: Synthesis of 3,3',5,5'-tetramethylbiphenyl-4,4'-diallyl ether

For a 2000 ml eggplant type beaker, put 3,3',5,5'-tetramethyl-4,4'-biphenyldiol (China:Gansu Chemical Industry Research Institute) 150g (0.619mol), 50 % water-containing 5%-Pd/C-STD type (manufactured by NECHEMCAT Co., Ltd.) 1.32g (0.310mmol), triphenylphosphine (Beixing Chemical Co., Ltd.) 1.624g (6.19mmol), potassium carbonate (Japan Soda 171 g (1.24 mol), 136 g (1.36 mol) of allyl acetate (manufactured by Showa Denko Co., Ltd.), and 68.1 g of isopropyl alcohol were reacted at 85 ° C for 8 hours in a nitrogen atmosphere. After the reaction, a portion was sampled and diluted with ethyl acetate, and analyzed by gas chromatography to confirm 3,3',5,5'-tetramethylbiphenyl-4,4'-di The ratio of allyl ether to monoallyl ether was changed to 97:3.

Thereafter, 200 g of toluene was added to the reaction liquid, and Pd/C and the precipitated solid were removed by filtration, and isopropyl alcohol and toluene were distilled off by an evaporator. After repeating this reaction and the post-treatment operation four times, 127.5 g of a distillate was obtained by a molecular distillation apparatus (manufactured by Daikoku Co., Ltd.) (the separation yield was 66%, the diallyl ether was 97.9%, and the balance was Monoallyl ether), non-distillate 31.7 g (diallyl ether 97.5%). These analyses were carried out by gas chromatography. The distillate had a melting point of 51.7 ° C solid and a viscosity at 60 ° C of 29 mPa ‧ (measured by a B-type viscometer (DV-E (type: LVDV-E) manufactured by BROOKFIELD).

[Synthesis Example 3]: Synthesis of 1,4-cyclohexanedimethanol diallyl ether

In a 1000 ml beaker, 100 g (0.693 mol) of 1,4-cyclohexanediol (manufactured by Eastman Chemicals), 110.9 g (1.39 mol) of a 50% aqueous sodium hydroxide solution, and tetrabutylammonium bromide (LION AKZO) were placed. 1.12 g (3.47 mmol) and 132.7 g (1.73 mol) of allyl chloride were heated at 40 ° C under a nitrogen stream, and the reaction temperature was gradually increased as the reaction progressed, and the temperature was raised to 70 in 3 hours. After °C, it was further reacted for 17 hours. The reaction solution was cooled to room temperature, and 200 ml of toluene was added thereto to extract the reactant, and the organic layer was washed twice with pure water. After distilling off the toluene by an evaporator, the preliminary fraction was removed by distillation under reduced pressure to obtain a fraction of 84.6 g (diallyl ether 94%, residual monoallyl) having a boiling point of 80.4 ° C / 28 Pa. ether). These analyses were carried out by gas chromatography. Further, the viscosity of the distillate at 25 ° C was 8.5 mPa ‧ (measured by a B-type viscosity meter (DV-E (type: LVDV-E) manufactured by BROOKFIELD).

[Synthesis Example 4]: Synthesis of 1,6-hexanediol diallyl ether

In a 1000 ml beaker, 100 g (0.846 mol) of 1,6-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.), 135.4 g (1.69 mol) of a 50% aqueous sodium hydroxide solution, and tetrabutylammonium bromide (LION AKZO ( 1.36 g (4.23 mmol) and allyl chloride 161.9 g (2.12 mol) were first heated at 40 ° C under a nitrogen stream, and the reaction temperature was gradually increased as the reaction progressed, and the temperature was raised over 2 hours. After 70 ° C, it was further reacted for 10 hours. The reaction solution was cooled to room temperature, and 200 ml of toluene was added thereto to extract the reactant, and the organic layer was washed twice with pure water. After the toluene was distilled off by an evaporator, and the initial fraction was removed by distillation under reduced pressure, 84.6 g of a distillate having a boiling point of 72 ° C / 133 Pa (97% of diallyl ether, remaining monoallyl) was obtained. ether). These analyses were carried out by gas chromatography. Further, the viscosity of the distillate at 25 ° C was 2.3 mPa ‧ (measured by a B-type viscosity meter (DV-E (type: LVDV-E) manufactured by BROOKFIELD).

[Examples 11 to 15]

An epoxidation reaction was carried out in the same manner as in Example 1 except that the allyl phenyl ether of Example 1 was substituted with the compound shown in Table 2 below. The results are shown in Table 2 below.

[Example 16]

The product obtained in Example 13 was isolated from monoepoxypropyl monoallyl ether and identified in the present example. The experimental sequence is as follows.

For a 300 mL three-necked beaker equipped with a dropping funnel and a Dairy condenser, put sodium tungstate (manufactured by Nippon Inorganic Chemical Industry Co., Ltd.) at 0.950 g (2.88 mmol) and tungstic acid (manufactured by Nippon Inorganic Chemicals Co., Ltd.) 0.720 g (2.88 mmol), trioctylamine (manufactured by Kyoei Chemical Co., Ltd.), 2.04 g (5.76 mmol), and phenylphosphonic acid (manufactured by Nissan Chemical Co., Ltd.), 0.911 g (5.76 mmol), 3,3', 92.9 g (0.288 mol) of 5,5'-tetramethylbiphenyl-4,4'-diallyl ether, and stirred with a magnetic stirrer while heating to 70 ° C in an oil bath The temperature was not more than 75 ° C and 84.0 g (0.864 mol) of a 35% aqueous hydrogen peroxide solution was added dropwise. After the completion of the dropwise addition, stirring was continued for 2 hours, and the reaction liquid was cooled to room temperature. Thereafter, 40 g of ethyl acetate was further added to make the upper layer an organic layer and the lower layer an aqueous layer, and the organic layer was separated.

As a result of analysis of the organic layer, the conversion of 3,3',5,5'-tetramethylbiphenyl-4,4'-diallyl ether was 54.2%, and the selectivity of the monoepoxide was selected. It was 64.9%, and the selectivity to the diepoxide was 15.5% (refer to Example 13 and Table 2).

Thereafter, the organic layer was washed with an aqueous solution of sodium sulfite, and the solvent of the organic layer was distilled off and dried using an evaporator and a vacuum pump to obtain a crude reaction product, which was then purified by column chromatography (cerium oxide gel). 60N (spherical, neutral): manufactured by Kanto Chemical Co., Ltd.; hexane: ethyl acetate = 10:1 to 3:1), and 3,3',5,5'-tetramethylbiphenyl -4,4'-diglycidyl ether and 3,3',5,5'-tetramethylbiphenyl-4,4'-monoallyl monoepoxypropyl ether. From the results of NMR ( ¹ H, ¹³ C) and mass analysis (MS) of the obtained product, it was confirmed that the obtained product was 3,3',5,5'-tetramethylbiphenyl-4,4' Di-epoxypropyl ether and 3,3',5,5'-tetramethylbiphenyl-4,4'-monoallyl monoepoxypropyl ether. The measurement results of the monoallyl monoepoxypropyl ether body are shown in Figs.

The measurement conditions of MS are as follows:

Device: JEOL JMS-SX102A

Sample heating temperature: 80 ° C → [32 ° C / min] → 400 ° C

Sample concentration: The NMR measurement solution was diluted 10 times with dichloromethane.

Sample amount: 0.5 μl* heated at 80 ° C by solvent evaporation and then introduced into MS

Ionization method: EI (electronic ionization method)

Scanning range: m/z10～800

[Example 17]

0.1 g (0.30 mmol), 1,1,1 of the monoallyl monoepoxypropyl ether body synthesized in Example 16 was added to a 50 ml three-neck beaker equipped with a reflux cooler, a thermometer, a stirring device and a rubber cap. 0.077 g (0.35 mmol) of 3,5,5,5-heptamethyltrioxane and 1 ml of toluene were stirred at room temperature under a stream of argon. To the mixed solution, 0.002 g of a solution of 3% diethylenetetramethyldioxane platinum complex isopropanol (platinum amount: 6.0 × 10 ^-5 g) was added, and the reaction solution was stirred at room temperature. After stirring at room temperature for 6 hours, the toluene solvent was removed under reduced pressure to give 0.13 g of crude material. Thereafter, it was purified by column chromatography (cerium oxide gel 60 N (spherical, neutral): manufactured by Kanto Chemical Co., Ltd.; toluene: ethyl acetate = 10:1) to obtain the following structural formula. (3):

【化5】

The monoepoxypropyl ether shown was 0.13 g. From the results of NMR ( ¹ H, ¹³ C, ²⁹ Si) and mass analysis (MS) of the obtained product, the obtained product was determined to be a compound of the formula (3) (see FIGS. 4 to 7). Namely, it shows that the monoallyl monoepoxypropyl ether compound synthesized in Example 16 can be reacted with a compound having a Si-H group by a hydrogenation reaction of hydrazine.

The measurement conditions of MS are as follows:

Device: JEOL JMS-SX102A

Sample heating temperature: 80 ° C → [32 ° C / min] → 400 ° C

Sample concentration: The NMR measurement solution was diluted 10 times with dichloromethane.

Sample amount: 0.5 μl* heated at 80 ° C by solvent evaporation and then introduced into MS

Ionization method: EI (electronic ionization method)

Scanning range: m/z10～800

[Industrial availability]

According to the method for producing a glycidyl ether compound of the present invention, by using a tungsten compound, a tertiary organic amine, and a phenylphosphonic acid as a catalyst, hydrogen peroxide can be reacted with an allyl ether compound to produce a corresponding one. A epoxidized propyl ether compound, which is highly resistant to the incorporation of impurities such as organic chlorine, can be manufactured in the field of electronic materials safely and in good yield with low yield, and is widely used in various industrial fields including the chemical industry. An epoxy resin which is a useful material of a raw material of various polymers of an adhesive or a coating resin. Further, the monoallyl monoepoxypropyl ether compound of the present invention is subjected to a hydrazine hydrogenation reaction with a compound having a Si-H group, since a biphenyl ring can be introduced to a compound having various Si-H groups. An oxypropyl ether group is excellent in the synthesis of an epoxy resin used for a resist or a sealing material for high heat resistance and high etching resistance.

Fig. 1 is a graph showing the results of ¹ H-NMR measurement of the product obtained in Example 16.

Fig. 2 is a graph showing the results of ¹³ C-NMR measurement of the product obtained in Example 16.

Fig. 3 is a graph showing the results of measurement of mass analysis (MS) of the product obtained in Example 16.

Fig. 4 is a graph showing the results of ¹ H-NMR measurement of the product obtained in Example 17.

Fig. 5 is a graph showing the results of ¹³ C-NMR measurement of the product obtained in Example 17.

Fig. 6 is a graph showing the results of ²⁹ Si-NMR measurement of the product obtained in Example 17.

Fig. 7 is a graph showing the results of measurement of mass analysis (MS) of the product obtained in Example 17.

Claims (13)

A method for producing a glycopropyl ether compound, which comprises reacting a compound having an allyl ether bond with hydrogen peroxide, and epoxidizing the carbon-carbon double bond of the allyl group to produce a corresponding epoxy A propyl ether compound characterized by using a tungsten compound, a tertiary amine, and a phenylphosphonic acid as a reaction catalyst. The method for producing a glycidyl ether compound according to claim 1, wherein the tungsten compound is a partially neutralized salt of tungstic acid. The method for producing a glycidyl ether compound according to claim 1 or 2, wherein the tungsten compound is a mixture of sodium tungstate and tungstic acid, a mixture of sodium tungstate and mineral acid, or a mixture of tungstic acid and an alkali compound. The method for producing a glycidyl propyl ether compound according to any one of claims 1 to 3, wherein the tertiary amine is a trialkylamine, and the total number of carbon atoms bonded to the alkyl group of the nitrogen atom is 6 or more. the following. The method for producing a glycidyl ether compound according to any one of claims 1 to 4, wherein the compound having the allyl ether bond is a compound having a complex allyl ether bond. The method for producing a glycidyl ether compound according to any one of claims 1 to 4, wherein the compound having an allyl ether bond is a compound having two allyl ether bonds, and is more self-reactive. The product is a step in which only one of the allyl ether linkages is subjected to an epoxidized monoallyl monoepoxypropyl ether compound. The method for producing a glycidyl propyl ether compound according to any one of claims 1 to 6, wherein an organic solvent is not used as a reaction solvent. The method for producing a glycidyl propyl ether compound according to any one of claims 1 to 7, wherein the compound having an allyl ether bond has the following formula (1): [Chemical 1] In the formula, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or a carbon number of 6 to 10 Or an aryl group, or R ¹ and R ² together may form an alkylene group having 2 to 6 carbon atoms or a cycloalkylene group having 3 to 12 carbon atoms; and R ³ , R ⁴ , R ⁵ and R ⁶ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms or an aryl group having 6 to 10 carbon atoms, and n is an integer of 0 or 1} The structure represented. The method for producing a glycidyl propyl ether compound according to any one of claims 1 to 8, wherein the compound having an allyl ether bond is selected from the group consisting of diallyl ether of bisphenol-A, bisphenol-F At least one of a group consisting of diallyl ether and 3,3',5,5'-tetramethylbiphenyl-4,4'-diallyl ether. The method for producing a glycidyl propyl ether compound according to any one of claims 1 to 7, wherein the compound having an allyl ether bond is selected from the group consisting of α,ω-polyolefin diol having a carbon number of 2 to 20. At least one of a group consisting of allyl ether, 1,4-cyclohexanedimethanol diallyl ether, and tricyclo[5.2.1.0 ^2,6 ]decane dimethanol diallyl ether. The method for producing a glycidyl ether compound according to any one of claims 1 to 7, wherein the compound having an allyl ether bond is a phenol-formaldehyde ‧ allyl alcohol polycondensate or a cresol-formaldehyde ene A propanol polycondensate. A monoallyl monoepoxypropyl ether compound having a biphenyl skeleton, which is a general formula (2) as follows: In the formula, R ⁷ , R ⁸ , R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, a cycloalkyl group having 3 to 10 carbon atoms or The aryl group having 6 to 10 carbon atoms is represented by. A monoallyl monoepoxypropyl ether compound having a biphenyl skeleton according to claim 12, wherein R ⁷ , R ⁸ , R ⁹ and R ¹⁰ in the formula are a methyl group.