JP2017066094A - Manufacturing method of epoxy compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for manufacturing an epoxy compound at high yield by oxidizing a compound having at least one or more ethylenic double bond by using an oxidant such as hydrogen peroxide with enhanced effective utilization ratio of the oxidant.SOLUTION: There is provided a manufacturing method of an epoxy compound by oxidizing a compound having at least one or more ethylenic double bond by using an oxidant, including using a porous carrier which carries quaternary ammonium salt of polyoxomethalate anion having saturated or unsaturated hydrocarbon group with 8 or more carbon atoms as a catalyst.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing an epoxy compound. Specifically, the present invention relates to a method for producing an epoxy compound by epoxidizing a compound having at least one ethylenically unsaturated double bond with an oxidizing agent and a catalyst.

  A cured product is obtained by reacting the epoxy compound with various curing agents and a curing catalyst. These epoxy compounds are useful as intermediates for making coatings, adhesives, inks, sealant components or other compounds useful for a variety of end uses including pharmaceuticals and medical supplies.

As a method for producing an epoxy compound, a method for epoxidizing an olefin with an oxidizing agent is known. Among them, a species that is a compound that essentially requires a tungsten atom exhibits catalytic activity in an olefin epoxidation reaction, and is a catalyst. It is effective as an ingredient. For example, it is known that olefin epoxidation easily proceeds in a catalyst system in which aminomethylphosphonic acid is added to sodium tungstate and trimethyloctylammonium hydrogen sulfate using hydrogen peroxide (Non-patent Document 1). . In addition, the use of heteropolyacids having a structure in which a polyatom is coordinated to a heteroatom via oxygen as a catalyst has been studied, and among them, Q ₃ XW ₄ O _24-2n (Q is Represents a cation of a quaternary ammonium salt, X represents a P or As atom, and n represents 0, 1 or 2). Patent Document 2). In addition, for the purpose of preventing the quaternary ammonium salt to be used from remaining in the raw material and the target product, a quaternary ammonium salt-containing polymer fixed to polystyrene has also been developed. (Patent Document 1)

The above-mentioned Q ₃ XW ₄ O _24-2n has high activity, but it is difficult to recover, and there is a drawback that it cannot be used repeatedly because the catalyst activity decreases when the catalyst is reused.

  Further, although a quaternary ammonium salt-supported catalyst has been disclosed (Non-patent Document 3), the yield of this catalyst is only about 30% in the epoxidation of diallyl ether (Comparative Example 1 of the present application). There was room for improvement in terms of activity and repeated use.

JP 2013-194089 A

R. Noyori et al. Bull. Chem. Soc. Jpn, 1997, 70, 905 C. Venturello et al. J. et al. Org. Chem. 1988, 53, 1553 N. Mizuno et al. Chem. Cat. Chem. 2015, 1097-1104,

  The present invention has been made in view of the above-described situation, and an epoxy compound can be produced with a high yield and an improved effective utilization rate of an oxidant, and furthermore, an epoxy that is easy to recover a catalyst. It is in providing the manufacturing method of a compound.

  It has been found that the above problems can be solved by using, as a catalyst, a porous carrier carrying a quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms. .

That is, the present invention can be described as follows.
Item 1 A compound having at least one ethylenic double bond in the presence of a porous carrier carrying a quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms is epoxy A method for producing an epoxy compound, characterized by comprising:
Item 2. The method for producing an epoxy compound according to Item 1, wherein the quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms has an aralkyl group.
Item 3. The method for producing an epoxy compound according to Item 1 or 2, wherein the polyoxometalate anion has an atom selected from molybdenum, tungsten, vanadium and niobium.
Item 4 The method for producing an epoxy compound according to any one of Items 1 to 3, wherein the polyoxometalate anion contains silicon or phosphorus.
Item 5. The method for producing an epoxy compound according to any one of Items 1 to 4, wherein the compound having at least one ethylenic double bond is a compound having an allyloxy group.

  By using the production method of the present invention, an epoxy compound can be produced in a high yield and with an improved utilization rate of an oxidant, and the catalyst can be easily recovered.

  The present invention relates to a quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms in a method for producing an epoxy compound in which a compound having at least one ethylenic double bond is epoxidized. It is characterized by epoxidation in the presence of a porous carrier carrying

  The compound having at least one ethylenic double bond may be a chain or a cyclic organic compound, for example, a hydrocarbon, ester, alcohol, ether having at least one ethylenic double bond. One or two or more of halogen-substituted hydrocarbons can be used, and a compound having at least one ethylenic double bond having an allyloxy group is preferable. Specifically, ethylene, propylene, 1-butene, butadienes, 1-hexene, 1-pentene, isoprene, diisobutylene, 1-heptene, 1-octene, 1-nonene, 1-undecene, 1-dodecene, 1 -Tridecene, 1-tetradecene, 1-pentadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, propylene trimer and tetramers, having an ethylenic double bond at the end of 1,3-butadiene, etc. Alkenes or branched alkenes having an ethylenic double bond inside the molecule such as linear alkene, 2-butene, 2-octene, 2-methyl-2-hexene, 2,3-dimethyl-2-butene, cyclopentene, cyclohexene, 1-phenyl-1-cyclohexene, 1-methyl-1-cyclohexene, cyclohepte Cyclooctene, cyclodecene, cyclopentadiene, cyclodecatriene, cyclooctadiene, dicyclopentadiene, methylenecyclopropane, methylenecyclopentane, methylenecyclohexane, vinylcyclohexane, vinylcyclohexane, cyclooctene, norbornene, and other cyclic olefinic hydrocarbons, Esters having ethylenic double bonds such as allyl butyrate, allyl acetate, allyl methacrylate, vinyl acetate, allyl acrylate, alcohols having ethylenic double bonds such as allyl alcohol, ethylene glycol monoallyl ether, allyl glycidyl ether, allyl Ethers having ethylenic double bonds such as methyl ether, allyl ethyl ether, diallyl ether, allyl chloride, alcohol Halogenated hydrocarbons such as having an ethylenic double bond such as Le bromide and the like.

  As the oxidizing agent of the present invention for epoxidizing a compound having at least one ethylenic double bond, one that can generate oxygen ions, oxygen radicals, peroxides and superperoxides can be used, and t-butyl peroxide, Organic peroxides such as peracetic acid, hydrogen peroxide, a mixed gas of oxygen and hydrogen, dinitrogen monoxide, iodosylbenzene, and the like are suitable. Among these, it is preferable to use hydrogen peroxide.

  In the method for producing an epoxy compound of the present invention, when hydrogen peroxide is used as an oxidant, the usage form of hydrogen peroxide is practically 0.01 to 70% by weight aqueous solution or alcohol solution. Is preferred.

  The amount of the oxidizing agent used is the molar ratio to the ethylenic double bond in the compound having at least one ethylenic double bond as the reaction substrate (number of moles of ethylenic double bond in the reaction substrate / oxidant The number of moles) is preferably 100/1 or less, more preferably 10/1 or less, preferably 1/100 or more, and more preferably 1/50 or more.

  The method for producing an epoxy compound of the present invention is carried out in the presence of a porous carrier carrying a quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms. By supporting a quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms on a porous carrier, the catalyst is used as a solid phase, and a reaction such as a reaction substrate or hydrogen peroxide. The catalyst is easily recovered by so-called heterogeneous reaction in which the product is in the gas phase or liquid phase.

  A quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms is a quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 12 or more carbon atoms. The quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 14 or more carbon atoms is particularly preferable. There is no particular upper limit to the carbon number of the saturated or unsaturated hydrocarbon group of the quaternary ammonium salt of the polyoxometalate anion, but it may be 24 or less.

  The quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms preferably has an aralkyl group, and particularly preferably has a benzyl group. By having an aralkyl group, even a porous carrier carrying a quaternary ammonium salt of a polyoxometalate anion already used in the reaction can be reused because it retains high catalytic activity. Therefore, it is preferable.

  The quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms of the present invention has an atom selected from molybdenum, tungsten, vanadium and niobium as the polyoxometalate anion. Of these, tungsten is particularly preferable.

  The quaternary ammonium salt of the polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms of the present invention preferably has silicon or phosphorus as the polyoxometalate anion, and preferably has phosphorus. More preferred.

Specific examples of the quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms according to the present invention are shown below.
The polyoxometalate anion is represented by the following general formula (1) when the hetero atom is a silicon atom or a phosphorus atom.
[XM _n O _m ] ^q- (1)
(In the formula, X represents a silicon atom or a phosphorus atom. M represents at least one element selected from the group consisting of molybdenum, tungsten, vanadium and niobium. Further, n, m and q represent the element M. Will be determined by the valence of
M is preferably molybdenum or tungsten, and particularly preferably tungsten.
Examples of combinations of (n, m) include (4, 24), (9, 34), (10, 36), (11, 39), (12, 40), and the like. q is a positive integer. More specifically, (PW ₄ O ₂₄ ) ³⁻ , (PW ₁₀ O ₃₆ ) ⁷⁻ , (PW ₉ O ₃₄ ) ⁹⁻ , (SiW ₁₀ O ₃₆ ) ⁸⁻ , (SiW ₉ O ₃₄ ) ³⁻ , (SiW ₁₂ O ₄₀ ) ⁴⁻ can be exemplified.
The quaternary ammonium that is a counter cation of the polyoxometalate anion is represented by the following formula (2).
(In the formula, for R ^{1 to} R ⁴ , R ¹ is a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms, and R ^{2 to} R ⁴ are independently saturated or unsaturated hydrocarbons having 1 or more carbon atoms. Group.)
R ¹ is preferably a saturated or unsaturated hydrocarbon group having 8 to 24 carbon atoms, more preferably a saturated or unsaturated hydrocarbon group having 12 to 20 carbon atoms, and a saturated or unsaturated hydrocarbon group having 14 to 18 carbon atoms. Particularly preferred is a group. Examples of the saturated or unsaturated hydrocarbon group include an alkyl group, an alkenyl group, a cycloalkyl group, and an aralkyl group.
R ^{2 to} R ⁴ are preferably a saturated or unsaturated hydrocarbon group having 1 to 24 carbon atoms, more preferably a saturated or unsaturated hydrocarbon group having 1 to 20 carbon atoms, and 1 to 1 carbon atoms. Particular preference is given to 18 saturated or unsaturated hydrocarbon groups. The saturated or unsaturated hydrocarbon group includes an alkyl group, an alkenyl group, a cycloalkyl group (provided that R ^{2 to} R ⁴ have 3 or more carbon atoms), an aralkyl group (provided that R ^{2 to} R ⁴ have 7 carbon atoms). The above can be illustrated.
In the present invention, at least one of R ^{2 to} R ⁴ is an aralkyl group having 7 to 24 carbon atoms in that it has a higher catalytic activity and maintains a higher catalytic activity in repeated use. Preferably, it is a C7-20 aralkyl group, more preferably a C7-18 aralkyl group. The aralkyl group is preferably a benzyl group.

As the porous carrier for supporting the quaternary ammonium salt of the polyoxometalate anion of the present invention, alumina (Al ₂ O ₃ ), zirconia (ZrO ₂ ), titania (TiO ₂ ), silica, clay, zinc oxide, oxidation Tin, magnesium oxide, lanthanum oxide, barium oxide, hydrotalcite, activated carbon, tungsten oxide, zinc phosphate, lead phosphate, lanthanum phosphate, zeolite, ion exchange resin, silica-alumina, tungsten oxide-tin oxide, oxidation Examples thereof include composite oxides such as tin-alumina, and one or more can be used. Among these, a porous carrier having alumina or tin oxide as a constituent component is preferable.

  As the porous carrier for supporting the quaternary ammonium salt of the polyoxometalate anion of the present invention, in the case of a catalyst using a tungsten species, the porous carrier and other than the tungsten species in terms of repeated use of the catalyst. As a component, it is preferable to have at least one selected from the group consisting of Mg, Ca, La, Re, Fe, Zn, Al, In, Sn, Pb, P, Sb, Bi and F other than tungsten, La, It is particularly preferable to contain at least one selected from the group consisting of Zn, Al, Sn and Pb.

As a method for supporting a quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms on a porous carrier, a polysiloxane having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms can be used. A quaternary ammonium salt of an oxometalate anion is dispersed in an organic solvent and then activated with an oxidizing agent. Thereafter, a porous carrier is added to the dispersion and impregnated. After impregnation, the organic solvent is distilled off to obtain a porous carrier carrying a quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms.
The quaternary ammonium salt of the polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms is preferably added in an amount of 3 to 50 parts by weight with respect to 100 parts by weight of the porous carrier, It is particularly preferable to add parts by weight.
The organic solvent is preferably a halogenated hydrocarbon solvent, and more preferably dichloromethane or 1,2-dichloroethane.
The oxidizing agent is preferably hydrogen peroxide.

As a porous carrier for supporting a quaternary ammonium salt of a polyoxometalate anion, a porous carrier to be used in the case of containing another atom described in “0024” in the case of a catalyst using a tungsten species And a quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms. For example, a method of supporting other atoms on a porous carrier in advance and further supporting a quaternary ammonium salt of a polyoxometalate anion, or supporting other atoms on a porous carrier together with a quaternary ammonium salt of a polyoxometalate anion. And a method of further supporting other atoms after a quaternary ammonium salt of a polyoxometalate anion is supported on a porous carrier.
The amount is preferably 0.01 parts by weight or more, more preferably 0.1 parts by weight or more, and preferably 1000 parts by weight or less, based on 100 parts by weight of the quaternary ammonium salt of the polyoxometalate anion. More preferably, it is 500 parts by weight or less.

  The amount of the catalyst used in the production method of the present invention is an ethylenic compound in the compound having at least one ethylenic double bond which is a reaction substrate for the metal species (for example, tungsten species) of the polyoxometalate anion in the catalyst. The molar ratio of double bonds (number of moles of ethylenic double bonds in reaction substrate / number of moles of metal species of polyoxometalate anion (for example, tungsten species)) is 1/1 to 100000/1. It is preferable that it is 1/1 to 10000/1 or less.

  In the production method of the present invention, water and / or an organic solvent can be used as necessary. As the organic solvent, one kind or two or more kinds can be used, and it does not react with a compound having at least one ethylenic double bond as a reaction substrate, an oxidizing agent such as hydrogen peroxide, or an epoxy compound produced. Those are preferred. Examples of such organic solvents include methanol, ethanol, normal propanol or isopropanol, normal butanol, isobutanol, 2-butanol, t-butanol, etc. Monohydric alcohol solvents, polyhydric alcohol solvents such as ethylene glycol, propylene glycol, glycerin, ether solvents such as ethyl ether, isopropyl ether, dioxane, tetrahydrofuran, ethyl acetate, formic acid ester or acetate ester of polyhydric alcohol, dimethyl carbonate Ester solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, ketone solvents such as acetylacetone, nitrogen compound solvents such as nitriles such as dimethylformamide and acetonitrile, triethyl phosphate, diethyl phosphate Phosphorus compound solvents such as phosphates such as xylyl, halogenated hydrocarbon solvents such as chloroform, dichloromethane, 1,2-dichloroethane, aliphatic hydrocarbons such as normal hexane and normal heptane, aromatics such as toluene and xylene Hydrocarbon solvents and cyclic hydrocarbons such as cyclohexane and cyclopentane are preferred.

  Among the above solvents, it is preferable to use water, an alcohol solvent having 1 to 4 carbon atoms, dimethyl carbonate, 1,2-dichloroethane, acetonitrile, dimethylformaldehyde, or a mixture thereof. In the case of using water or an aqueous solvent containing a solvent that is further soluble in water if necessary, a phase transfer catalyst and a surfactant can be coexistent.

  As reaction conditions in the production method of the present invention, the reaction temperature may be from −20 ° C. to the reflux temperature of the solvent, preferably 0 to 80 ° C., and more preferably 40 to 70 ° C. or less. The reaction time is preferably several minutes or more, more preferably 30 minutes or more, preferably within 48 hours, and more preferably within 24 hours.

The present invention will be described in more detail with reference to the following examples. However, the present invention is not limited to these examples.
In the present example and comparative example, it was determined by measuring under the following conditions using gas chromatography (manufactured by Shimadzu Corporation, GC2010).
Measurement conditions / column: InertCap Wax
Carrier gas: Nitrogen Measurement temperature: vaporization chamber 250 ° C., column 35 ° C. up to 250 ° C. at 10 ° C./min, detector 250 ° C.

Preparation of the catalyst _{1 ([C 16 H 33 BnMe} 2 N] 3 PW 4 O 24 / Zn-SnO 2)
After adding 100 mL of 1.6 mM Zn (NO ₃ ) aqueous solution to 33.2 mmol of SnO ₂ and stirring at room temperature for 1 hour, the solvent was distilled off at 50 ° C. using an evaporator. Thereafter, for 2 hours at 200 ° C., which was used as a Zn-SnO _2.
Next, after adding 68 mmol of 35 wt% hydrogen peroxide water to 10 mmol of H ₂ WO ₄ and stirring at 60 ° C. for 2 hours, adding 2.6 mmol of 75 wt% phosphoric acid and further diluting with 20 ml of ion-exchanged water, For 30 minutes. Thereafter, a solution of 7.5 mmol of [C ₁₆ H ₃₃ BnMe ₂ N] Cl dissolved in 20 mL of dichloromethane was added dropwise over 50 minutes, followed by stirring at room temperature for 30 minutes. After stirring, the reaction solution was transferred to a separatory funnel and the dichloromethane phase was recovered. The recovered organic phase was dried over sodium sulfate, sodium sulfate was removed by filtration, and dichloromethane was distilled off under reduced pressure. After dissolving 0.76 g of the solid obtained after distilling off dichloromethane in 50 mL of dichloromethane, adding 2.5 mmol of 35 wt% aqueous hydrogen peroxide, adding 5.0 g of Zn-SnO ₂ synthesized earlier, For 1 hour. Then, it was made to dry with an evaporator. The catalyst thus prepared is hereinafter referred to as _{[C 16 H 33 BnMe 2 N} ] 3 PW 4 O 24 / Zn-SnO 2.

Preparation of the catalyst Example _{2 ([C 18 H 37 BnMe} 2 N] 3 PW 4 O 24 / Zn-SnO 2)
The catalyst was prepared in the same manner as in Catalyst Production Example 1 except that [C ₁₆ H ₃₃ BnMe ₂ N] Cl was changed to [C ₁₈ H ₃₇ BnMe ₂ N] Cl, and [C ₁₈ H ₃₇ BnMe ₂ N] ₃ PW ₄ the O ₂₄ / Zn-SnO ₂ was produced.

Catalyst production example 3 ([(C ₁₈ H ₃₇ ) ₂ Me ₂ N] ₃ PW ₄ O ₂₄ / Zn-SnO ₂ )
Production Example 1 of the catalyst, was prepared similarly except for changing the _{[C 16 H 33 BnMe 2 N} ] Cl to _{[(C 18 H 37) 2} Me 2 N] Cl, [(C 18 H 37) 2 Me ₂ N] ₃ PW ₄ O ₂₄ / Zn—SnO ₂ was produced.

Catalyst production example 4 ([(C ₈ H ₁₇ ) ₃ MeN] ₃ PW ₄ O ₂₄ / Zn-SnO ₂ )
The catalyst was produced in the same manner as in Catalyst Production Example 1 except that [C ₁₆ H ₃₃ BnMe ₂ N] Cl was changed to [(C ₈ H ₁₇ ) ₃ MeN] Cl, and [(C ₈ H ₁₇ ) ₃ MeN] ₃ It was produced _{PW 4 O 24 / Zn-SnO} 2.

Preparation of Catalyst _{5 ([C 16 H 33 Me} 3 N] 3 PW 4 O 24 / Zn-SnO 2)
The catalyst was prepared in the same manner as in Catalyst Production Example 1 except that [C ₁₆ H ₃₃ BnMe ₂ N] Cl was changed to [C ₁₆ H ₃₃ Me ₃ N] Cl, and [C ₁₆ H ₃₃ Me ₃ N] ₃ PW ₄ the O ₂₄ / Zn-SnO ₂ was produced.

Catalyst production example 6 ([(C ₆ H ₁₃ ) ₄ N] ₃ PW ₄ O ₂₄ / Zn—SnO ₂ )
The catalyst was prepared in the same manner as in Catalyst Production Example 1 except that [C ₁₆ H ₃₃ BnMe ₂ N] Cl was changed to [(C ₆ H ₁₃ ) ₄ N] Cl, and [(C ₆ H ₁₃ ) ₄ N] ₃ It was produced _{PW 4 O 24 / Zn-SnO} 2.

Examples 1 to 5 and Comparative Example 1
[Epoxidation reaction of diallyl ether]
Using the catalysts obtained in Catalyst Production Examples 1 to 6, 0.18 g of catalyst, 5.00 mmol of diallyl ether, 1.00 mmol of 35 wt% aqueous hydrogen peroxide solution and 3 of dimethyl carbonate in a glass container equipped with a stirrer 0.000 mL was charged, and the reaction vessel was heated to 60 ° C. and stirred for 4 hours. After the reaction, the product and diallyl ether were quantified by gas chromatography, and hydrogen peroxide was quantified by iodine titration. The results are shown in Table 1.

Examples 6-8
[Reuse experiment in epoxidation of diallyl ether]
Using the catalysts obtained in Catalyst Production Examples 1 to 3, the first reaction was carried out in a glass container equipped with a stirrer 0.88 g of catalyst, 50.0 mmol of diallyl ether, 10.0 mmol of 35 wt% aqueous hydrogen peroxide and 30.0 mL of dimethyl carbonate was charged. In the second reaction, the catalyst used in the first reaction was recovered by filtration, and 0.60 g of catalyst, 17.2 mmol of diallyl ether, 3.40 mmol of hydrogen peroxide aqueous solution, and 10.0 mL of dimethyl carbonate were charged. . In each case, the reaction vessel was heated to 60 ° C. and stirred for 4 hours. After the reaction, the product and diallyl ether were quantified by gas chromatography, and hydrogen peroxide was quantified by iodine titration. The results are shown in Table 2.

In Tables 1 and 2, the yield is based on the number of moles of H ₂ O ₂ supplied to the reaction system, based on the mole% of the produced epoxy compound [(number of moles of epoxy reaction product / mol of H ₂ O ₂ The H ₂ O ₂ utilization rate is the mol% of the generated oxidation reaction product based on the number of moles of H ₂ O ₂ consumed by the reaction [(number of moles of oxidation reaction product). / a consumption moles × 100 of _H 2 _{O 2} was, the number of moles of consumed _H 2 _{O 2} is [(moles of _H 2 _{O 2} is supplied to the reaction system) - (residual _H 2 _{O 2} The iodine titration method was used to determine the amount of H ₂ O ₂ remaining in the reaction system.

In Table 1, it can be seen that Examples 1 to 5 have higher reaction yield and H ₂ O ₂ utilization rate than Comparative Example 1, and polyoxo having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms. It has been shown that a porous support carrying a quaternary ammonium salt of a metalate anion has a high catalytic activity.
In Table 2, Examples 6 to 8 show that high catalytic activity is maintained even when the porous carrier is repeatedly used.
From Tables 1 and 2, quaternary ammonium salts of polyoxometalate anions having saturated or unsaturated hydrocarbon groups having 8 or more carbon atoms and aralkyl groups (benzyl groups) described in Production Examples 1 and 2 of the catalyst It has been shown that the porous carrier carrying the catalyst has a particularly high catalytic activity and maintains a high catalytic activity even when it is repeatedly used.

The production method of the present invention can produce an epoxy compound in a high yield and improve the effective utilization rate of the oxidizing agent, and the catalyst can be easily recovered. Therefore, this invention is a useful method as a manufacturing method of the epoxy compound for supplying as an intermediate body and raw material used in manufacture of various industrial products.

Claims (5)

  Epoxidizing a compound having at least one ethylenic double bond in the presence of a porous carrier carrying a quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms The manufacturing method of the epoxy compound characterized by the above-mentioned.   The method for producing an epoxy compound according to claim 1, wherein the quaternary ammonium salt of a polyoxometalate anion having a saturated or unsaturated hydrocarbon group having 8 or more carbon atoms has an aralkyl group.   The method for producing an epoxy compound according to claim 1, wherein the polyoxometalate anion has an atom selected from molybdenum, tungsten, vanadium and niobium.   The method for producing an epoxy compound according to claim 1, wherein the polyoxometalate anion contains silicon or phosphorus. The method for producing an epoxy compound according to any one of claims 1 to 4, wherein the compound having at least one ethylenic double bond is a compound having an allyloxy group.