WO2011078060A1 - Process for production of glycidyl ether compounds, and monoallyl monoglycidyl ether compound - Google Patents

Abstract

Provided are: a process by which a compound having an allyl ether linkage can be efficiently converted into the corresponding glycidyl ether compound under mild conditions using hydrogen peroxide as the oxidizing agent; and a novel monoallyl monoglycidyl ether compound having a biphenyl skeleton. Specifically provided are: a process for the production of glycidyl ether compounds which comprises reacting a compound having an allyl ether linkage with hydrogen peroxide to epoxidize the carbon-carbon double bond of the allyl group and thus form the corresponding glycidyl ether compound, characterized by using, as the reaction catalyst, a tungsten compound, a tertiary amine, and phenylphosphonic acid; and a monoallyl monoglycidyl ether compound having a biphenyl skeleton. The monoallyl monoglycidyl ether compound can be produced by the process.

Description

Method for producing glycidyl ether compound 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 relates to an efficient epoxidation by oxidizing a carbon-carbon double bond of the allyl group of a compound having an allyl ether bond with hydrogen peroxide by using a predetermined catalyst. The present invention relates to a method for producing a characteristic glycidyl ether compound, and a monoallyl monoglycidyl ether compound produced by oxidation of a carbon-carbon double bond of the allyl group of a compound having an allyl ether bond with hydrogen peroxide.

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

As a conventionally known method for producing glycidyl ether, there is 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, the organochlorine compound always remains, and there is a disadvantage that the insulating properties are lowered when used in some applications, for example, electronics applications.

Therefore, direct epoxidation of an allyl ether carbon-carbon double bond 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 ether of bisphenol-A or polyallyl ether of novolac type phenol resin is added to toluene or the like. A method of epoxidation with hydrogen peroxide in the presence of a quaternary ammonium salt using sodium tungstate and a phosphoric acid catalyst in an organic solvent is disclosed. This method requires a very large amount of tungsten compound, and the epoxidation rate is not sufficient, so that it cannot be carried out as an industrial production method.

In the following Patent Document 3 (US Pat. No. 5,633,391), an olefin is epoxidized by contacting the olefin with bis (trimethylsilyl) peroxide as an oxidizing agent in an organic solvent in the presence of a rhenium oxide catalyst. Although a method is disclosed, an expensive catalyst and an oxidizing agent are required, and in the case of phenyl allyl ether, the yield is not sufficient.

In the following Patent Document 4 (Japanese Patent Laid-Open No. 7-145221) and Patent Document 5 (Japanese Patent Laid-Open No. 58-173118), a phenol novolak resin is allyl etherified with an allyl halide and then peroxygenated in an organic solvent. Although a method for epoxidation is disclosed, it is necessary to use peracids which are highly hazardous.

Patent Document 6 below (Japanese Patent Publication No. 2002-526383) discloses a method of epoxidation with hydrogen peroxide in the presence of a titanium-containing zeolite catalyst, a tertiary amine, a tertiary amine oxide, or a mixture thereof. However, although this method is useful when an olefin compound having a low molecular weight is used as a substrate, a substrate having a high molecular weight such as phenyl ether has poor catalytic efficiency and cannot be applied.

Japanese National Patent Publication No. 10-511722 Japanese Unexamined Patent Publication No. 60-60123 US Pat. No. 5,633,391 JP 7-145221 A JP 58-173118 A JP-T-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.

No example of synthesizing a monoallyl monoglycidyl ether compound having a biphenyl skeleton has been reported. Since monoallyl monoglycidyl ether compounds have allyl groups, they can be hydrosilylated with compounds having Si—H groups, and biphenyl glycidyl ether groups are introduced into various compounds having Si—H groups. be able to. For example, when synthesizing epoxy resins used for resists and sealants, hydrosilylation with various siloxane compounds having Si-H groups allows heat resistance and etching resistance to be achieved through a one-step reaction. It is considered that a high biphenyl skeleton and an epoxy group necessary for curing can be introduced at the same time, which is extremely useful. Therefore, the problem to be solved by the present invention is to provide a novel monoallyl monoglycidyl ether compound having a biphenyl skeleton having high heat resistance and etching resistance.

As a result of intensive studies and experiments to solve the above problems, the present inventor used a tungsten compound, a tertiary organic amine, and phenylphosphonic acid as a catalyst to produce an aqueous hydrogen peroxide solution and an allyl ether compound. By carrying out the reaction, it was found that the corresponding glycidyl ether compound was selectively produced with high efficiency, and the present invention was completed.

That is, the present invention is as follows.
[1] In a method for producing a corresponding glycidyl ether compound by reacting a compound having an allyl ether bond with hydrogen peroxide and epoxidizing the carbon-carbon double bond of the allyl group, tungsten as a reaction catalyst A method for producing the glycidyl ether compound, comprising using a compound, a tertiary amine, and phenylphosphonic acid.

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

[3] The glycidyl ether according to [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. Compound production method.

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

[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 step of isolating a monoallyl monoglycidyl ether compound in which the compound having an allyl ether bond is a compound having two allyl ether bonds and only one allyl ether bond is epoxidized from the reaction product The method for producing a glycidyl ether compound according to any one of the above [1] to [4].

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

｛式中、R¹、及びR²は、各々独立して、水素原子、炭素数１～６のアルキル基、炭素数２～６のアルケニル基、炭素数３～１２のシクロアルキル基又は炭素数６～１０のアリール基であり、あるいは、R¹とR²は一緒になって炭素数２～６のアルキリデン基又は炭素数３～１２のシクロアルキリデン基を形成してもよい。R³、R⁴、R⁵、及びR⁶は、各々独立して、水素原子、炭素数１～１０のアルキル基、炭素数２～１０のアルケニル基、炭素数３～１２のシクロアルキル基又は炭素数６～１０のアリール基であり、そして、ｎは０又は１の整数を表す。｝で表される構造を有する、前記［１］～［７］のいずれか１項に記載のグリシジルエーテル化合物の製造方法。 [8] The compound having an allyl ether bond is represented by the following formula (1):

{Wherein R ¹ and R ² are each independently 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. R ¹ and R ² may be taken together to form an alkylidene group having 2 to 6 carbon atoms or a cycloalkylidene group having 3 to 12 carbon atoms. 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 method for producing a glycidyl ether compound according to any one of the above [1] to [7], which has a structure represented by:

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

[10] The compound having an allyl ether bond is a C 2-20 α, ω-polyalkylene glycol diallyl ether, 1,4-cyclohexanedimethanol diallyl ether, and tricyclo [5.2.1.0 ^{2, 6} ] The process for producing a glycidyl ether compound according to any one of [1] to [7], which is at least one selected from the group consisting of decanedimethanol diallyl ether.

[11] The glycidyl 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. A method for producing an ether compound.

｛式中、Ｒ^７、Ｒ^８、Ｒ^９、及びＲ^１０は、それぞれ独立に、水素原子、炭素数１～１０のアルキル基、炭素数２～１０のアルケニル基、炭素数３～１０のシクロアルキル基又は炭素数６～１０のアリール基を示す。｝で表される、ビフェニル骨格を有するモノアリルモノグリシジルエーテル化合物。 [12] The following general formula (2):

{Wherein R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a cyclohexane having 3 to 10 carbon atoms. An alkyl group or an aryl group having 6 to 10 carbon atoms is shown. } The monoallyl monoglycidyl ether compound which has a biphenyl frame | skeleton represented by these.

[13] The 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.

According to the method for producing a glycidyl ether compound of the present invention, by using a tungsten compound, a tertiary organic amine, and phenylphosphonic acid as a catalyst, and reacting hydrogen peroxide with an allyl ether compound, the corresponding glycidyl ether is obtained. Epoxy resins, which are useful substances widely used in various industrial fields including the chemical industry as raw materials for various polymers such as electronic materials and adhesives and paint resins, can be produced. It is possible to manufacture safely, with good yield, and at low cost by a simple operation while minimizing the mixing of impurities. Therefore, the method for producing a glycidyl ether compound of the present invention has a great industrial effect. In addition, since the monoallyl monoglycidyl ether compound according to the present invention has an allyl group, it can be hydrosilylated with a compound having an Si—H group, and biphenyl can be added to various compounds having an Si—H group. Since a glycidyl ether group can be introduced, it is extremely useful as a raw material for epoxy resins used for resists and sealing materials.

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

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 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%, more preferably 10 to 60%. From the viewpoint of industrial productivity and the energy cost of separation, hydrogen peroxide is preferred to have a high concentration, but excessively high concentration and / or excessive hydrogen peroxide is not used. This is preferable from the viewpoints of economy and safety. Reactivity is low when the concentration of hydrogen peroxide is less than 1%. The amount of hydrogen peroxide used is not particularly limited, but is 0.5 to 10 equivalents, preferably 0 to the carbon-carbon double bond of the allyl group of the compound having an allyl ether bond to be epoxidized. Selected from the range of 8 to 2 equivalents. If it is out of this range, one raw material will remain excessively, which is not economical.

As the tungsten compound used as a catalyst in the method for producing a glycidyl ether compound of the present invention, a compound that generates a tungstate anion in water is suitable. For example, tungstic acid, tungsten trioxide, tungsten trisulfide, tungsten hexachloride, phosphorus Examples include tungstic acid, ammonium tungstate, potassium tungstate dihydrate, sodium tungstate dihydrate, and the like. Tungstic acid, tungsten trioxide, phosphotungstic acid, sodium tungstate dihydrate, and the like are preferable. These tungsten compounds may be used alone or in combination of two or more.

The catalytic activity of these compounds that produce tungstate anions in water is higher when a counter cation of 0.2 to 0.8 is present relative to 1.0 tungstate anions. As a method for preparing such a tungsten composition, for example, tungstic acid and an alkali metal salt of tungstic acid may be mixed in the above ratio, or tungstic acid and an alkali compound (alkali metal or alkaline earth metal hydroxide) may be used. , Carbonates, etc.) or a combination of alkali metal or alkaline earth metal salts of tungstic acid and acidic compounds such as mineral acids such as phosphoric acid and sulfuric acid. Partially neutralized salts of acids can be formed. Specific examples of these 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 amount of the tungsten compound used as a catalyst is 0.0001 to 20 mol%, preferably 0.01 to 0.01%, based on the number of carbon-carbon double bonds of the allyl group of the compound having an allyl ether bond as a substrate. It is selected from the range of 20 mol%. If it is less than 0.0001 mol%, the reactivity is low, and if it is more than 20 mol%, it is economically disadvantageous.

The tertiary amine used as the catalyst is a tertiary organic amine (trialkylamine) having a total of 6 or more, preferably 10 or more carbon atoms of the alkyl group bonded to the nitrogen atom, and has a high epoxidation reaction activity. preferable.

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 alkylamine, N, N-dimethyl-cured tallow alkylamine, N, N-dimethyloleylamine, N, N-diisopropyl-2-ethylhexylamine, N, N-dibutyl-2-ethylhexylamine, N-methyldioctylamine, N-methyldidecylamine, Examples thereof include N-methyldicocoalkylamine, N-methyl hydrogenated beef tallow alkylamine, and N-methyldioleylamine. 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, considering 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. The amount used is preferably from 0.0001 to 10 mol%, more preferably from 0.01 to 10 mol%, based on the number of carbon-carbon double bonds of the allyl group of the compound having an allyl ether bond of the substrate. It is. If it is less than 0.0001 mol%, the reactivity is low, and if it is more than 10 mol%, it is economically disadvantageous.

In the method for producing a glycidyl ether compound of the present invention, phenylphosphonic acid is further used as a (co-) catalyst. The amount used is preferably from 0.0001 to 10 mol%, more preferably from 0.01 to 10 mol%, based on the number of carbon-carbon double bonds of the allyl group of the compound having an allyl ether bond of the substrate. It is. If it is less than 0.0001 mol%, the reactivity is low, and if it is more than 10 mol%, it is economically disadvantageous.

The substrate for epoxidation in the method for producing a glycidyl ether compound of the present invention 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 one. And two or more. Compounds 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, Examples thereof include cyclohexyl allyl ether and cyclohexane methanol monoallyl ether.

｛式中、R¹、及びR²は、各々独立して、水素原子、炭素数１～６のアルキル基、炭素数２～６のアルケニル基、炭素数３～１２のシクロアルキル基、又は炭素数６～１０のアリール基であり、あるいは、R¹とR²は一緒になって炭素数２～６のアルキリデン基又は炭素数３～１２のシクロアルキリデン基を形成してもよい。R³、R⁴、R⁵、及びR⁶は、各々独立して、水素原子、炭素数１～１０のアルキル基、炭素数２～１０のアルケニル基、炭素数３～１２のシクロアルキル基又は炭素数６～１０のアリール基であり、そして、ｎは０又は１の整数を表す。｝で表される化合物が挙げられる。ここでｎが０の場合は、２つのベンゼン環が直接結合（ビフェニル骨格）していることを示す。これらの中でもR¹～R⁶が各々独立して水素原子又はメチル基であり、ｎが１または０のものがより好ましい。 The compounds 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, neopentyl glycol Α, ω-alkylenediol diallyl ethers having 2 to 20 carbon atoms such as diallyl ether, α, ω-polyalkylene glycol diallyl ethers having 2 to 20 carbon atoms, 1,4-cyclohexanedimethanol diallyl ether, tricyclo [ 5.2.1.0 ^2,6 ] decanedimethanol diallyl ether and the following general formula (1):

{Wherein R ¹ and R ² are each independently 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 carbon. R 6 may be an aryl group having 6 to 10 carbon atoms, or R ¹ and R ² may be combined to form an alkylidene group having 2 to 6 carbon atoms or a cycloalkylidene group having 3 to 12 carbon atoms. 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 compound represented by this is mentioned. Here, when n is 0, it indicates 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 more preferably 1 or 0.

Specific examples of such compounds include bisphenol-A diallyl ether, bisphenol-F diallyl ether, 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'-biphenol diallyl ether, 2,2'-diisopropylbiphenol diallyl ether, 4,4'-ethylidene bisphenol diallyl ether 4,4′-cyclohexylidene bisphenol diallyl ether, 4,4 ′-(1-α-methylbenzylidene) bisphenol diallyl ether, 4,4 ′-(3,3,5-trimethylcyclohexylidene) bisphenol diallyl ether , 4, 4 - (1-methyl - benzylidene) bisphenol diallyl ether, 3,3 ', 5,5'-tetramethyl-4,4'-diallyl ether.

Examples of the compound having three or more allyl ether bonds include phenol-formaldehyde / allyl alcohol polycondensate or cresol-formaldehyde / allyl alcohol polycondensate.

These substrates can be used without an organic solvent or with an organic solvent if necessary, by mixing an aqueous hydrogen peroxide solution and the above-described catalyst to allow the epoxidation reaction to proceed, without using an organic solvent. Performing the epoxidation reaction is advantageous in terms of reduction of production cost, simplification of production equipment (for example, omission of explosion-proof equipment, etc.), waste disposal, and improvement of work environment. In the case of using a solvent, the reaction rate becomes slow and, depending on the solvent, an undesirable reaction such as a hydrolysis reaction may easily proceed. When the viscosity of the compound having an allyl ether bond as a reaction substrate is too high or is a solid, a minimum necessary organic solvent may be used. The organic solvent that can be used is preferably an aromatic hydrocarbon, an aliphatic hydrocarbon or an alicyclic hydrocarbon, and examples thereof include toluene, xylene, hexane, octane, and cyclohexane. It is advantageous in terms of production cost to keep the amount used to the minimum necessary, and it is preferably used at 50 parts by mass or less, more preferably 30 parts by mass or less with respect to 100 parts by mass of the compound having an allyl ether bond. The When the amount of the organic solvent used exceeds 50 parts by mass with respect to 100 parts by mass of the compound having an allyl ether bond, the substrate concentration decreases and the reactivity decreases.

Also, considering the industrially stable production method for epoxidation, the catalyst and substrate are first charged into the reactor, and hydrogen peroxide is consumed in the reaction while keeping the reaction temperature as constant as possible. It is better to add gradually while confirming that it is. By adopting such a method, even if hydrogen peroxide is abnormally decomposed in the reactor and oxygen gas is generated, the amount of hydrogen peroxide accumulated is small and the pressure rise can be minimized.

If the reaction temperature is too high, there will be many side reactions, and hydrogen peroxide will also be easily decomposed. If it is too low, the consumption rate of hydrogen peroxide will slow down and may accumulate in the reaction system. The reaction temperature is preferably selected in the range of −10 to 120 ° C., more preferably 20 ° C. to 100 ° C.

After completion of the reaction, there may be almost no difference in specific gravity between the aqueous layer and the organic layer. In that case, an organic extraction solvent is prepared by mixing the aqueous layer with a saturated aqueous solution of an inorganic compound and making a difference in specific gravity with the organic layer. Two-layer separation can be carried out without using. In particular, since the specific gravity of the tungsten compound is heavy, in order to bring the aqueous layer to the lower layer, a tungsten compound exceeding the above-mentioned usage amount that is originally necessary as a catalyst may be used. In this case, it is desirable to increase the efficiency of the tungsten compound by reusing the tungsten compound from the aqueous layer.

Conversely, depending on the substrate, the specific gravity of the organic layer may be close to 1.2. In such a case, water is added to bring the specific gravity of the aqueous layer closer to 1, so that It is also possible to bring an organic layer under the layer. The extraction of the reaction solution can also be carried out using an organic solvent such as toluene, cyclohexane, hexane, methylene chloride, etc., and an optimal separation method can be selected according to the situation.

｛式中、Ｒ^７、Ｒ^８、Ｒ^９、及びＲ^１０は、それぞれ独立に、水素原子、炭素数１～１０のアルキル基、炭素数２～１０のアルケニル基、炭素数３～１０のシクロアルキル基又は炭素数６～１０のアリール基を示す。｝で表されるモノアリルモノグリシジルエーテルを得ることができる。Ｒ^７、Ｒ^８、Ｒ^９、及びＲ^１０は、メチル基であることができる。 Thus, after concentrating the organic layer isolate | separated from the water layer, the obtained glycidyl ether compound can be taken out by normal methods, such as distillation, chromatographic separation, recrystallization, and sublimation. When the compound having an allyl ether bond is a compound having two allyl ether bonds, a monoallyl monoglycidyl ether compound in which only one allyl ether bond is epoxidized from the reaction product by performing the above separation and purification operation Can be isolated. For example, when a diallyl ether compound having a biphenyl skeleton is used as a substrate, the organic layer contains monoallyl monoglycidyl ether, diglycidyl ether, and unreacted diallyl ether compound, which are described later in Example 16. For example, the following general formula (2):

{Wherein R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a cyclohexane having 3 to 10 carbon atoms. An alkyl group or an aryl group having 6 to 10 carbon atoms is shown. } Can be obtained. R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ can be methyl groups.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

[Example 1]
To a 300 mL three-necked flask equipped with a dropping funnel and a Dimroth condenser, 0.950 g (2.88 mmol) of sodium tungstate (manufactured by Nippon Inorganic Chemical Co., Ltd.), 0.720 g of tungstic acid (manufactured by Nippon Inorganic Chemical Co., Ltd.) ( 2.88mmol), Trioctylamine (Guangei Chemical Co., Ltd.) 2.04g (5.76mmol), Phenylphosphonic acid (Nissan Chemical Co., Ltd.) 0.911g (5.76mmol), Allyl phenyl ether 80g (0.576mol) While stirring with a magnetic stirrer, the mixture was heated to 70 ° C. with an oil bath, and 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. 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 so that the upper layer was an organic layer and the lower layer was an aqueous layer.

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

In addition, the conversion rate and the selectivity were calculated by the following calculation formula based on the result analyzed by gas chromatography.
Conversion rate (%) = (1−number of moles of raw material remaining / number of moles of raw material used) × 100
Selectivity (%) = {(number of moles of target compound / number of moles of raw material 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 rate of allyl phenyl ether was 3.6%, and only a very 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 very small amount of glycidyl 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 with the catalyst components and the charged molar ratios shown in Table 1 below. The results are also shown in Table 1 below.

[Synthesis Example 1] Synthesis of diallyl ether of bisphenol-F In a 2000 ml eggplant-shaped flask, 200 g (0.999 mol) of bisphenol-F-ST (Mitsui Chemicals), 50% water content 5% -Pd / C- STD type (manufactured by NE Chemcat Co., Ltd.) 2.13 g (0.499 mmol), triphenylphosphine (manufactured by Hokuko Chemical Co., Ltd.) 2.62 g (9.99 mmol), potassium carbonate (manufactured by Asahi Glass Co., Ltd.) 276 g (2.00 mol) ), Allyl acetate (made by Showa Denko KK) 220 g (2.20 mol) and isopropanol 200 g were added and 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, and it was confirmed that the ratio of bisphenol-F diallyl ether to monoallyl ether was 99: 1.

Thereafter, 400 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. This reaction and post-treatment operation were repeated four times, and then a distillate 748 g (isolation yield 66%, bisphenol-F diallyl ether 98.7%, the rest was monoallyl) with a molecular distillation apparatus (manufactured by Daishin Kogyo Co., Ltd.). Ether) and 368 g of non-distilled product (bisphenol-F diallyl ether 88%). These analyzes were performed by gas chromatography. The viscosity of the distillate at 25 ° C. was 25 mPa · s (measured with a B-type viscometer (DV-E manufactured by BROOKFIELD (model: LVDV-E))). The isomer ratio was o, o '-: o, p'-: p, p '-= 17:52:31 (analyzed value by gas chromatography).

Synthesis Example 2 Synthesis of 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diallyl ether 3,3 ′, 5,5′-tetramethyl-4 was added to a 2000 ml eggplant-shaped flask. , 4'-biphenyldiol (China: Made in Gansu Chemical Research Institute) 150g (0.619mol), 50% water content 5% -Pd / C-STD type (made by N.E. Chemcat Co., Ltd.) 1.32g (0.310mmol) , Triphenylphosphine (Hokuko Chemical Co., Ltd.) 1.624 g (6.19 mmol), potassium carbonate (Nippon Soda Co., Ltd.) 171 g (1.24 mol), allyl acetate (Showa Denko Co., Ltd.) 136 g (1.36 mol) , And 68.1 g of isopropanol were added and 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. The ratio of 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diallyl ether to monoallyl ether was 97. : Confirmed to be up to 3.

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. This reaction and post-treatment operation were repeated four times, and then a distillate of 127.5 g (isolation yield: 66%, diallyl ether: 97.9%, the remainder being monoallyl ether) was obtained using a molecular distillation apparatus (manufactured by Otsuka Kogyo Co., Ltd.). As a result, 31.7 g of non-distillate (97.5% diallyl ether) was obtained. These analyzes were performed by gas chromatography. The distillate was a solid having a melting point of 51.7 ° C., and the viscosity at 60 ° C. was 29 mPa · s (measured with a B-type viscometer (DV-E (model: LVDV-E) manufactured by BROOKFIELD)).

[Synthesis Example 3]: Synthesis of 1,4-cyclohexanedimethanol diallyl ether In a 1000 ml flask, 100 g (0.693 mol) of 1,4-cyclohexanediol (manufactured by Eastman Chemical), 110.9 g of a 50% aqueous sodium hydroxide solution (1.39) mol), tetrabutylammonium bromide (manufactured by Lion Akzo Co., Ltd.) 1.12 g (3.47 mmol) and allyl chloride 132.7 g (1.73 mol) are added and heated at 40 ° C in a nitrogen stream at first. At the same time, the reaction temperature was gradually raised, the temperature was raised to 70 ° C. over 3 hours, and the reaction was further continued for 17 hours. The reaction solution was cooled to room temperature, 200 ml of toluene was added to extract the reaction product, and the organic layer was washed twice with pure water. After distilling off toluene with an evaporator, the initial fraction was removed by distillation under reduced pressure to obtain 84.6 g of a distillate having a boiling point of 80.4 ° C./28 Pa (diallyl ether 94%, the rest being monoallyl ether). These analyzes were performed by gas chromatography. The viscosity of the distillate at 25 ° C. was 8.5 mPa · s (measured with a B-type viscometer (DV-E (model: LVDV-E) manufactured by BROOKFIELD)).

[Synthesis Example 4]: Synthesis of 1,6-hexanediol diallyl ether In a 1000 ml flask, 100 g (0.846 mol) of 1,6-hexanediol (manufactured by Tokyo Chemical Industry Co., Ltd.), 135.4 g of 50% aqueous sodium hydroxide solution ( 1.69 mol), 1.36 g (4.23 mmol) of tetrabutylammonium bromide (manufactured by Lion Akzo Co., Ltd.), 161.9 g (2.12 mol) of allyl chloride, and initially heating at 40 ° C. under a nitrogen stream. The reaction temperature was gradually raised as the reaction proceeded, the temperature was raised to 70 ° C. over 2 hours, and the reaction was further continued for 10 hours. The reaction solution was cooled to room temperature, 200 ml of toluene was added to extract the reaction product, and the organic layer was washed twice with pure water. After distilling off toluene with an evaporator, the initial distillation was removed by distillation under reduced pressure to obtain 84.6 g of a distillate having a boiling point of 72 ° C./133 Pa (diallyl ether 97%, the rest being monoallyl ether). These analyzes were performed by gas chromatography. The viscosity of the distillate at 25 ° C. was 2.3 mPa · s (measured with a B-type viscometer (DV-E (model: LVDV-E) manufactured by BROOKFIELD)).

[Examples 11 to 15]
The epoxidation reaction was carried out in the same manner as in Example 1 except that allyl phenyl ether in Example 1 was replaced with the compounds 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 identified in this example. The experimental procedure is described below.
To a 300 mL three-necked flask equipped with a dropping funnel and a Dimroth condenser, 0.950 g (2.88 mmol) of sodium tungstate (manufactured by Nippon Inorganic Chemical Co., Ltd.), 0.720 g of tungstic acid (manufactured by Nippon Inorganic Chemical Co., Ltd.) ( 2.88 mmol), trioctylamine (manufactured by Guangei Chemical Co., Ltd.) 2.04 g (5.76 mmol), phenylphosphonic acid (manufactured by Nissan Chemical Co., Ltd.) 0.911 g (5.76 mmol), 3,3 ′, 5,5′- 92.9 g (0.288 mol) of tetramethylbiphenyl-4,4′-diallyl ether was added and heated to 70 ° C. in an oil bath while stirring with a magnetic stirrer, and then 84.0 g (0.864 mol) was added dropwise such 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 so that the upper layer was an organic layer and the lower layer was an aqueous layer.

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

Thereafter, the organic layer was washed with an aqueous sodium sulfite solution, and the organic layer was evaporated and dried using an evaporator and a vacuum pump to obtain a crude reaction product, which was then purified by column chromatography (silica gel 60N (spherical, medium). ): Manufactured by Kanto Chemical Co., Ltd., developing solvent: hexane: ethyl acetate = 10: 1-3: 1), 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diglycidyl ether and 3, 3 ′, 5,5′-tetramethylbiphenyl-4,4′-monoallylmonoglycidyl ether was obtained. From the NMR ( ¹ H, ¹³ C) and mass spectrometry (MS) results of the obtained product, the obtained product was found to be 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-di It was confirmed that they were glycidyl ether and 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-monoallyl monoglycidyl ether. The measurement results of the monoallyl monoglycidyl ether are shown in FIGS.

The measurement conditions for MS were as follows:
Device: JEOL JMS-SX102A
Sample heating temperature: 80 ℃ → [32 ℃ / min] → 400 ℃
Sample concentration: Diluted NMR measurement solution 10 times with dichloromethane Sample volume: 0.5 μl * Volatilized and removed by solvent with heating at 80 ° C, then introduced into MS Ionization method: EI (Electron ionization method)
Scan range: m / z 10 to 800

に示すモノグリシジルエーテル０．１３ｇが得られた。得られた生成物のＮＭＲ（^１Ｈ、^１３Ｃ、^２９Ｓｉ）および質量分析（ＭＳ）の結果から、得られた生成物は構造式（３）に示される化合物であることが確認された（図４～７参照）。すなわち、実施例１６で合成したモノアリルモノグリシジルエーテル化合物は、ヒドロシリル化反応により、Ｓｉ－Ｈ基を有する化合物と反応させることができることが示された。 [Example 17]
In a 50 ml three-necked flask equipped with a reflux condenser, a thermometer, a stirrer, and a serum cap, 0.1 g (0.30 mmol) of monoallyl monoglycidyl ether synthesized in Example 16, 1,1,1,3,5 , 5,5-heptamethyltrisiloxane 0.077 g (0.35 mmol) and toluene 1 ml were added, and the mixture was stirred at room temperature under an argon stream. To the mixed solution, 0.002 g of 3% divinyltetramethyldisiloxane platinum complex isopropyl alcohol solution (platinum amount: 6.0 × 10 ⁻⁵ g) was added to the reaction solution and stirred at room temperature. After stirring at room temperature for 6 hours, the toluene solvent was removed under reduced pressure to obtain 0.13 g of a crude reaction product. Then, by column chromatography purification (silica gel 60N (spherical, neutral): manufactured by Kanto Chemical Co., Ltd., developing solvent; toluene: ethyl acetate = 10: 1), the following structural formula (3):

As a result, 0.13 g of monoglycidyl ether shown in FIG. 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 the structural formula (3) ( (See FIGS. 4-7). 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 a hydrosilylation reaction.

The measurement conditions for MS were as follows:
Device: JEOL JMS-SX102A
Sample heating temperature: 80 ℃ → [32 ℃ / min] → 400 ℃
Sample concentration: Diluted NMR measurement solution 10 times with dichloromethane Sample volume: 0.5 μl * Volatilized and removed by solvent with heating at 80 ° C, then introduced into MS Ionization method: EI (Electron ionization method)
Scan range: m / z 10 to 800

According to the method for producing a glycidyl ether compound of the present invention, by using a tungsten compound, a tertiary organic amine, and phenylphosphonic acid as a catalyst, and reacting hydrogen peroxide with an allyl ether compound, the corresponding glycidyl ether is obtained. Epoxy resins, which are useful substances widely used in various industrial fields including the chemical industry as raw materials for various polymers such as electronic materials and adhesives and paint resins, can be produced. It is possible to manufacture safely, with good yield, and at low cost by a simple operation while minimizing the mixing of impurities. The monoallyl monoglycidyl ether compound of the present invention can introduce a biphenyl glycidyl ether group into a compound having various Si—H groups by a hydrosilylation reaction with a compound having an Si—H group. It is useful for synthesizing epoxy resins used for resists and sealing materials having high properties and etching resistance.

Claims (13)

In a method for producing a corresponding glycidyl ether compound by reacting a compound having an allyl ether bond with hydrogen peroxide and epoxidizing the carbon-carbon double bond of the allyl group, a tungsten compound, 3 A method for producing the glycidyl ether compound, comprising using a secondary amine and phenylphosphonic acid. The method for producing a glycidyl ether compound according to claim 1, wherein a partially neutralized salt of tungstic acid is used as the tungsten compound. 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 production of a glycidyl 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 of the alkyl group bonded to the nitrogen atom is 6 or more and 50 or less. Method. 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 a plurality of allyl ether bonds. The compound having an allyl ether bond is a compound having two allyl ether bonds, and further comprising isolating a monoallyl monoglycidyl ether compound in which only one allyl ether bond is epoxidized from the reaction product. Item 5. The method for producing a glycidyl ether compound according to any one of Items 1 to 4. The method for producing a glycidyl ether compound according to any one of claims 1 to 6, wherein organic hot metal is not used as the reaction hot metal. The compound having an allyl ether bond is represented by the following formula (1):

{Wherein R ¹ and R ² are each independently 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. R ¹ and R ² may be taken together to form an alkylidene group having 2 to 6 carbon atoms or a cycloalkylidene group having 3 to 12 carbon atoms. 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 method for producing a glycidyl ether compound according to any one of claims 1 to 7, which has a structure represented by The compound having an allyl ether bond is selected from the group consisting of diallyl ether of bisphenol-A, diallyl ether of bisphenol-F, and 3,3 ′, 5,5′-tetramethylbiphenyl-4,4′-diallyl ether The method for producing a glycidyl ether compound according to any one of claims 1 to 8, which is at least one of the above. The compound having an allyl ether bond is an α, ω-polyalkylene glycol diallyl ether, 1,4-cyclohexanedimethanol diallyl ether having 2 to 20 carbon atoms, and tricyclo [5.2.1.0 ^2,6 ] deoxy. The method for producing a glycidyl ether compound according to any one of claims 1 to 7, which is at least one selected from the group consisting of candimethanol 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 / allyl alcohol polycondensate. . The following general formula (2):

{Wherein R ⁷ , R ⁸ , R ⁹ , and R ¹⁰ are each independently a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, an alkenyl group having 2 to 10 carbon atoms, or a cyclohexane having 3 to 10 carbon atoms. An alkyl group or an aryl group having 6 to 10 carbon atoms is shown. } The monoallyl monoglycidyl ether compound which has a biphenyl frame | skeleton represented by these. The monoallyl monoglycidyl ether compound which has a biphenyl skeleton of Claim 12 whose R < ⁷ >, R <^8> , R < ⁹ > and R < ¹⁰ > are methyl groups in a formula.

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