KR20120096552A - Process for production of glycidyl ether compounds, and monoallyl monoglycidyl ether compound - Google Patents

Abstract

The present invention provides a method for efficiently preparing a corresponding glycidyl ether compound from a compound having allyl ether bonds using hydrogen peroxide as an oxidizing agent under mild conditions, and a novel monoallyl monoglycidyl ether compound having a biphenyl skeleton. do.
According to the present invention, in the method for producing a corresponding glycidyl ether compound by reacting a compound having an allyl ether bond with hydrogen peroxide to epoxidize a carbon-carbon double bond of the allyl group, a tungsten compound, 3 Provided are a method for producing the glycidyl ether compound, and a monoallyl monoglycidyl ether compound having a biphenyl skeleton obtainable by the production method, characterized by using a tertiary amine and phenylphosphonic acid.

Description

Production method and monoallyl monoglycidyl ether compound of a glycidyl ether compound {PROCESS FOR PRODUCTION OF GLYCIDYL ETHER COMPOUNDS, AND MONOALLYL MONOGLYCIDYL ETHER COMPOUND}

The present invention relates to a method for producing a glycidyl ether compound and a monoallyl monoglycidyl ether compound. More specifically, the present invention provides a glycidyl ether compound characterized in that, by using a predetermined catalyst, the carbon-carbon double bond of the allyl group of the compound having an allyl ether bond is oxidized efficiently with hydrogen peroxide to epoxidize it efficiently. And a monoallyl monoglycidyl ether compound produced by oxidation of hydrogen-peroxide of a carbon-carbon double bond of the allyl group of a compound having an allyl ether bond.

Glycidyl ether, which is known as a raw material for epoxy resins, is industrially produced on a large scale and widely used in various fields.

Conventionally known methods for producing glycidyl ether include a method of obtaining glycidyl ether by reacting a corresponding alcohol or phenol with epichlorohydrin under basic conditions in the presence or absence of a catalyst. In this method, there is a drawback that the organic chlorine compound always remains and the insulating property is lowered for use in some applications, for example, electronics.

Therefore, the direct epoxidation of the carbon-carbon double bond of the allyl group using an allyl ether using an oxidizing agent has also been studied. In the following Patent Document 1 (Japanese Patent Laid-Open No. 10-511722) and Patent Document 2 (Japanese Patent Laid-Open No. 60-60123), diallyl ethers of bisphenol-A and polyallyl ethers of novolac-type phenol resins are used. A method of epoxidation with hydrogen peroxide in an organic solvent such as toluene using sodium tungstate and a phosphate catalyst in the presence of a quaternary ammonium salt is disclosed. This method requires a very large amount of tungsten compound, and the epoxidation rate is not sufficient, which cannot be used as an industrial production method.

The following Patent Document 3 (US Patent No. 5633391) discloses a method of epoxidizing an olefin by bringing the olefin into contact with bis (trimethylsilyl) peroxide as an oxidizing agent in the presence of a rhenium oxide catalyst in an organic solvent. However, In the case of phenyl allyl ether, the yield is not sufficient.

In the following Patent Documents 4 (Japanese Patent Laid-Open No. 7-145221) and Patent Document 5 (Japanese Patent Laid-Open No. 58-173118), phenol novolak resins are allyl-etherylated by halogenated allyl and then subjected to peracid in an organic solvent. Although the method of epoxidizing is disclosed, it is necessary to use high risk peracid.

Further, Patent Document 6 (Japanese Laid-Open Patent Publication No. 2002-526483) discloses a method of epoxidation with hydrogen peroxide in the presence of a titanium-containing zeolite catalyst and a tertiary amine, tertiary amine oxide or a mixture thereof. This method is useful when a low molecular weight olefin compound is used as a substrate, but the catalyst efficiency is poor in a large molecular weight substrate such as phenyl ether and thus cannot be applied.

Japanese Patent Publication Hei 10-511722 Japanese Patent Laid-Open No. 60-60123 United States Patent No. 5633391 Japanese Patent Laid-Open No. 7-145221 Japanese Patent Laid-Open No. 58-173118 Japanese Patent Publication 2002-526483

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

No examples of synthesizing monoallyl monoglycidyl ether compounds having a biphenyl backbone have been reported. Since the monoallyl monoglycidyl ether compound has an allyl group, it can be hydrosilylation-reacted with the compound which has Si-H group, and a biphenylglycidyl ether group can be introduce | transduced into the compound which has various Si-H groups. For example, when synthesizing an epoxy resin for use in resists, sealants, and the like, by hydrosilylation with a siloxane compound having various Si-H groups, the biphenyl skeleton having high heat resistance and etching resistance and curing by one step reaction is hardened. It is thought that the epoxy group required for the reaction can be introduced at the same time, which is very useful. Accordingly, an object of the present invention is to provide a novel monoallyl monoglycidyl ether compound having a biphenyl skeleton having high heat resistance and etching resistance.

MEANS TO SOLVE THE PROBLEM As a result of earnest research and experiment in order to solve the said subject, as a result, the corresponding glycidyl ether was made by making a hydrogen peroxide aqueous solution and an allyl ether compound react using tungsten compound, tertiary organic amine, and phenylphosphonic acid as a catalyst. The discovery that the compounds are selectively produced with high efficiency has led to the completion of the present invention.

That is, this invention is as follows.

[1] A method of producing a corresponding glycidyl ether compound by epoxidizing a carbon-carbon double bond of the allyl group by reacting a compound having an allyl ether bond with hydrogen peroxide, wherein the reaction catalyst is a tungsten compound or a tertiary amine , And phenylphosphonic acid are used. The method for producing the glycidyl ether compound.

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

[3] The glycidyl ether 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 a mixture of tungstic acid and alkali compound. Method of Preparation of the Compound.

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

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

[6] The compound having an allyl ether bond is a compound having two allyl ether bonds, and further has a step of isolating a monoallyl monoglycidyl ether compound of which only one allyl ether bond is epoxidized from the reaction product. The manufacturing method of the glycidyl ether compound in any one of [1]-[4].

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

[8] The compound having the allyl ether bond is represented by the following formula (1):

[In formula, R <^1> and R <^2> is respectively independently a hydrogen atom, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C3-C12 cycloalkyl group, or a C6-C10 aryl group, or R ¹ and R ² may form a C2-C6 alkylidene group or a C3-C12 cycloalkylidene group together. 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 represents an integer of 0 or 1]. The manufacturing method of the glycidyl ether compound in any one of said [1]-[7] which has a structure shown by these.

[9] Compounds having an allyl ether bond include diallyl ethers of bisphenol-A, diallyl ethers of bisphenol-F, and 3,3 ', 5,5'-tetramethylbiphenyl-4,4'-diallyl The manufacturing method of the glycidyl ether compound in any one of said [1]-[8] which is at least 1 sort (s) chosen from the group which consists of ethers.

[10] The compound having an allyl ether bond is selected from α, ω-polyalkylene glycol diallyl ether having 2 to 20 carbon atoms, 1,4-cyclohexanedimethanol diallyl ether, and tricyclo [5.2.1.0 ^2,6 ] The manufacturing method of the glycidyl ether compound in any one of said [1]-[7] which is at least 1 sort (s) chosen from the group which consists of decandimethanol diallyl ether.

[11] The 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 a cresol-formaldehyde allyl alcohol polycondensate. Manufacturing method.

[12] The following general formula (2):

[In formula, R <^7> , R <^8> , R <^9> and R <^10> are respectively independently a hydrogen atom, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C3-C10 cycloalkyl group, or a C6-C10 Aryl group.] Monoallyl monoglycidyl ether compound having a biphenyl skeleton represented by.

[13] A monoallyl monoglycidyl ether compound having a biphenyl skeleton according to the above [12], wherein R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are methyl groups.

(Effects of the Invention)

According to the method for producing a glycidyl ether compound of the present invention, a corresponding glycidyl ether compound can be produced by reacting hydrogen peroxide and allyl ether compound using a tungsten compound, a tertiary organic amine, and phenylphosphonic acid as a catalyst. Epoxy resin, a useful material widely used in various industries such as chemical industry as raw material of various polymers such as electronic materials, adhesives, paint resins, etc. It can be produced with good yield and low cost. Therefore, the manufacturing method of the glycidyl ether compound of this invention brings about industrially huge effect. Moreover, since the monoallyl monoglycidyl ether compound which concerns on this invention has an allyl group, it can carry out hydrosilylation reaction with the compound which has a Si-H group, and the biphenyl glycidyl ether is carried out to the compound which has various Si-H groups. Since a group can be introduce | transduced, it is very useful as an epoxy resin raw material used for resists, sealing materials, etc.

1 shows the measurement results of ¹ H-NMR of the product obtained in Example 16. FIG.
Fig. 2 shows the measurement results of ¹³ C-NMR of the product obtained in Example 16.
3 shows the results of measurement of mass spectrometry (MS) of the product obtained in Example 16. FIG.
4 shows the results of measurement of ¹ H-NMR of the product obtained in Example 17. FIG.
Fig. 5 shows the measurement results of ¹³ C-NMR of the product obtained in Example 17.
6 shows the measurement results of ²⁹ Si-NMR of the product obtained in Example 17. FIG.
7 shows the results of measurement of mass spectrometry (MS) of the product obtained in Example 17. FIG.

Hereinafter, the present invention will be described in detail.

In the manufacturing method of the glycidyl ether compound of this invention, hydrogen peroxide is used as an oxidizing agent. Hydrogen peroxide can be used as an aqueous hydrogen peroxide solution. The concentration of hydrogen peroxide is not particularly limited, but is generally selected from the range of 1 to 80%, preferably 5 to 80%, and more preferably 10 to 60%. Higher concentrations of hydrogen peroxide are preferable from the viewpoint of industrial productivity and energy cost at separation, but on the other hand, it is preferable from the viewpoint of economic efficiency and safety to use excessively high concentration and / or excess hydrogen peroxide. . If the concentration of hydrogen peroxide is less than 1%, the reactivity is low. Although there is no restriction | limiting in particular also about the usage-amount of hydrogen peroxide, It selects from 0.5-10 equivalent, Preferably it is 0.8-2 equivalent with respect to the carbon-carbon double bond of the allyl group of the compound which has the allyl ether bond to epoxidize. Outside this range, one raw material remains in excess and is not economical.

As a tungsten compound used as a catalyst in the manufacturing method of the glycidyl ether compound of this invention, the compound which produces a tungstate anion in water is preferable, For example, tungstic acid, tungsten trioxide, tungsten trisulfide, tungsten hexachloride. Phosphotungstic acid, ammonium tungstate, potassium tungstate dihydrate, sodium tungstate dihydrate and the like, but tungstic acid, tungsten trioxide, phosphotungstic acid, sodium tungstate dihydrate and the like are preferable. These tungsten compounds may be used independently and may mix and use 2 or more types.

The catalytic activity of the compound which produces | generates a tungstic acid anion in these waters is higher in the counter cation of 0.2-0.8 with respect to tungstic acid anion 1.0. As a preparation method of such a tungsten composition, tungstic acid and the alkali metal salt of tungstic acid may be mixed in the said ratio, tungstic acid and an alkali compound (hydroxide, carbonate, etc. of an alkali metal or alkaline earth metal, etc.) may be mixed, or the alkali of tungstic acid may be mixed, for example. Metal salts or alkaline earth metal salts can be combined with acidic compounds such as mineral acids such as phosphoric acid and sulfuric acid, and partial neutralizing salts of tungstic acid can be formed by such preparation. As these preferable specific examples, the mixture of sodium tungstate and tungstic acid, the mixture of sodium tungstate and mineral acid, or the mixture of tungstic acid and an alkali compound is mentioned.

The amount of the tungsten compound used as a catalyst is selected from the range of 0.0001 to 20 mol%, preferably 0.01 to 20 mol%, based on the number of carbon-carbon double bonds of the allyl group of the compound having the allylether bond of the substrate as the tungsten element. Less than 0.0001 mol% is low in reactivity, while more than 20 mol% is economically disadvantageous.

As a tertiary amine used as a catalyst, the sum total of carbon number of the alkyl group couple | bonded with the nitrogen atom is 6 or more, Preferably, 10 or more tertiary organic amine (trialkylamine) is preferable because of the high activity of an epoxidation reaction.

Such tertiary organic amines include triethylamine, tributylamine, tri-n-octylamine, tri- (2-ethylhexyl) amine, N, N-dimethyloctylamine, N, N-dimethyllaurylamine, N, N-dimethylmyristylamine, N, N-dimethylpalmitylamine, N, N-dimethylstearylamine, N, N-dimethylbehenylamine, N, N-dimethylcocoalkylamine, N, N-dimethyl tallow ( Iii) alkylamine, N, N-dimethyl cured tallow alkylamine, N, N-dimethyloleylamine, N, N-diisopropyl-2-ethylhexylamine, N, N-dibutyl-2-ethylhexylamine , N-methyldioctylamine, N-methyldidecylamine, N-methyldicoalkylalkylamine, N-methyl cured tallow alkylamine, N-methyldioleylamine, etc. are mentioned. The total number of carbon atoms of the alkyl group 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 alone or in combination of two or more thereof. The amount is preferably 0.0001-10 mol%, more preferably 0.01-10 mol%, based on the number of carbon-carbon double bonds of the allyl group of the compound having an allylether bond of the substrate. Less than 0.0001 mol% is low in reactivity, while more than 10 mol% is economically disadvantageous.

In the method for producing a glycidyl ether compound of the present invention, phenylphosphonic acid is further used as the (auxiliary) catalyst. The amount is preferably 0.0001-10 mol%, more preferably 0.01-10 mol%, based on the number of carbon-carbon double bonds of the allyl group of the compound having an allylether bond of the substrate. Less than 0.0001 mol% is low in reactivity, while more than 10 mol% is economically disadvantageous.

There is no restriction | limiting in particular as a board | substrate which epoxidizes in the manufacturing method of the glycidyl ether compound of this invention as long as it is a compound which has an allyl ether bond, The number of allyl ether bonds contained in a compound may be one, or two or more may be sufficient as it. good. Examples of the compound having one allyl ether bond include phenyl allyl ether, o-, m-, p-cresol monoallyl ether, biphenyl-2-ol monoallyl ether, biphenyl-4-ol monoallyl ether, butyl allyl ether, and cyclo Hexyl allyl ether, cyclohexanemethanol monoallyl ether, etc. can be illustrated.

Examples of the compound having two allyl ether bonds include 1,5-pentanediol diallyl ether, 1,6-hexanediol diallyl ether, 1,9-nonanediol diallyl ether, 1,10-decanediol diallyl ether, and neopentyl. C2-C20 alpha, omega-alkylene diol diallyl ethers, such as glycoldiallyl ether, C2-C20 alpha, omega- polyalkylene glycol diallyl ether, and 1, 4- cyclohexane dimethanol Diallyl ether, tricyclo [5.2.1.0 ^2,6 ] decanedimethanol diallyl ether, and the following general formula (1):

[In formula, R <^1> and R <^2> is a hydrogen atom, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C3-C12 cycloalkyl group, or a C6-C10 aryl group each independently, or R <^1> and R <^2> may form a C2-C6 alkylidene group or a C3-C12 cycloalkylidene group together. 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 represents an integer of 0 or 1]. Here, when n is 0, it shows that two benzene rings are directly bonded (biphenyl skeleton). Among these, R <^1> -R <^6> is respectively independently a hydrogen atom or a methyl group, and it is more preferable that n is 1 or 0.

Specific examples of such compounds include diallyl ethers of bisphenol-A, diallyl ethers of bisphenol-F, 2,6,2 ', 6'-tetramethylbisphenol-A diallyl ether, and 2,2'-diallyl bisphenol- A diallyl ether, 2,2'-di-t-butylbisphenol-A diallyl ether, 4,4'-biphenoldiallyl ether, 2,2'-diisopropylbiphenoldiallyl ether, 4,4 '-Ethylidenebisphenoldiallyl ether, 4,4'-cyclohexylidenebisphenoldiallyl ether, 4,4'-(1-α-methylbenzylidene) bisphenoldiallyl ether, 4,4 '-(3, 3,5-trimethylcyclohexylidene) bisphenoldiallyl ether, 4,4 '-(1-methyl-benzylidene) bisphenoldiallyl ether, 3,3', 5,5'-tetramethylbiphenyl-4, 4'- diallyl ether, etc. are mentioned.

Examples of the compound having three or more allyl ether bonds include phenol-formaldehyde-allyl alcohol polycondensates, cresol-formaldehyde-allyl alcohol polycondensates, and the like.

These substrates can be subjected to an epoxidation reaction by not using an organic solvent or by mixing an aqueous solution of hydrogen peroxide with the catalyst described above using an organic solvent, if necessary, and carrying out an epoxidation reaction without using an organic solvent. It is advantageous in terms of reduction, simplification of manufacturing equipment (e.g., elimination of explosion-proof equipment, etc.), waste disposal, and improvement of working environment. When using a solvent, since reaction rate becomes slow and undesirable reactions, such as a hydrolysis reaction, may advance easily depending on a solvent, it is necessary to select suitably. When the viscosity of the compound having an allyl ether bond as the reaction substrate is too high or when it is a solid, the minimum organic solvent required may be used. As an organic solvent which can be used, an aromatic hydrocarbon, an aliphatic hydrocarbon, or an alicyclic hydrocarbon is preferable, For example, toluene, xylene, hexane, octane, cyclohexane, etc. are mentioned. The amount to be used to be fixed to the minimum required is advantageous in terms of production cost and the like, and is preferably used in an amount of 50 parts by mass or less, more preferably 30 parts by mass or less, based on 100 parts by mass of the compound having an allyl ether bond. When the usage-amount of an organic solvent exceeds 50 mass parts with respect to 100 mass parts of compounds which have an allyl ether bond, substrate concentration will become low and reactivity will fall.

In addition, as a method of epoxidation, when producing industrially and stably, the catalyst and the substrate are first introduced into the reactor, and the reaction temperature is kept as constant as possible, while hydrogen peroxide is gradually added while confirming that the reaction is consumed. I like it. By adopting this method, even if oxygen gas is abnormally decomposed in the reactor and oxygen gas is generated, the accumulation of hydrogen peroxide is small and the pressure rise can be minimized.

If the reaction temperature is too high, side reactions increase and hydrogen peroxide is also easily decomposed. If the reaction temperature is too low, the consumption rate of hydrogen peroxide is slowed and accumulates in the reaction system, so the reaction temperature is preferably -10 to 120 ° C, more preferably. It selects in the range of 20 degreeC-100 degreeC.

After completion of the reaction, there may be little difference in specific gravity between the aqueous layer and the organic layer. In this case, two-layer separation can be performed without using an organic extraction solvent by mixing a saturated aqueous solution of an inorganic compound with the organic layer to give a specific gravity difference. . In particular, the specific gravity of the tungsten compound is heavy, and in order to bring the aqueous layer to the lower layer, a tungsten compound exceeding the above-mentioned amount used as a catalyst originally may be used. In this case, it is preferable to reuse the tungsten compound from the water layer to increase the efficiency of the tungsten compound.

On the contrary, since the specific gravity of the organic layer may be close to 1.2 depending on the substrate, in this case, the organic layer may be brought to the upper layer and the lower layer by adding water to make the specific gravity of the aqueous layer close to one. In addition, the extraction may be performed using an organic solvent such as toluene, cyclohexane, hexane, methylene chloride or the like for extraction of the reaction solution, and an optimum separation method may be selected depending on the situation.

Thus, the obtained glycidyl ether compound can be taken out by the usual method, such as distillation, chromatographic separation, recrystallization, and sublimation, after concentration of the organic layer separated from the aqueous layer. When the compound having an allyl ether bond is a compound having two allyl ether bonds, the above separation and purification operation can be used to isolate a monoallyl monoglycidyl ether compound of which only one allyl ether bond is epoxidized from the reaction product. have. For example, when the diallyl ether compound having a biphenyl skeleton is used as a substrate, the organic layer includes a monoallyl monoglycidyl ether, a diglycidyl ether, and an unreacted diallyl ether compound. By purification such as column chromatography described in Example 16, for example, the following general formula (2):

[In formula, R <^7> , R <^8> , R <^9> and R <^10> are respectively independently a hydrogen atom, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C3-C10 cycloalkyl group, or a C6-C10 Aryl group] can be obtained monoallyl monoglycidyl ether. R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ may be methyl groups.

[Example]

Hereinafter, although an Example demonstrates this invention further more concretely, this invention is not limited to a following example.

Example 1

In a 300 mL three-necked flask equipped with a dropping funnel and a dimross cooling tube, sodium tungstate [manufactured by Nihon Muki Kagaku Kogyo Co., Ltd.] 0.950 g (2.88 mmol), tungstic acid [manufactured by Nihon Muki Kagaku Kogyo Co., Ltd.] 0.720 g (2.88 mmol), trioctylamine (manufactured by Koeikagaku Co., Ltd.) 2.04 g (5.76 mmol), phenylphosphonic acid (manufactured by Nissan Kagaku Co., Ltd.) 0.911 g (5.76 mmol), allyl phenyl ether 80 g ( 0.576 mol), warmed to 70 ° C. in an oil bath while stirring with a magnetic stirrer, and then 84.0 g (0.864 mol) of 35% aqueous hydrogen peroxide solution was added dropwise so that the reaction temperature did not exceed 75 ° C. did. After completion of the dropwise addition, stirring was continued for 2 hours, and the reaction solution was cooled to room temperature. Thereafter, 40 g of ethyl acetate was added, and the organic layer was separated by placing an organic layer on the upper layer and a water layer on the lower layer.

As a result of analyzing this organic layer, the conversion rate of allyl phenyl ether was 55.8%, and the selectivity to glycidyl phenyl ether was 66.3%.

In addition, the conversion rate and selectivity were calculated by the following formula based on the result analyzed by gas chromatography.

Conversion rate (%) = (1-number of moles of remaining raw materials / number of moles of raw materials used) x 100

Selectivity (%) = {(moles of target compound / moles of raw material used) x 10000} / conversion (%)

Comparative Example 1

The reaction was carried out under the same conditions as in Example 1 except that no phenylphosphonic acid was added. As a result, the conversion rate of allyl phenyl ether was 3.6%, and only a small amount of glycidyl 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 rate of allyl phenyl ether was 5.3%, and only a small amount of glycidyl phenyl ether was detected by gas chromatography.

Example 2-Example 10

The epoxidation reaction was performed like Example 1 with the catalyst component and addition molar ratio shown in the following Table 1. The results are also shown in Table 1 below.

Synthesis Example 1 Synthesis of diallyl ether of bisphenol-F

In a 2000 ml eggplant flask, 200 g (0.999 mol) of bisphenol-F-ST (manufactured by Mitsui Chemical Co., Ltd.), 50% function 5% -Pd / C-STD type [N.E. CHEMCAT Co., Ltd.] 2.13g (0.499mmol), triphenylphosphine [Hokko Kagaku Co., Ltd.] 2.62g (9.99mmol), potassium carbonate [Asahigarasu Co., Ltd.] 276g (2.00mol), 220 g (2.20 mol) of allyl acetate [made by Showa Denko Co., Ltd.), and 200 g of isopropanol were put, and it was made to react at 85 degreeC in nitrogen atmosphere for 8 hours. After the reaction, the sample was partially sampled, diluted with ethyl acetate and analyzed by gas chromatography to confirm that the ratio of bisphenol-F diallyl ether to monoallyl ether was up to 99: 1.

Thereafter, 400 g of toluene was added to the reaction solution to remove Pd / C and the precipitated solid by filtration, and isopropanol and toluene were distilled off by an evaporator. After repeating this reaction and the post-treatment operation four times, 748 g of distillate (66% of isolation yield, 98.7% of bisphenol-F diallyl ethers) by a molecular distillation apparatus (manufactured by Daika Kogyo Co., Ltd.), Monoallyl ether) and 368 g of a non-eluate (bisphenol-F diallyl ether 88%) were obtained. These analyzes were performed by gas chromatography. The viscosity at 25 degrees C of the effluent was 25 mPa * s {B-type viscometer [The DV-E (model: LVDV-E) made from BROOKFIELD] measured}. In addition, the isomer ratio was o, o '-: o, p'-: p, p '-= 17:52:31 (analytical value by gas chromatography).

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

3,3 ', 5,5'-tetramethyl-4,4'-biphenyldiol (China: Gansu Chemical Institute) 150g (0.619mol), 50% function 5% -Pd / C -STD type [NE CHEMCAT Co., Ltd.] 1.32 g (0.310 mmol), triphenylphosphine [Hokko Kagaku Co., Ltd.] 1.624 g (6.19 mmol), potassium carbonate [Nihon Soda Co., Ltd.] 171 g (1.24 mol), acetic acid 136 g (1.36 mol) of allyl [Showa Denko Co., Ltd.] and 68.1 g of isopropanol were put, and it reacted at 85 degreeC in nitrogen atmosphere for 8 hours. After the reaction, partly sampled, diluted with ethyl acetate and analyzed by gas chromatography, the ratio of 3,3 ', 5,5'-tetramethylbiphenyl-4,4'-diallylether to monoallylether was 97: We confirmed to be three.

Thereafter, 200 g of toluene was added to the reaction solution, Pd / C and the precipitated solid were removed by filtration, and isopropanol and toluene were distilled off by an evaporator. After this reaction and the post-treatment operation were repeated four times, 127.5 g of effluent (66% of isolation yield, 97.9% of diallyl ether, and the other monoallyl ether) by a molecular distillation apparatus (manufactured by Daika Kogyo Co., Ltd.), non-effluent 31.7 g (diallyl ether 97.5%) was obtained. These analyzes were performed by gas chromatography. The effluent was a solid having a melting point of 51.7 ° C., and the viscosity at 60 ° C. was 29 mPa · s {B-type viscometer (DV-E (model: LVDV-E, manufactured by Brookfield))}.

Synthesis Example 3 Synthesis of 1,4-cyclohexanedimethanol diallyl ether

100 g (0.693 mol) of 1,4-cyclohexanediol (made by Eastman Chemical), 110.9 g (1.39 mol) of 50% aqueous sodium hydroxide solution, and tetrabutylammonium bromide (manufactured by Lion Arc Co., Ltd.) in a 1000 ml flask 3.47 mmol) and 132.7 g (1.73 mol) of allyl chloride were added, and the mixture was first heated at 40 ° C. under a nitrogen stream, and gradually heated up to 70 ° C. over 3 hours with the progress of the reaction. The reaction was further time. The reaction solution was cooled to room temperature, 200 ml of toluene was added to extract the reactant, and the organic layer was washed twice with pure water. After distilling and removing toluene by the evaporator, 84.6 g (diallyl ether 94% and the remainder monoallyl ether) of the distillate of boiling point 80.4 degreeC / 28Pa were obtained after removing supernatant by vacuum distillation. These analyzes were performed by gas chromatography. In addition, the viscosity at 25 degrees C of the effluent was 8.5 mPa * s (B-type viscometer [BOOKFIELD DV-E (model: LVDV-E)]}.

Synthesis Example 4 Synthesis of 1,6-hexanediol diallyl ether

100 g (0.846 mol) of 1,6-hexanediol (manufactured by Tokyo Kasei Co., Ltd.), 135.4 g (1.69 mol) of 50% aqueous sodium hydroxide solution, tetrabutylammonium bromide [manufactured by Lion Arc Co., Ltd.] 1.36 in a 1000 ml flask. g (4.23 mmol) and 161.9 g (2.12 mol) of allyl chloride were added, and the mixture was first heated at 40 ° C under a nitrogen stream, and the reaction temperature was gradually increased with the progress of the reaction, and the temperature was raised to 70 ° C over 2 hours. The reaction was further carried out for 10 hours. The reaction solution was cooled to room temperature, 200 ml of toluene was added to extract the reactant, and the organic layer was washed twice with pure water. After distilling and removing toluene by the evaporator, 84.6 g (97% of diallyl ether and the remainder of monoallyl ether) of the distillate of boiling point 72 degreeC / 133Pa were obtained after removing supernatant by distillation under reduced pressure. These analyzes were performed by gas chromatography. In addition, the viscosity in 25 degreeC of the distillate was 2.3 mPa * s {measured by the Brookfield viscometer (BOOKFIELD DV-E (model: LVDV-E)]).

[Example 11? Example 15]

The epoxidation reaction was performed like Example 1 except having replaced the allyl phenyl ether of Example 1 with the compound shown in Table 2 below. The results are also shown in Table 2 below.

[Example 16]

Monoglycidyl monoallyl ether was isolated from the product obtained in Example 13, and was identified in this example. The experimental procedure is described below.

In a 300 mL three-necked flask equipped with a dropping funnel and a dimross cooling tube, sodium tungstate [manufactured by Nihon Muki Kagaku Kogyo Co., Ltd.] 0.950 g (2.88 mmol), tungstic acid [manufactured by Nihon Muki Kagaku Kogyo Co., Ltd.] 0.720 g (2.88 mmol), trioctylamine (manufactured by Koeikagaku Co., Ltd.) 2.04 g (5.76 mmol), phenylphosphonic acid (manufactured by Nissan Kagaku Co., Ltd.) 0.911 g (5.76 mmol), 3,3 ', 92.9 g (0.288 mol) of 5,5'-tetramethylbiphenyl-4,4'-diallyl ether was added and heated to 70 DEG C in an oil bath while stirring with a magnetic stirrer, followed by 84.0 g of 35% aqueous hydrogen peroxide solution (0.864). mol) was added dropwise so that the reaction temperature did not exceed 75 ° C. After completion of the dropwise addition, stirring was continued for 2 hours, and the reaction solution was cooled to room temperature. Thereafter, 40 g of ethyl acetate was added, and the organic layer was separated by placing an organic layer on the upper layer and a water layer on the lower layer.

As a result of analyzing the organic layer, the conversion rate of 3,3 ', 5,5'-tetramethylbiphenyl-4,4'-diallyl ether was 54.2%, and the selectivity of monoepoxy was 64.9% and diepoxy. The selectivity of was 15.5% (see Example 13, Table 2).

Thereafter, the organic layer was washed with an aqueous sodium sulfite solution, and the solvent was distilled off and dried using an evaporator and a vacuum pump to obtain a reactant of the crude. Thereafter, column chromatography was purified [silica gel 60N (spherical, Neutral): Kanto-Kagaku, developing solvent; Hexane: ethyl acetate = 10: 1 to 3: 1] to 3,3 ', 5,5'-tetramethylbiphenyl-4,4'-diglycidyl ether and 3,3', 5,5 '-Tetramethylbiphenyl-4,4'-monoallyl monoglycidyl ether was obtained. The product obtained from the results of NMR ( ¹ H, ¹³ C) and mass spectrometry (MS) of the obtained product was 3,3 ', 5,5'-tetramethylbiphenyl-4,4'-diglycidyl ether and 3 It was confirmed that it is, 3 ', 5,5'- tetramethylbiphenyl-4,4'- monoallyl monoglycidyl ether. The measurement result of the monoallyl monoglycidyl ether body is shown in FIGS.

The measurement conditions of MS were as follows:

Device: JEOL JMS-SX102A

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

Sample concentration: 10-fold dilution of NMR solution with dichloromethane

Sample amount: 0.5 μl * Volatilized off by solvent at 80 ° C and introduced into MS

Ionization method: EI (electron ionization method)

Scan Range: m / z10? 800

Example 17

0.1 g (0.30 mmol) of monoallyl monoglycidyl ether body synthesized in Example 16 in a 50 ml three-necked flask equipped with a reflux condenser, thermometer, stirring device, and serum cap, 1,1,1,3,5,5 0.077 g (0.35 mmol) of and 5-heptamethyl trisiloxane, and 1 ml of toluene were added, and it stirred at room temperature under argon stream. 0.002 g (platinum amount: 6.0x10 <^-5> g) of 3% divinyl tetramethyl disiloxane platinum complex isopropyl alcohol solutions were added to this mixed solution, and it stirred at room temperature. After stirring for 6 hours at room temperature, toluene solvent was removed under reduced pressure to obtain 0.13 g of a reactant of crude. Then column chromatography purification [silica gel 60N (spherical, neutral): Kantokagaku Corporation, developing solvent; Toluene: ethyl acetate = 10: 1]

0.13 g of monoglycidyl ether shown in the following was obtained. From the results of NMR ( ¹ H, ¹³ C, ²⁹ Si) and mass spectrometry (MS) of the obtained product, it was confirmed that the obtained product was a compound represented by Structural Formula (3) (see FIGS. 4 to 7). That is, it was shown that the monoallyl monoglycidyl ether compound synthesized in Example 16 can be reacted with a compound having a Si—H group by hydrosilylation reaction.

The measurement conditions of MS were as follows:

Device: JEOL JMS-SX102A

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

Sample concentration: 10-fold dilution of NMR solution with dichloromethane

Sample amount: 0.5 μl * Volatilized off by solvent at 80 ° C and introduced into MS

Ionization method: EI (electron ionization method)

Scan Range: m / z10? 800

According to the method for producing a glycidyl ether compound of the present invention, a corresponding glycidyl ether compound can be produced by reacting hydrogen peroxide and allyl ether compound using a tungsten compound, a tertiary organic amine, and phenylphosphonic acid as a catalyst. Epoxy resin, a useful material widely used in various industries such as chemical industry as raw material of various polymers such as electronic materials, adhesives, paint resins, etc. It can be manufactured with good yield and low cost. In addition, since the monoallyl monoglycidyl ether compound of the present invention can introduce a biphenylglycidyl ether group into a compound having various Si-H groups by hydrosilylation with a compound having a Si-H group, heat resistance and etching resistance It is useful for the synthesis | combination of the epoxy resin used for such high resists, sealing materials, etc.

Claims (13)

A method for producing a corresponding glycidyl ether compound by epoxidizing a carbon-carbon double bond of the allyl group by reacting a compound having an allyl ether bond with hydrogen peroxide, wherein the reaction catalyst is a tungsten compound, a tertiary amine, and phenyl A method for producing a glycidyl ether compound, characterized by using phosphonic acid. The method of claim 1,
A method for producing a glycidyl ether compound, characterized by using a partially neutralized salt of tungstic acid as the tungsten compound. The method according to claim 1 or 2,
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 according to any one of claims 1 to 3,
Said tertiary amine is trialkylamine, The sum total carbon number of the alkyl group couple | bonded with the nitrogen atom is 6 or more and 50 or less, The manufacturing method of the glycidyl ether compound characterized by the above-mentioned. The method according to any one of claims 1 to 4,
The compound having an allyl ether bond is a method of producing a glycidyl ether compound, characterized in that the compound having a plurality of allyl ether bonds. The method according to any one of claims 1 to 4,
The compound having an allyl ether bond is a compound having two allyl ether bonds, and further has a step of isolating a monoallyl monoglycidyl ether compound of which only one allyl ether bond is epoxidized from the reaction product. Method for producing a glycidyl ether compound. 7. The method according to any one of claims 1 to 6,
An organic solvent is not used as a reaction solvent. A method for producing a glycidyl ether compound. The method according to any one of claims 1 to 7,
The compound having the allyl ether bond is represented by the following formula (1):

{In formula, R <^1> and R <^2> is a hydrogen atom, a C1-C6 alkyl group, a C2-C6 alkenyl group, a C3-C12 cycloalkyl group, or a C6-C10 aryl group each independently, or R ¹ and R ² may form a C2-C6 alkylidene group or a C3-C12 cycloalkylidene group together. 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 represents an integer of 0 or 1.}. A method for producing a glycidyl ether compound, characterized by the above-mentioned. The method according to any one of claims 1 to 8,
The compound having an allyl ether bond consists of diallyl ether of bisphenol-A, diallyl ether of bisphenol-F, and 3,3 ', 5,5'-tetramethylbiphenyl-4,4'-diallyl ether It is at least 1 sort (s) chosen from the group, The manufacturing method of the glycidyl ether compound characterized by the above-mentioned. The method according to any one of claims 1 to 7,
The compound having the allyl ether bond includes a C 2-20 α, ω-polyalkylene glycol diallyl ether, 1,4-cyclohexanedimethanol diallyl ether, and tricyclo [5.2.1.0 ^2,6 ] decane It is at least 1 sort (s) chosen from the group which consists of methanol diallyl ether, The manufacturing method of the glycidyl ether compound characterized by the above-mentioned. The method according to any one of claims 1 to 7,
The compound having an allyl ether bond is a phenol-formaldehyde-allyl alcohol polycondensate or cresol-formaldehyde-allyl alcohol polycondensate. General formula (2) below:

{In formula, R <^7> , R <^8> , R <^9> , and R <^10> are respectively independently a hydrogen atom, a C1-C10 alkyl group, a C2-C10 alkenyl group, a C3-C10 cycloalkyl group, or a C6-C10 Monoallyl monoglycidyl ether compound which has a biphenyl skeleton characterized by the aryl group}. The method of claim 12,
In the formula, R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are methyl groups, wherein the monoallyl monoglycidyl ether compound having a biphenyl skeleton.

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