JP5655483B2 - Production method of epoxy compound - Google Patents

Description

  The present invention relates to a novel process for producing an epoxy compound, and more particularly, an epoxy compound industrially useful as a raw material for a diol or a polyol in an aqueous medium containing an olefin, a secondary alcohol and molecular oxygen. The present invention relates to a method of producing a highly active, highly selective and safe product by reacting.

  Several methods are known about the manufacturing method of an epoxy compound, especially the manufacturing method of propylene oxide.

  For example, a chlorohydrin method in which propylene is passed through chlorohydrin is known. In the chlorohydrin method, a large amount of calcium chloride is produced as a by-product because chlorhydrin is dehydrochlorinated with lime milk, and this by-product calcium chloride is treated and discharged. There are problems such as high load.

  Further, a Halcon method is known in which propylene is oxidized using ethylbenzene hydroperoxide, which is a peroxide, as an oxidizing agent. According to this method, the oxygen element source of the epoxy compound is derived from oxygen atoms in the peroxide.

  Therefore, the Halcon method requires an equimolar amount or more of the peroxide to the epoxy compound to be produced. For this reason, there are problems in terms of safety and economy due to the use of a large amount of peroxide. Furthermore, by-product 1-phenylethanol is generally converted to styrene and sold as a by-product.

  As a method that does not require a large amount of by-product processing or sales, a method for producing an epoxy compound using hydrogen peroxide as a peroxide has been proposed (for example, see Patent Document 1). This method is known as a clean method because the by-product compound is water in addition to the epoxy compound.

  However, in the method proposed in Patent Document 1, hydrogen peroxide is required in an amount equivalent to or higher than that of the generated epoxy compound, so that a large amount of peroxide is necessary, and expensive peroxide is used. As a result, there were problems in safety and economy.

  Accordingly, a method for producing an epoxy compound that does not require the use of a highly dangerous peroxide in the production of an epoxy compound has been desired and proposed.

  For example, using a catalyst comprising a heteropoly compound peroxide and a noble metal compound, a method for producing an epoxy compound with propylene and molecular oxygen (see, for example, Patent Document 2), a porous metal oxide modified with a titanium compound and palladium There has been proposed a method for producing an epoxy compound by directly oxidizing propylene with molecular oxygen using a catalyst containing a catalyst (see, for example, Patent Document 3). However, in the method proposed in Patent Document 2, the peroxide of the heteropoly compound constituting the catalyst has a problem in the stability of the catalyst because it is poor in thermal stability. Further, in the method proposed in Patent Document 3, since the selectivity of the epoxy compound is as low as 55% at the maximum, there is still room for improvement for industrial use. Furthermore, although these methods do not use peroxides, they are reactions in organic solvents, so there is a high risk of leakage or fire, and caution is required during production. It had a problem.

  On the other hand, if an aqueous medium typified by water can be used as a solvent, it is much safer than the case where an organic solvent is used. Can be separated, and the medium is inexpensive.

  As a method for producing an epoxy compound that can use water as a solvent, for example, an epoxy compound is prepared by directly oxidizing an olefin with oxygen and hydrogen using a catalyst composed of a noble metal of group 8 to 10 of the periodic table and titanosilicate. Has been proposed (for example, see Patent Document 4).

JP 04-005028 A (see page 1) JP 2006-068622 A (see page 4) Japanese Patent No. 4002971 (see page 2) Japanese Patent Laid-Open No. 04-352771 (see claims)

  However, in the method proposed in Patent Document 4, the reaction efficiency to the epoxy compound is low, and since it is a reaction system in which hydrogen and oxygen coexist, it is necessary to take safety measures against the explosion, which is called a safety measure. It has a problem that requires a great deal of labor.

  Therefore, a novel process for producing an epoxy compound having high safety, high activity and high selectivity has been desired.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have reacted water with olefin, secondary alcohol and molecular oxygen in the presence of water-soluble palladium complex and crystalline titanosilicate using water as a solvent. The inventors have found that a novel method for producing an epoxy compound is a highly safe, highly active and highly selective method for producing an epoxy compound, and thus completed the present invention.

  That is, the present invention relates to a method for producing an epoxy compound characterized by reacting an olefin, a secondary alcohol and molecular oxygen in an aqueous medium in the presence of a water-soluble palladium complex and crystalline titanosilicate. is there.

  The present invention is described in detail below.

  In the production method of the present invention, the reaction is carried out in the presence of a water-soluble palladium complex and crystalline titanosilicate. Here, even if the reaction is carried out in the presence of only one of the water-soluble palladium complex and the crystalline titanosilicate, it does not constitute a method for producing an epoxy compound having excellent activity and the like.

  Any water-soluble palladium complex can be used as long as it belongs to the category of water-soluble palladium complexes. For example, the water-soluble palladium complex can be prepared from a nitrogen compound containing a palladium compound and a ligand. Is possible.

  As the palladium compound, any compound can be used as long as it belongs to the category of palladium compounds. For example, inorganic palladium compounds such as palladium chloride, palladium bromide, palladium nitrate, palladium sulfate; palladium acetate, tetraamminedichloropalladium, Organic palladium compounds such as bis (benzonitrile) dichloropalladium, dichlorobis (triphenylphosphine) palladium, tetrakis (triphenylphosphine) palladium, bis (dibenzylideneacetone) palladium, tris (dibenzylideneacetone) dipalladium, etc. These palladium compounds can be used alone or as a mixture of two or more. And since it is excellent in especially the solubility to a solvent and the reactivity at the time of epoxy compound manufacture, it is preferable that it is an organic palladium compound, and it is more preferable that it is palladium acetate.

  The nitrogen-containing aromatic compound functions as a ligand in a water-soluble palladium complex, and particularly when the water-soluble palladium complex having a ligand composed of a nitrogen-containing aromatic compound is used as the palladium complex, the activity, etc. This is an excellent method for producing an epoxy compound. The nitrogen-containing aromatic compound is preferably a compound having high solubility in an aqueous medium, such as sodium pyridine-3-sulfonate, disodium 4,7-diphenyl-1,10-phenanthroline disulfonate. Nitrogen-containing aromatic compounds such as hydrates and disodium 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline disulfonate can be mentioned, and these nitrogen-containing aromatic compounds can be used alone or in combination of two kinds. It can be used as a mixture of the above. And since it becomes the manufacturing method of the epoxy compound which is excellent especially in the solubility to an aqueous medium, and is excellent in the reactivity at the time of epoxy compound manufacture, 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline disulfonic acid Disodium and / or 4,7-diphenyl-1,10-phenanthroline disulfonic acid disodium hydrate is preferred.

  The water-soluble palladium complex used in the production method of the present invention may be prepared by any method as long as it is possible to prepare a water-soluble palladium complex. For example, the palladium compound and the nitrogen-containing compound in the presence of a solvent. It can be prepared by mixing aromatic compounds. In this case, the solvent is preferably a solvent other than alcohols. For example, water can be used as the solvent. Other solvents include, for example, halogen solvents such as chloroform, chlorobenzene and o-dichlorobenzene; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran and dimethoxyethane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; methyl acetate, Carboxylic acid esters such as ethyl acetate; Carboxylic acid amides such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide, N-methylpyrrolidone; Acetonitrile, propiononitrile, benzonitrile, etc. These nitriles can be used, and these solvents can be used alone or as a mixture of two or more.

  Further, the ratio of the palladium compound and the nitrogen-containing aromatic compound in preparing the water-soluble palladium complex is not subject to any limitation as long as the epoxy compound can be produced. Since it becomes a manufacturing method of an epoxy compound, it is preferable that it is 1-40 mol of this nitrogen-containing aromatic compound with respect to 1 mol of this palladium compound, and especially this nitrogen-containing aromatic with respect to 1 mol of this palladium compound. It is preferable that it is 1-6 mol of compounds. There is no restriction | limiting as temperature in preparing this water-soluble palladium complex, For example, it is -20-80 degreeC, and it is preferable that it is room temperature or its vicinity since it does not involve especially complicated operation | work. The pressure at that time is not limited and is preferably at or near atmospheric pressure because it is easy to operate and does not involve any particularly complicated work. Further, the atmosphere may be any atmosphere such as air; an inert gas such as nitrogen, helium, argon, carbon dioxide, or the like.

The crystalline titanosilicate used in the present invention has a general formula nSiO in which a part of silicon forming a crystal lattice of crystalline SiO ₂ having a zeolite structure (sometimes referred to as silicalite) is replaced with titanium. It is a synthetic zeolitic material represented by ₂ · (1-n) TiO ₂ . Here, n is usually 0.8 to 0.999. The structure of the crystalline titanosilicate is not particularly limited, and any structure belonging to the category called crystalline titanosilicate can be used. Examples of the structure include BEA type, DON type, ITQ type, MFI type, MOR type, and MWW type. Among them, it is possible to produce an epoxy compound with high activity and high selectivity. The structure is preferably MFI type.

  The method for synthesizing the crystalline titanosilicate is not particularly limited, and can be synthesized by the methods described in, for example, JP-A-56-096720 and JP-A-60-127217.

  According to JP-A-56-96720, crystalline titanosilicate is synthesized by hydrolyzing a tetraalkylorthosilicate and a tetraalkylorthotitanate with a tetraalkylammonium hydroxide aqueous solution and then hydrothermally synthesizing. Examples of the tetraalkylorthosilicate include tetramethylorthosilicate, tetraethylorthosilicate, tetrapropylorthosilicate, tetrabutylorthosilicate, tetrapentylorthosilicate, tetrahexylorthosilicate, tetraheptylorthosilicate, tetraoctylorthosilicate, Examples thereof include trimethylethyl silicate, dimethyldiethyl silicate, methyltriethyl silicate, dimethyldipropyl silicate and ethyltripropyl silicate. Of these, tetraethylorthosilicate is preferred because of its availability.

  Examples of the tetraalkyl orthotitanate include tetramethyl orthotitanate, tetraethyl orthotitanate, tetrapropyl orthotitanate, tetrabutyl orthotitanate, tetraoctyl orthotitanate, trimethylethyl titanate, dimethyldiethyl titanate, methyltriethyl titanate, dimethyldipropyl titanate. And ethyl tripropyl titanate. Among these, tetraethyl orthotitanate and tetrabutyl orthotitanate are preferable because they are easily available.

  Furthermore, examples of the tetraalkylammonium hydroxide include tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and the like. Propyl ammonium is preferred.

  There are no particular limitations on the charging ratio of these reaction raw materials when synthesizing the crystalline titanosilicate. For example, the amount of tetraalkylorthosilicate used is usually 1 to 100 per mol of tetraalkylorthotitanate. Equivalent, preferably 5 to 35 equivalents. The usage-amount of the tetraalkylammonium hydroxide is 0.1-1 equivalent normally with respect to 1 mol of tetraalkyl orthosilicate, Preferably it is 0.2-0.6 equivalent. Moreover, the density | concentration of the tetraalkylammonium hydroxide aqueous solution is 3 to 50 weight% normally, Preferably it is 5 to 40 weight%.

  The hydrolysis temperature for synthesizing the crystalline titanosilicate is not particularly limited, and is, for example, -20 to 60 ° C, preferably -10 to 40 ° C. The reaction time is usually 10 minutes to 100 hours, preferably 30 minutes to 50 hours. Further, if necessary at the time of hydrolysis, a solvent may be used. Examples of the solvent include alcohols such as methanol, ethanol, propanol, butanol and octanol; ketones such as acetone and methyl ethyl ketone; diethyl ether, tetrahydrofuran and dimethoxy. And ethers such as ethane. As long as a uniform hydrolysis product can be obtained in the hydrolysis reaction, the mixing order and mixing method of the reaction raw materials of tetraalkylorthosilicate, tetraalkylorthotitanate and tetraalkylammonium hydroxide aqueous solution are not particularly limited, For example, all of the above compounds may be mixed at once, or an aqueous alkylammonium hydroxide solution may be added dropwise to a mixture of tetraalkylorthosilicate and tetraalkylorthotitanate. Further, an alkyl ammonium hydroxide aqueous solution and then a tetraalkyl orthotitanate may be added to the tetraalkyl orthosilicate. The alcohol by-produced by hydrolysis does not necessarily have to be removed, but it is preferable to reduce the amount by heating in advance.

  The hydrolysis product obtained as described above is subjected to hydrothermal synthesis by adding water as necessary. The amount of water used for hydrothermal synthesis is not particularly limited. For example, it is usually 15 to 100 equivalents, preferably 25 to 80 equivalents per mole of silicon atom, together with water added during the hydrolysis reaction. Adjust to. In the hydrothermal synthesis reaction, this mixed solution is heated in a sealed container under a temperature condition of usually 60 to 300 ° C., preferably 100 to 200 ° C., usually 1 to 100 hours, preferably 6 to 50 hours. It is carried out by holding. At this time, the pressure can be applied by either self-pressure or under pressure, and usually under self-pressure. The reaction system is not necessarily stirred, and crystallization proceeds sufficiently even in a stationary state. The solid powder thus crystallized by hydrothermal synthesis is sufficiently washed with ion-exchanged water and then subjected to a firing treatment. The temperature of the baking treatment is not particularly limited, and is usually 300 to 700 ° C., preferably 350 to 600 ° C., for example. The firing time is usually 1 to 50 hours, preferably 2 to 20 hours, whereby crystalline titanosilicate can be produced.

  The crystalline titanosilicate used in the present invention may contain boron, aluminum, phosphorus, calcium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, gallium, zirconium, etc., if necessary. It is also possible to add a source of these metal oxides to form a crystalline titanosilicate containing a different element. The crystalline titanosilicate may be used as it is, or may be used after being molded. In the case of molding and using, a binder is generally used, and examples of the binder include silica and alumina.

  The amount of the water-soluble palladium complex used in the production method of the present invention can be appropriately selected depending on the reaction format. For example, when the epoxy compound is produced in a fixed bed continuous flow type, batch type, or semi-batch type. In this case, the amount used may be determined based on the reaction rate and heat balance. Among them, the reaction during the production proceeds efficiently, so that the palladium in the water-soluble palladium complex with respect to the solvent has a molar concentration of 0. It is preferably 0.001 to 100 mmol / l, and particularly preferably 0.01 to 10 mmol / l.

The amount of the crystalline titanosilicate used in the production method of the present invention can be appropriately selected depending on the reaction mode. For example, when producing an epoxy compound in a fixed bed continuous flow system, the reaction rate and heat balance are determined. The amount used may be determined according to the above, and among them, since the reaction during the production proceeds efficiently, the weight hourly space velocity (WHSV) is preferably 0.01 to 1000 hr ⁻¹ , particularly 0. 0.1 to 100 hr ⁻¹ is preferable. Here, the weight hourly space velocity (WHSV) represents the total weight of olefins supplied per unit time (hr) per unit catalyst weight. In addition, when the epoxy compound is produced in a batch system or a semi-batch system of a suspended bed, it is preferably 0.0001 to 30% by weight, particularly 0.001 to 10% by weight, based on the solvent. It is preferable that

  Further, the ratio of the water-soluble palladium complex to the crystalline titanosilicate can be appropriately selected. The number of moles of palladium in the water-soluble palladium complex is 0.0001 to the weight of the crystalline titanosilicate. 100 mmol / g, particularly 0.001 to 10 mmol / g is preferable because the reaction proceeds efficiently.

  The method for producing an epoxy compound of the present invention is carried out in a liquid phase, and an aqueous medium is used as a solvent at that time. By using an aqueous medium as a solvent, a highly active and highly selective epoxy is used. This not only makes it possible to produce a compound, but also provides a method for producing it safely. Further, by using an aqueous medium as a solvent, the recovery efficiency when separating and recovering the product epoxy compound and the solvent is excellent. As the aqueous medium at that time, for example, water, distilled water, industrial water, domestic water, tap water, or the like, water or an organic solvent may be mixed. Examples of the organic solvent at that time include the above-mentioned alcohols; ethers such as dimethyl ether, diethyl ether, tetrahydrofuran, and dimethoxyethane; ketones such as methyl ethyl ketone and methyl isobutyl ketone; carboxylic acid esters such as methyl acetate and ethyl acetate; Carboxylic acid amides such as N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylpropionamide and N-methylpyrrolidone; nitriles such as acetonitrile, propiononitrile and benzonitrile, and the like. it can. Among them, water or a mixed solvent of water and the above alcohol is preferable because it is a production method excellent in productivity of the epoxy compound. In addition, when mixing and using water and an organic solvent, water and the organic solvent may be mixed uniformly, and you may isolate | separate into two layers, without carrying out perfect mixing.

  The olefin in the production method of the present invention generates an epoxy compound, and any olefin can be used as long as it belongs to the category called olefin, such as propylene, butene, Pentene, hexene, heptene, octene, nonene, decene, dodecene, cyclopropene, cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, methylcyclopentene, ethylcyclopentene, propylcyclopentene, butylcyclopentene, methylcyclohexene, ethylcyclohexene, Propylcyclohexene, butylcyclohexene, dimethylcyclohexene, trimethylcyclohexene, cyclopentylpropene, cyclopentylbutene, Black pliers Le Pen Ten, cyclohexyl propene, cyclohexyl butene, styrene, phenyl propene, phenyl butene and the like, because the reaction proceeds efficiently, preferably, the olefin is 3 to 10 carbon atoms.

  Any molecular oxygen can be used as the molecular oxygen in the production method of the present invention as long as it belongs to the category of molecular oxygen. For example, pure oxygen composed of oxygen gas; nitrogen, helium, argon, carbon dioxide, etc. In addition to oxygen diluted with an inert gas, air may be used. Further, the amount of the molecular oxygen used is not limited as long as the production method of the present invention can be carried out, and in particular, the reaction during production of the epoxy compound proceeds efficiently. 0.01-100 mol is preferable with respect to mol, and 0.1-50 mol is especially preferable. The oxygen pressure during the reaction is not particularly limited, and is preferably 0.2 to 5 MPa, for example, normal pressure to 10 MPa, high activity, high selectivity, and high catalyst stability. It is preferably 2 to 2 MPa.

  As the secondary alcohol in the production method of the present invention, any alcohol can be used as long as it belongs to the category of secondary alcohol, for example, 2-propanol, 2-butanol, 2-pentanol, 3 -Pentanol, 2-hexanol, 3-hexanol, 2-heptanol, 3-heptanol, 4-heptanol, 2-octanol, 3-octanol, 4-octanol, 2-nonanol, 3-nonanol, 4-nonanol, 5- Nonanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-tridecanol, 3-tridecanol, 4-tridecanol, 5-tridecanol, 6-tridecanol, 7-tridecanol, 2-pentadecanol, 3- Pentadecanol, 4-pentadecanol, 5 Pentadecanol, 6-pentadecanol, 7-pentadecanol, 8-pentadecanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, cyclononanol, cyclodecanol, dicyclohexylmethanol, 1-phenyl Examples include ethanol, 1-phenylpropanol, 1-phenylbutanol, 1-phenylpentanol, 1-phenylhexanol, 1-phenylheptanol, 1-phenyloctanol, 1-phenylnonanol, 1-phenyldecanol and the like. In particular, since the reaction during production proceeds efficiently, 2-propanol, 2-butanol, 2-pentanol, 3-pentanol, 2-hexanol, 3-hexanol, 2-heptanol, 3-heptanol, 4- Ptanol, 2-octanol, 3-octanol, 4-octanol, 2-nonanol, 3-nonanol, 4-nonanol, 5-nonanol, 2-decanol, 3-decanol, 4-decanol, 5-decanol, 2-tridecanol, 3-tridecanol, 4-tridecanol, 5-tridecanol, 6-tridecanol, 7-tridecanol, cyclopentanol, cyclohexanol, cycloheptanol, cyclooctanol, cyclononanol, cyclodecanol, dicyclohexylmethanol, 1-phenylethanol, Secondary alcohols having 3 to 13 carbon atoms such as 1-phenylpropanol, 1-phenylbutanol, 1-phenylpentanol, 1-phenylhexanol, 1-phenylheptanol and benzhydrol are preferred. Good. More preferred are 2-propanol, 2-butanol, and 3-pentanol.

  In addition, the amount of secondary alcohol used is not limited as long as the production method of the present invention can be carried out, and in particular, the reaction during the production proceeds efficiently. .1 to 1000 mol is preferable, particularly 1 to 100 mol is preferable.

  The epoxy compound obtained by the production method of the present invention is not particularly limited. For example, propylene oxide, butene oxide, pentene oxide, hexene oxide, heptene oxide, octene oxide, nonene oxide, decene oxide, dodecene oxide, cyclopropene oxide. , Cyclobutene oxide, cyclopentene oxide, cyclohexene oxide, cycloheptene oxide, cyclooctene oxide, cyclononene oxide, cyclodecene oxide, methylcyclopentene oxide, ethylcyclopentene oxide, propylcyclopentene oxide, butylcyclopentene oxide, methylcyclohexene oxide, ethylcyclohexene Oxide, propylcyclohexene oxide, butylcyclohexene oxide, dimethyl Le cyclohexene oxide, trimethyl cyclohexene oxide, cyclopentyl propene oxide, cyclopentyl butene oxide, cyclopentyl point pen Ten oxide, cyclohexyl propene oxide, cyclohexyl butene oxide, styrene oxide, phenyl propene oxide, and phenyl-butene oxide and the like.

  There is no restriction | limiting in the reaction temperature at the time of performing the manufacturing method of the epoxy compound of this invention, and since it becomes possible to manufacture an epoxy compound with a high reaction rate, suppressing a side reaction, it must be 0-200 degreeC. Particularly, it is preferably 20 to 150 ° C, more preferably 40 to 100 ° C. The reaction pressure is preferably normal pressure to 20 MPa, particularly preferably normal pressure to 5 MPa. In the production method of the present invention, olefin can be used in a gas or liquid state, and when used in a liquid state, it may be reacted under pressure.

  In the method for producing an epoxy compound of the present invention, any method can be used as long as it is possible to react an olefin, a secondary alcohol and molecular oxygen in an aqueous medium in the presence of a water-soluble palladium complex and a crystalline titanosilicate. For example, a batch type in which olefin, secondary alcohol, molecular oxygen, water-soluble palladium complex, crystalline titanosilicate, and aqueous medium are charged into the reactor at once, olefin in the reactor, Semi-batch, continuous supply of secondary alcohol and molecular oxygen, olefin, secondary alcohol and molecular oxygen are continuously supplied, and unreacted gas and reaction liquid are continuously withdrawn from a fixed bed or suspension. Any method such as a continuous type of muddy bed can be used. Further, the produced epoxy compound can be separated and recovered by a known method such as sequential distillation of the reaction mixture, and the production method of the present invention can be provided with such an accompanying process. In the production method of the present invention, since the water-soluble palladium complex and crystalline titanosilicate are present in the aqueous medium phase after the reaction, the separated and recovered aqueous medium phase can be reused as it is.

  The production method of the present invention can produce a ketone compound simultaneously with an epoxy compound, and the ketone compound can be easily returned to a secondary alcohol as a raw material by hydrogenation, The secondary alcohol can be recycled as a raw material.

  By reacting an olefin, secondary alcohol and molecular oxygen in an aqueous medium in the presence of a water-soluble palladium complex and crystalline titanosilicate, an epoxy compound can be produced with high activity and high selectivity, It is possible to provide a novel method for producing an epoxy compound, which is a safe production method because an aqueous medium is used as a solvent and no peroxide is used.

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

Preparation example (Preparation of crystalline titanosilicate)
Crystalline titanosilicate was prepared according to Japanese Patent No. 3697737.

  44.1 g of tetraethylorthotitanate and then 198 g of tetraethylorthosilicate were placed in a four-necked flask having an internal volume of 1000 ml equipped with a thermometer and a stirrer and mixed under a nitrogen stream. After cooling this mixed solution to 0 ° C., 345 g of a 25 wt% tetrapropylammonium hydroxide aqueous solution was added dropwise over 1 hour with a feed pump. Further, this solution was aged at room temperature for 1 hour. After stirring, the mixture became a homogeneous solution. This four-necked flask was heated to about 90 ° C. in an oil bath, and ethanol and water generated by hydrolysis were distilled off.

  After adding 604 g of ion-exchanged water to the distilled and removed mixture, 400 ml thereof was put into a 500 ml Hastelloy pressure-resistant reaction vessel equipped with a thermometer and a stirrer, and the temperature was raised to 170 ° C. under self-pressure for 2 hours. The mixture was stirred for 48 hours for hydrothermal synthesis. The contents of the autoclave were centrifuged and washed thoroughly with ion exchange water at 60 ° C. The obtained white powder was dried at 90 ° C. for 15 hours and then calcined at 550 ° C. for 5 hours to obtain 21.5 g of crystalline titanosilicate. The obtained crystalline titanosilicate was confirmed to have an MFI type structure by an X-ray diffractometer (XRD).

(Reaction evaluation)
Reaction evaluation was performed using a 200 ml stainless steel autoclave (manufactured by Pressure Glass Industrial Co., Ltd., (trade name) TPR-1 type). The analysis of the reaction solution and gas was performed with a gas chromatograph (manufactured by Shimadzu Corporation, (trade name) GC-14A), and a capillary column (manufactured by GL Sciences, (trade name) TC-FFAP, 60 m × 0.25 mm (inner diameter)). The reaction product was quantified using a flame ionization detector (FID) using a film thickness of 0.25 μm.

Example 1
0.011 g (0.05 mmol) of palladium acetate (manufactured by Wako Pure Chemical Industries) and 0.056 g of disodium 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline disulfonate (manufactured by Tokyo Chemical Industry) (1 mol of palladium) 10 ml of distilled water was added to the solution and stirred at room temperature for dissolution, and then allowed to stand overnight to prepare a water-soluble palladium complex solution. The whole amount of the water-soluble palladium complex solution was put in an autoclave, and charged with 31 g (0.5 mol; 40 ml) of 2-propanol, 35 ml of distilled water, and 0.2 g of crystalline titanosilicate obtained by the preparation example.

  Next, after replacing the autoclave with nitrogen, oxygen 0.4 MPa, propylene 50 mmol, and nitrogen 0.2 MPa were added, and the mixture was stirred at a reaction temperature of 80 ° C. for 1.5 hours to produce propylene oxide.

  The reaction results are shown in Table 1.

Example 2
The reaction was performed in the same manner as in Example 1 except that 31 g (0.5 mol; 40 ml) of 2-propanol was changed to 4 g (0.06 mmol; 5 ml) and 35 ml of distilled water was changed to 70 ml.

  The reaction results are shown in Table 1.

Example 3
The reaction was performed in the same manner as in Example 2 except that 4 g (0.06 mmol; 5 ml) of 3-pentanol (manufactured by Kanto Chemical) was used instead of 4 g (0.06 mmol; 5 ml) of 2-propanol.

  The reaction results are shown in Table 1.

Example 4
Instead of 0.056 g of disodium 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline disulfonate (corresponding to 2 mol per 1 mol of palladium), 4,7-diphenyl-1,10 -Reaction was carried out in the same manner as in Example 1, except that 0.055 g of disodium phenanthroline disulfonate (Tokyo Kasei) (corresponding to 2 mol per 1 mol of palladium) was used.

  The reaction results are shown in Table 1.

Example 5
0.011 g (0.05 mmol) of palladium acetate and 0.056 g of disodium 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline disulfonate (corresponding to 2 mol per 1 mol of palladium) After adding 10 ml of water and stirring and dissolving at room temperature, it was left overnight to prepare a water-soluble palladium complex solution. The whole amount of the water-soluble palladium complex solution was put in an autoclave, and 31 g (0.5 mol; 40 ml) of 2-propanol, 35 ml of water, 4.2 g (50 mmol) of 1-hexene (manufactured by Tokyo Chemical Industry), and the crystalline tita obtained by the preparation example. 0.2 g of nosilicate was added.

  Next, after replacing the autoclave with nitrogen, oxygen 0.4 MPa and nitrogen 0.2 MPa were added, and the mixture was stirred at a reaction temperature of 80 ° C. for 1.5 hours to produce hexene oxide.

  The reaction results are shown in Table 1.

比較例１
酢酸パラジウム０．０１１ｇおよび２，９−ジメチル−４，７−ジフェニル−１，１０−フェナントロリンジスルホン酸二ナトリウム（東京化成製）０．０５６ｇを添加しないこと以外は、実施例１と同様に反応を行った。

Comparative Example 1
The reaction was conducted in the same manner as in Example 1 except that 0.011 g of palladium acetate and 0.056 g of disodium 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline disulfonate (manufactured by Tokyo Chemical Industry) were not added. went.

  Formation of an epoxy compound could not be confirmed.

Comparative Example 2
The reaction was performed in the same manner as in Example 1 except that 80 ml of chlorobenzene was used instead of 32 g of 2-propanol.

  Formation of an epoxy compound could not be confirmed.

  The present invention relates to a production method capable of producing an industrially useful epoxy compound as a diol or polyol raw material with excellent safety and efficiency.

Claims (4)

Water-soluble palladium comprising palladium acetate and disodium 2,9-dimethyl-4,7-diphenyl-1,10-phenanthroline disulfonate and / or disodium 4,7-diphenyl-1,10-phenanthroline disulfonate A process for producing an epoxy compound comprising reacting an olefin, a secondary alcohol and molecular oxygen in an aqueous medium in the presence of a complex and crystalline titanosilicate . The method for producing an epoxy compound according to claim 1 , wherein the crystalline titanosilicate is a crystalline titanosilicate having an MFI type structure. The method for producing an epoxy compound according to claim 1 or 2 , wherein the olefin is an olefin having 3 to 10 carbon atoms. Secondary alcohols, 2-propanol, according to claim 1, characterized in that one or more secondary alcohol selected from the group consisting of 2-butanol and 3-pentanol A process for producing an epoxy compound.