JP2003146977A - Method for producing epoxy compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for catalytically oxidizing a compound having at least one ethylenic double bond with an oxidizing agent such as hydrogen peroxide to produce the corresponding epoxy compound, by which the epoxy compound can be produced in a high yield and at the improved effective utilization rate of the oxidizing agent. SOLUTION: This method for producing the epoxy compound, comprising oxidizing the compound having at least one ethylenic double bond with the oxidizing agent is characterized by using a heteropolyoxometalate anion salt which has two defective structure sites and contains silicon atom as a heterogeneous atom, as a homogeneous catalyst.

Description

Detailed Description of the Invention

[0001]

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

[0002]

BACKGROUND OF THE INVENTION Epoxy compounds (epoxides) are compounds useful as intermediates and raw materials used in the production of various industrial products. For example, as a production example of an industrial product using an epoxy compound as an intermediate compound, ethylene oxide is converted to ethylene glycol or polyethylene glycol, and an alcohol is alkoxylated with propylene oxide to obtain polypropylene polyether or the like. Polyether polyols have been formed. The industrial products produced in this way are consumed in large quantities in the production of polyurethanes and synthetic elastomers. Epoxy compounds are also important intermediates in the production of alkylene glycols such as propylene glycol and dipropylene glycol and alkanolamines, which are one of the important industrial products as raw materials for solvents and surfactants.

As a method for synthesizing an epoxy compound, there is an epoxidation reaction of a compound having an ethylenically unsaturated double bond such as an olefin, which is one of industrially important chemical conversion methods. In this synthetic method, 1
One oxygen atom is added to the carbon-carbon double bond to synthesize an epoxy compound.For example, as a method for producing ethylene oxide from ethylene, a method using a silver catalyst is used as a method for producing propylene oxide from propylene. The chlorohydrin method and the Halcon method using organic hydroperoxide are well known. Although these methods have been industrially put to practical use, for example, the chlorohydrin method has a problem that low-concentration salt vapor is generated.

In such an epoxidation reaction, olefin is converted into an epoxy compound by using hydrogen peroxide as an oxidizing agent, but a poly atom is coordinated to the hetero atom via oxygen with the hetero atom as the center. The use of structured heteropolyoxometalates as catalysts has been studied. As the heteropolyoxometallate used as a catalyst, a catalyst having a deficient structure in which an atom that should be present in the crystal structure is missing and containing a metal element, that is, one in which a poly atom is substituted with another metal element is a catalyst. It is known to exert an action. Usually, a heteropolyoxometalate containing such a metal is used, but there is room for improvement to enhance the catalytic activity in the epoxidation reaction.

The following studies have been conducted on heteropolyoxometalates having a defective structure.
J. Inorg. Nucl. Chem. , 39 [12]
(1977) (English) p. 2151-2154 describes an ultraviolet-visible absorption spectrum analysis of an isomer obtained by isomerizing a deficient undecatungstosilicate in which a tungsten atom, which is a poly atom, is replaced with an iron or vanadium atom in an aqueous solution. There is. Inorg. Chem. , 2
5 [13] (1986) (US) p. 2124-2119
In this study, potassium decatungstosilicate or rubidium salt lacking two tungsten atoms, which are poly atoms, was synthesized, and its crystal structure was analyzed by infrared absorption spectrum (I
R), cyclic voltammetry (CV), X-ray analysis and nuclear magnetic resonance (NMR) analysis.
Stability in aqueous solution is described.

Tetrahedron Letter
s, 29 [7] (1988) (English) p. 823-826
Describes that in the oxidation of cyclohexene with hydrogen peroxide, undecatungstosilicic acid tetrabutylammonium salt lacking one tungsten atom, which is a poly atom, is used as a homogeneous catalyst. In this oxidation reaction, 1,2-dichloroethane is used as an organic solvent, but the oxidizing agent is present in the aqueous phase, and the catalyst is dissolved in the second phase which is insoluble in water. Cyclohexene is known as a substrate that is easily oxidized, and it is considered that the reaction proceeds even if the catalytic activity is low. Moreover, the mechanism of this reaction is not clearly understood.

Acta Cryst. , C52 (199
6) (English) p. 757-759 describes the crystal structure of decatungsto cesium silicate decahydrate 9 hydrate lacking two polyatomic tungsten atoms.
Chem. Mater. , 13 [3] (2001)
(US) p. No. 1074-1081 describes that decatungst silicate clusters lacking two tungsten atoms, which are poly atoms, are bound to silica for immobilization. However, the epoxidation yield of cyclooctene is 0.12% per mole of W atom after reaction for 24 hours.
It is very difficult to use industrially. Further, in these studies, since the application to the epoxidation reaction of olefins, which is an industrially important method for producing an epoxy compound, has not been sufficiently investigated, heteropolyoxometallates can be used in the epoxidation reaction. There was room to devise a suitable catalyst.

[0008]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above circumstances, and a compound having at least one ethylenic double bond is catalytically oxidized using an oxidizing agent such as hydrogen peroxide. Accordingly, it is an object of the present invention to provide a method for producing a corresponding epoxy compound, which is capable of producing an epoxy compound in a high yield and with an improved effective utilization rate of an oxidizing agent.

[0009]

Means for Solving the Problems As a result of various studies on the method for producing an epoxy compound by oxidizing a compound having at least one ethylenic double bond with an oxidizing agent, the present inventors have found that heteropolyoxometalate Focusing on the industrial usefulness of the method used for the catalyst, a homogeneous catalyst containing a salt of a heteropolyoxometallate anion having two deficient structural sites and a hetero atom being a silicon atom is suitable for the above oxidation reaction. It has been found that, in particular, such a catalyst exerts an excellent catalytic action even if it does not contain a metal element other than a poly atom. In other words, it was conventionally thought that a structure in which the poly atom was replaced with another metal element was good for the heteropolyoxometalate to exert its catalytic action. It has been found that those having the above-mentioned properties and not containing other metal elements exert a catalytic action, and those having two defect structure sites with two missing polyatoms have one defect structure site or three defect structure sites. It has been found that it exerts a superior catalytic action as compared with those having it. Thus, the heteropolyoxometallate having a two-deficient structural site exceeds the range expected from the conventional state of the art,
It has been conceived that it exerts a functioning effect as a catalyst in the epoxidation reaction. The homogeneous catalyst here is a catalyst in which the reactant phase and the catalyst phase act in a uniform phase. Further, as such a catalyst, it is preferable that the poly atom is a tungsten and / or molybdenum atom, that the structure of the heteropolyoxometalate anion is a Keggin type, and that the pH at the time of preparing the catalyst is specified. The present invention has also been completed, and has reached the present invention.

That is, the present invention is a method for producing an epoxy compound by oxidizing a compound having at least one ethylenic double bond with an oxidizing agent, wherein the above-mentioned method for producing an epoxy compound has a bi-deficient structural site. However, it is a method for producing an epoxy compound, wherein a salt of a heteropolyoxometallate anion in which a hetero atom is a silicon atom is used as a homogeneous catalyst. In such a production method, the epoxy compound is produced in a homogeneous system. The present invention is described in detail below.

The homogeneous catalyst used in the method for producing an epoxy compound of the present invention has a heteroatom which is a silicon atom, and a heteropolyoxometametal in which a metal element as a polyatom is coordinated to the heteroatom through an oxygen atom. It contains a salt of the rate anion, but is characterized by having two deficient structural sites in which two polyatoms that should be in the crystal structure are missing. The following effects (1) to (8) and the like are mainly mentioned as the effects of such a catalyst.

That is, (1) the isomerization reaction for producing aldehydes, ketones, etc. is unlikely to occur, and the selectivity to the epoxy compound is high, and (2) the epoxy compound of the desired product is ring-opened with water. With glycols produced,
A small amount of glycol monoalkyl ethers or the like formed by reaction with a compound having at least one ethylenic double bond as a reaction substrate, which also results in extremely high selectivity to epoxy compounds, ( 3) Even if a large amount of water or alcohol is present in the reaction system, side reactions such as isomerization reaction and ring-opening reaction are less likely to occur, and the selectivity of the epoxy compound is increased, so that low concentrations of hydrogen peroxide, etc. It is possible to use an oxidant, (4) When the oxidant is hydrogen peroxide, decomposition into oxygen is small, and the effective utilization rate of the oxidant for an epoxy compound is high. Even if the ratio of hydrogen peroxide used to a compound having at least one ethylenic double bond is low, the reaction activity is high and the selectivity is good, (6) The catalyst activity is high, (7) Ketones less acetone or the like produced as a by-product not easily available organic peroxides produced from acetone, the decreases danger of explosion,
(8) The consumption of an oxidizing agent such as hydrogen peroxide is less likely to occur due to the accumulation of organic peroxide during the reaction.

The heteropolyoxometallate anion has a crystal structure in which 10 polyatoms are coordinated to a silicon atom, which is a heteroatom, through oxygen, and one kind or two or more kinds can be used. Examples of the poly atom include atoms such as molybdenum, tungsten, vanadium, and niobium, and of these, molybdenum and / or tungsten atoms are preferable. That is, in the present invention, the heteropolyoxometallate anion is represented by the following general formula (1); [SiM ₁₀ O ₃₆ ] ^q- (1) (wherein M is the same or different and represents a molybdenum or tungsten atom). And q is a positive integer.) It is preferably a Keggin-type heteropolyoxometallate anion. Note that q will be determined by the valence of M. As the form of the above-mentioned heteropolyoxometallate anion, a two-deficient Keggin type is preferable, and a γ type is more preferable. For example, Inorganic
Syntheses, 27, p88, J. Mol. Am. Che
m. Soc. , 120, p9267.

Examples of the counter cation forming the salt of the heteropolyoxometallate anion include a proton, an alkali metal cation (lithium ion, sodium ion, potassium ion, rubidium ion, cesium ion), and an alkaline earth metal cation (beryllium). Ion, magnesium ion, calcium ion, strontium ion, barium ion) and quaternary ammonium salt (tetramethylammonium salt, tetraethylammonium salt, tetrapropylammonium salt, tetrabutylammonium salt, tributylmethylammonium salt, trioctylmethylammonium salt) Salt, trilaurylmethylammonium salt, benzyltrimethylammonium salt, benzyltriethylammonium salt, benzyltributylammonium Salt), quaternary phosphonium salts (tetramethyl phosphonium salt, tetraethyl phosphonium salt, tetrapropyl phosphonium salts,
A cation containing an organic cation such as a tetrabutylphosphonium salt, a tetraphenylphosphonium salt, an ethyltriphenylphosphonium salt, a benzyltriphenylphosphonium salt), a quaternary arcene, or a cetylpyridinium salt is preferable. . One or two cations
More than one type can be used.

The amount of the homogeneous catalyst used is, for example, at least 1 ethylenic double bond as a reaction substrate.
Molar ratio to the ethylenic double bond in the compound having (number of moles of the ethylenic double bond in the reaction substrate / two deficient structural sites, a salt of a heteropolyoxometallate anion in which the heteroatom is a silicon atom) The number of moles) is 1000
It is preferably set to 00/1 to 1/10.
More preferably, it is 10000/1 to 1/1.

As a method for preparing the salt of the heteropolyoxometallate anion, for example, Inorganic
synthesizes, 27, p. 88 is suitable, and the salt of the heteropolyoxometalate anion thus produced is dissolved in ion-exchanged water to form an aqueous solution, and the pH is adjusted to be suitably used as a catalyst in the present invention. You can get what you can. The catalyst in the present invention has pH dependency, and the pH of the aqueous solution of the salt of the heteropolyoxometallate anion is preferably -2.0 to 10.0. More preferably, it is -1.0 to 7.0. More preferably, it is 0-5.0.

The homogeneous catalyst of the present invention preferably comprises a salt of a heteropolyoxometalate anion as an essential component, which is the main component, but as long as the effects of the present invention are exhibited, the impurities produced in the catalyst preparation process are included. Alternatively, it may contain other components. The crystal structure of the salt of the heteropolyoxometalate anion can be determined or estimated by X-ray analysis, elemental analysis, FT-IR spectroscopy measurement, or the like.

The reaction substrate, oxidizing agent, production conditions and the like in the method for producing an epoxy compound of the present invention will be described below. Examples of the compound having at least one ethylenic double bond which is a reaction substrate used in the present invention include:
It may be an acyclic compound or a cyclic organic compound, and for example, one or more of hydrocarbons, esters, alcohols, ethers, halogen-substituted hydrocarbons and the like can be used. 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-etradecene, 1-pentadecene, 1
-Heptadecene, 1-octadecene, 1-nonadecene,
1-Eicosene Propylene trimers and tetramers, linear alkene having an ethylenic double bond at the terminal such as 1,3-butadiene; 2-butene, 2-octene, 2
-Methyl-2-hexene, 2,3-dimethyl-2-butene and other alkenes and branched alkenes having an ethylenic double bond in the molecule; cyclopentene, cyclohexene, 1
-Phenyl-1-cyclohexene, 1-methyl-1-cyclohexene, cycloheptene, cyclooctene, cyclodecene, cyclopentadiene, cyclodecatriene,
Alicyclic olefinic hydrocarbons such as cyclooctadiene, dicyclopentadiene, methylenecyclopropane, methylenecyclopentane, methylenecyclohexane, vinylcyclohexane, vinylcyclohexane, cyclooctene, norbornene and the like can be mentioned. Among these, unsaturated hydrocarbons having 2 to 15 carbon atoms are preferable. More preferably, it is an unsaturated hydrocarbon having 2 to 12 carbon atoms.

The compound having at least one ethylenic double bond may also be, for example, --COOH, --CN or C.
Groups such as OOR, -OR (R represents an alkyl, cycloalkyl, aryl or allylalkyl substituent), aryl, allylalkyl, halogen, nitro, sulfonic acid, carbonyl (eg ketone, aldehyde), hydroxyl, ether. It may have a group. Examples of such compounds include allyl alcohol, allyl chloride,
Examples thereof include allyl methyl ether, allyl vinyl ether, diallyl ether, allyl phenyl ether, methyl methacrylate, acrylic acid and the like.

As the compound having at least one ethylenic double bond, an aryl compound having a carbon-carbon double bond and having 6 or more carbon atoms can be used. Examples of such compounds include styrene and α
-Substituted styrenes such as methylstyrene, divinylbenzenes, stilbenes, arkenes; amines having a carbon-carbon double bond, thiols, sulfides, disulfides, compounds having Se, Te, Sb and As , Phosphines, phosphites and the like.

Examples of the oxidizing agent in the present invention include:
Those capable of generating oxygen ions, oxygen radicals, peroxides and superperoxides can be used, and examples thereof include hydrogen peroxide, t-butyl peroxide, organic peroxides such as peracetic acid, a mixed gas of oxygen and hydrogen, Nitrous oxide,
Iodosylbenzene and the like are preferable. Among these,
Preference is given to using hydrogen peroxide.

The above-mentioned hydrogen peroxide is an ideal oxidizing agent if the reaction is selective, but conventionally, when the water generated in the reaction system causes ring-opening of the generated epoxy compound, resulting in a low yield. Alternatively, when the price of the produced epoxy compound is low, hydrogen peroxide becomes relatively expensive and the manufacturing cost may be relatively high. However, in the present invention, the selectivity to the epoxy compound is high and the hydrogen peroxide is high. These problems can be solved because the effective utilization rate of the epoxy compound is high and the productivity of the epoxy compound by the catalyst is high.

In the method for producing an epoxy compound of the present invention, when hydrogen peroxide is used as an oxidizing agent, the practical use forms of hydrogen peroxide are 0.01 to 70% by weight aqueous solution and alcohols. Is preferred, but 1
00% hydrogen peroxide can also be used.

The amount of the oxidizing agent used is a molar ratio to the ethylenic double bond in the compound having at least one ethylenic double bond as the reaction substrate (the number of moles of the ethylenic double bond in the reaction substrate). / Mol of oxidizing agent) is 10
It is preferably set to 0/1 to 1/100.
More preferably, it is 10/1 to 1/50.

As the reaction method in the production method of the present invention, it is preferable to carry out the epoxidation reaction by bringing a catalyst into contact with a compound having at least one ethylenic double bond and an oxidizing agent. Further, it is preferable from the viewpoint of reaction activity that the catalyst, the compound having at least one ethylenic double bond and the oxidizing agent are dissolved in a solvent to carry out in a liquid phase homogeneous system.

Water and / or an organic solvent is used as the solvent. 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 which is a reaction substrate, an oxidizing agent such as hydrogen peroxide, or the generated epoxy compound. Those are preferable. Examples of the organic solvent include, for example, methanol, ethanol, normal or isopropanol, tertiary butanol, etc. having 1 to 6 carbon atoms, 1, 2, 3
-Grade monohydric alcohols; polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; oligomers obtained by ring-opening ethylene oxide and propylene oxide such as diethylene glycol and triethylene glycol;
Ethyl ether, isopropyl ether, dioxane,
Ethers such as tetrahydrofuran; esters such as ethyl acetate, formic acid esters or acetic acid esters of polyhydric alcohols; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetylacetone; nitrogen compounds such as dimethylformamide, nitromethane, nitriles; phosphorus Phosphorus compounds such as phosphoric acid esters such as triethyl acid acid and diethylhexyl phosphate; halogenated hydrocarbons such as chloroform, dichloromethane and ethylene dichloride; aliphatic hydrocarbons such as normal hexane and normal heptane;
Examples thereof include aromatic hydrocarbons such as toluene and xylene; alicyclic hydrocarbons such as cyclohexane and cyclopentane.

Among the above solvents, water, alcohols having 1 to 4 carbon atoms, 1,2-dichloroethane, heptane, toluene, xylene, chlorobenzene, acetonitrile, benzonitrile, dimethyl sulfoxide, dimethylformamide, etc., and mixtures thereof. Is preferably used. When water is present, it is possible to coexist a phase transfer catalyst and a surfactant depending on the case.

The reaction system in the above epoxidation reaction is preferably neutral to acidic. In the present invention, the reaction system can be made acidic by using the above catalyst, but an acidic substance may be added to the reaction system. Examples of the acidic substance include Bronsted acid, Lewis acid and the like, and one kind or two or more kinds can be used.
Examples of Bronsted acids include mineral acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, boric acid; acetic acid, benzoic acid, formic acid,
Organic acids such as trichloroacetic acid, trifluoromethanesulfonic acid, and sulfonic acid; inorganic acids such as zeolites and mixed oxides are suitable, and examples of Lewis acids include aluminum chloride, ferric chloride, boron chloride compounds, and chlorides. Preferred are antimony compounds, stannic chloride, antimony fluoride, compounds of zinc and titanium, zeolites, mixed oxides and the like. Furthermore, inorganic or organic acid salts can be used.

As the reaction conditions in the above epoxidation reaction, for example, the reaction temperature is preferably 0 to 250 ° C.,
More preferably, the temperature is from room temperature to 180 ° C. The reaction time is
Several minutes to 150 hours are preferable, more preferably several minutes to 150 hours.
48 hours. The reaction pressure is preferably atmospheric pressure to 2 × 10 ⁷ Pa, more preferably atmospheric pressure to 5 × 10 ⁶ Pa. The reaction can also be carried out under reduced pressure.

The method for producing an epoxy compound of the present invention is a method for producing an epoxy compound in a high yield and with an improved effective utilization rate of an oxidizing agent, and is an intermediate or raw material used in the production of various industrial products. Is an epoch-making method as a production method for supplying an epoxy compound which is a useful compound. Examples of the epoxy compound obtained by the production method of the present invention include ethylene oxide which is a raw material of ethylene glycol and polyethylene glycol,
Although propylene oxide, which is a raw material for obtaining polyether polyols, is industrially important, these epoxy compounds are propylene glycol, diethylene, which is one of the important industrial products as a raw material for solvents and surfactants. It is also an important intermediate in the production of alkylene glycols such as propylene glycol and alkanolamines.

[0031]

The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

(Catalyst Preparation Method) A-1 Two-defective heteropolyoxometallate tetrabutylammonium salt (hereinafter abbreviated as POMTBA) (pH at catalyst preparation: 0.
5) Inorganic synthesises vol. Two
7, p88, 4.5 g of the two-deficient Keggin-type K ₈ [γ-SiW ₁₀ O ₃₆ ] 12H ₂ O prepared by the method described in p.
Dissolve in 1 liter of deionized water at room temperature, and add pH with nitric acid solution.
Was adjusted to 0.5. 3.3 g of tetrabutylammonium bromide (hereinafter abbreviated as TBABr) was added thereto as a solid, and stirring was continued for 15 minutes. The precipitate formed was filtered and the filtrate was dried for 3 hours at room temperature. 2.5 g of the filtered product was dissolved in 15 ml of acetonitrile, 300 ml of ion-exchanged water was added thereto, and the mixture was stirred for 30 minutes in ice water. The deposited precipitate was filtered, and the filtered product was dried at room temperature for 3 hours to obtain a purified solid (A-1).

A-2 to A-10 Purified solid A-2 was prepared according to the preparation method of A-1 except that the pH was set to the values shown in Table 1 in the preparation method of the two-defective POMTBA A-1. ~ A-10 was obtained. In addition, in Table 1,
The pH at the time of catalyst preparation means the pH just before the addition of TBABr.
H.

[0034]

[Table 1]

B-1 One-defective POMTBA (pH at the time of catalyst preparation: 1.0) Inorganic Syntheses vol. Two
7, p91 one defective type Keggin _{K 8 [β 2 -SiW 11 O} 39] 14H 2 O in 4.8g, prepared by the method described in the 6
It was dissolved in 0 ml of ion-exchanged water at room temperature, and the pH was adjusted to 1.0 with a nitric acid aqueous solution. 3.3g of TBABr there
Was added as a solid and stirring was continued for 15 minutes. The precipitate formed was filtered and the filtrate was dried for 3 hours at room temperature. 2.5 g of the filtered product was dissolved in 15 ml of acetonitrile, 300 ml of ion-exchanged water was added thereto, and the mixture was stirred for 30 minutes in ice water. The deposited precipitate was filtered and the filtered product was dried at room temperature for 3 hours to obtain a purified solid (B-1).

B-2 to B-5 Purified solids B-2 to B-5 were prepared according to the method for preparing B-1 to deficient POMTBA B-1 except that the pH was set to the value shown in Table 2. B-5 was obtained. In addition, in Table 2, the pH at the time of catalyst preparation is the pH immediately before the addition of TBABr.

[0037]

[Table 2]

C-1 Tri-deficient POMTBA (pH at the time of catalyst preparation: 1.0) Inorganic synthesises vol. Two
1.2 g of three-deficient Keggin-type Na ₁₀ [α-SiW ₉ O ₃₄ ] prepared by the method described in p.7, p87 is dissolved in 20 ml of ion-exchanged water at room temperature, and the pH is adjusted to 1. with an aqueous nitric acid solution.
Adjusted to 0. 1.1 g of TBABr was added thereto as a solid, and stirring was continued for 15 minutes. The precipitate formed was filtered and the filtrate was dried for 3 hours at room temperature. 1.0 of filtrate
g was dissolved in 5 ml of acetonitrile, 160 ml of ion-exchanged water was added thereto, and the mixture was stirred in ice water for 30 minutes. The deposited precipitate was filtered and the filtered product was dried at room temperature for 3 hours to obtain a purified solid (C-1).

C-2 to C-4 Purified solids C-2 to C-4 were prepared according to the C-1 preparation method except that the pH was set to the values shown in Table 3 in the preparation method for the three-defective POMTBA C-1. C-4 was obtained. In addition, in Table 3, the pH at the time of catalyst preparation is the pH immediately before the addition of TBABr.

[0040]

[Table 3]

D-1 Two-deficient heteropolyoxometalate cesium salt (hereinafter abbreviated as POMCs) (pH at the time of catalyst preparation: 1.0) Inorganic synthesises vol. Two
7, p88 two defective Keggin type K ₈ prepared by the method described in _{[γ-SiW 10 O 36]} 20 a 12H ₂ O 1.5g of
Dissolve it in ml of deionized water at room temperature and p.
The H was adjusted to 1.0. 0.84 of cesium chloride there
g was added as a solid and stirred for 15 minutes. The produced precipitate was filtered and dried at room temperature for 3 hours to obtain a filtered material D-1.

D-2 to D-4 In the method for preparing the two-deficient POMCs D-1, the filtrates D-2 to D were prepared according to the D-1 preparation method except that the pH was set to the value shown in Table 4. -4 was obtained. In Table 4, the pH at the time of preparing the catalyst is the pH immediately before the addition of cesium chloride.

[0043]

[Table 4]

Example 1 1-Butene Epoxidation Reaction A test tube with a lid was charged with 6 ml of acetonitrile and 7 μmol of A-1 (2-defective POMTBA) catalyst to dissolve the catalyst, and 1100 μmol of 35 wt% hydrogen peroxide was charged.
Cooled with water at 0 ° C. for 5 minutes. 1-Butene gas was bubbled into this solution at a flow rate of 83.5 ml / min for 3 minutes to dissolve 1-butene. This was reacted in a 40 ° C water bath for 2 hours. The product was analyzed and quantified by gas chromatography. The yield of the product was calculated from the ratio of the number of moles of hydrogen peroxide charged and the number of moles of the product. Product selectivity was calculated from the ratio of the total number of moles of product to the number of moles of each product.
Regarding the reaction results, the yield of 1,2-butene oxide (hereinafter abbreviated as BO) was 45.47%, and the selectivity to BO was 95.30%.

Examples 2 to 10 Instead of the A-1 catalyst in Example 1, A-2, A-3,
A-4, A-5, A-6, A-7, A-8, A-9, A
The epoxidation reaction of 1-butene was carried out using a -10 catalyst. The results after 2 hours of reaction time are summarized in Table 5. In addition, in Table 5, the pH at the time of catalyst preparation is the pH immediately before the addition of TBABr in the catalyst preparation.

Comparative Examples 1 to 5 One-defective POMTB in place of A-1 catalyst in Example 1
The epoxidation reaction of 1-butene was performed using the catalysts B-1, B-2, B-3, B-4, and B-5 which are A. The results after 2 hours of reaction time are summarized in Table 5.

Comparative Examples 6 to 9 In Example 1, three-defective POMTB was used instead of the A-1 catalyst.
The epoxidation reaction of 1-butene was performed using the C-1, C-2, C-3, and C-4 catalysts of A. The results after 2 hours of reaction time are summarized in Table 5.

From Table 5, it can be seen that the salt of the heteropolyoxometalate anion having a two-deficient structure site in a homogeneous catalyst has higher catalytic activity than that having a one- or three-deficiency structure site, and the selectivity of the epoxy compound is high. It can be seen that (the molar selectivity of BO) is high. In addition, the pH (T
The relationship between the pH immediately before the addition of BABr) and the butene oxide (BO) yield is shown in FIG. From FIG. 1 and Table 5, it can be seen that the catalyst activity depends on the pH at the time of catalyst preparation.

[0049]

[Table 5]

Example 11 Epoxidation reaction of allyl alcohol In a test tube with a lid, 6 ml of ion-exchanged water, D-1 (two deficient P
OMCs) 30 mg of catalyst was added to dissolve the catalyst, and 1000 μmol of allyl alcohol as a substrate, 35 wt%
Charge 200μmol of hydrogen peroxide, and 2 in a 32 ° C water bath.
Reacted for 4 hours. The product is analyzed by gas chromatography,
It was quantified. The yield of the product was calculated from the ratio of the number of moles of hydrogen peroxide charged and the number of moles of the product. Product selectivity was calculated from the ratio of the total number of moles of product to the number of moles of each product.

Examples 12 to 14 In Example 11, instead of the D-1 catalyst, two-defective POMC
The epoxidation reaction of allyl alcohol was carried out using the D-2, D-3, and D-4 catalysts of s. The results after 24 hours of reaction time are summarized in Table 6. In Table 6, the pH at the time of catalyst preparation is the pH immediately before the addition of cesium chloride in the catalyst preparation.

[0052]

[Table 6]

It can be seen from Table 6 that the salt of the heteropolyoxometalate anion having a two-deficient structure site in a homogeneous catalyst has a high catalytic activity and a high glycidol molar selectivity. Further, it can be seen that the catalytic activity depends on the pH at the time of preparing the catalyst.

[0054]

EFFECTS OF THE INVENTION The present invention is a method for producing an epoxy compound in a high yield and with an improved effective utilization rate of an oxidant because it has the above-mentioned constitution, and is used in the production of various industrial products. It is a useful method as a manufacturing method for supplying an epoxy compound as a body or a raw material.

[Brief description of drawings]

FIG. 1 is a graph showing a relationship between pH at the time of catalyst preparation and butene oxide (BO) yield in Examples.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Yasutaka Sumita             5-8 Nishiomitabicho, Suita City, Osaka Prefecture             Within Nippon Shokubai (72) Inventor Masahiro Wada             5-8 Nishiomitabicho, Suita City, Osaka Prefecture             Within Nippon Shokubai (72) Inventor Tetsutaka Mizuno             3-3-6-501 Hikarigaoka, Nerima-ku, Tokyo F term (reference) 4C048 AA01 BB07 BC02 CC01 UU03                       XX02                 4G069 AA06 BA27B BC59A BC60B                       BD05B BE01B BE17B BE32A                       BE32B CB73 DA02                 4H039 CA63 CC40

Claims (2)

[Claims] 1. A method for producing an epoxy compound by oxidizing a compound having at least one ethylenic double bond with an oxidizing agent, wherein the method for producing the epoxy compound has a bi-deficient structural site, and A process for producing an epoxy compound, which comprises using a salt of a heteropolyoxometallate anion having silicon atoms as a homogeneous catalyst. 2. The heteropolyoxometallate anion has the following general formula (1); [SiM ₁₀ O ₃₆ ] ^q- (1) (wherein M is the same or different and represents a molybdenum or tungsten atom. q is a positive integer, and is a Keggin-type heteropolyoxometallate anion represented by the formula (1).