JP2002241465A - Production method for epoxy compound - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method whereby a carbon-carbon unsaturated bond of an epoxy-group-containing compound is selectively hydrogenated in the presence of a catalyst which can be easily separated and regenerated after the hydrogenation. SOLUTION: In this method for producing an epoxy compound by selectively hydrogenating the carbon-carbon unsaturated bond of a compound having at least one carbon-carbon unsaturated bond and at least one epoxy group, a catalyst comprising a noble metal carried on zeolite is used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an epoxy compound. Specifically, the present invention relates to a method for selectively hydrogenating an unsaturated bond of a compound having an epoxy group and a carbon-carbon unsaturated bond using a specific catalyst. The epoxy resin obtained by the present invention is expected to be used for paints, coating materials, binder resins and the like.

[0002]

2. Description of the Related Art Epichlorohydrin and bisphenol A
The bisphenol A type epoxy resin obtained by the reaction with is widely used as a general-purpose type epoxy resin in coating materials, electric insulating materials, laminates, structural materials and the like. However, bisphenol-type epoxy resins have difficulty in weather resistance due to having an aromatic ring.In particular, for applications requiring weather resistance, cyclohexene-based alicyclic olefins epoxidized with peracetic acid are used as weather-resistant epoxy resins. It is commercially available. On the other hand, various attempts to produce a corresponding alicyclic epoxy resin by hydrogenating an aromatic ring of a bisphenol type epoxy resin instead of an epoxy resin using a peracid have been conventionally proposed. In this case, it is necessary to suppress the decomposition of the epoxy group as much as possible during the hydrogenation of the aromatic nucleus.

The prior art is disclosed in US Pat. No. 3,336,336.
No. 241, JP-A-10-204002 or JP-A-2000-226380 discloses at least one vi
A method of hydrogenating an organic compound having a c1,2-epoxy group and at least one C—C double bond using a catalyst in which rhodium or ruthenium is supported on activated carbon is described, and JP-A-11-217379 describes. A method using a catalyst in which rhodium or ruthenium is supported on a carbonaceous carrier having a specific surface area of 5 to 600 m ² / g has been proposed. Also,
U.S. Pat. No. 3,336,241 also proposes a method for hydrogenating rhodium using a catalyst supported on alumina. Further, U.S. Pat. No. 4,847,394 and JP-A-8-53370 propose a method using a homogeneous ruthenium catalyst obtained by reduction with a compound having a specific oxidation-reduction potential.

[0004]

However, when the reaction is repeatedly performed in the hydrogenation reaction method, an organic substance adheres to the catalyst, and the activity is reduced and deteriorated. In order to regenerate the deteriorated catalyst, it is effective to calcine and remove organic substances. However, in the case of activated carbon and carbonaceous carrier, the carrier also burns at the time of calcining, and the regeneration is difficult. There is. In the method using a homogeneous ruthenium catalyst,
Although the catalyst activity is sufficient, since it is an unsupported system, it is difficult to completely separate expensive ruthenium from the product, and there is a problem in recovery and reuse of the catalyst. In the method using alumina as a carrier, regeneration of the catalyst is easy, but there is a problem that the activity of the catalyst is low.

The present invention provides a supported catalyst which can selectively hydrogenate carbon-carbon unsaturated bonds in a selective hydrogenation reaction of an epoxy group-containing compound, and which can easily separate a reaction product from a catalyst. Another object of the present invention is to provide a method using a catalyst supported on an inorganic carrier capable of regenerating the catalyst by firing.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies to solve the above-mentioned problems, and as a result, it has been found that a catalyst in which a noble metal, particularly rhodium or ruthenium, is supported on a zeolite carrier is used in the hydrogenation. The present inventors have found that the carbon-carbon unsaturated bond of the epoxy group-containing compound can be selectively hydrogenated, and that the catalyst can be easily separated and regenerated, thereby completing the present invention. That is, the gist of the present invention is a method of producing an epoxy compound by selectively hydrogenating a carbon-carbon unsaturated bond of a compound having at least one carbon-carbon unsaturated bond and at least one epoxy group,
The present invention relates to a method for producing an epoxy compound, which comprises using a catalyst in which a noble metal is supported on zeolite.

In a preferred embodiment of the present invention, the noble metal is rhodium or ruthenium; at least one carbon-carbon unsaturated bond forms an aromatic ring: the zeolite is a crystalline aluminosilicate In particular, when the maximum pore diameter is 5 ° or more, for example, Y
Zeolite, mordenite zeolite or L-type zeolite; and the cation of the crystalline aluminosilicate is proton; silica / alumina (S
i / 2Al) is 6 or more.

[0008] In another preferred embodiment of the present invention, ethers are used as a hydrogenation reaction solvent; the hydrogenation reaction is carried out at a reaction temperature of 30 to 150 ° C and a hydrogen pressure of 1 to 30 MPa; The compound having a carbon-carbon unsaturated bond and at least one epoxy group is a compound obtained by reacting epichlorohydrin with a polyhydric phenol.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.
The starting material used in the present invention is a compound having at least one carbon-carbon unsaturated bond and at least one epoxy group. This may be any of a monomer, oligomer or polymer. Specific examples include an aromatic ring compound having an epoxy group, an unsaturated aliphatic compound, an unsaturated cyclic aliphatic compound, and an unsaturated polycyclic compound. Among them, a compound in which a carbon-carbon unsaturated bond forms an aromatic ring is preferable.

Specific examples of the aromatic ring compound include styrene oxide, phenylglycidyl ether, diglycidyl ether of hydroquinone, diglycidyl ether of resorcinol, and bisphenol A or bisphenol F represented by the following formula (I). Examples include epoxy resins using chlorohydrin as a raw material, and polyglycidyl ethers of phenol novolak resins or cresol novolak resins represented by the following formula (II).

[0011]

Embedded image (Wherein, R ¹ represents a hydrogen atom or a methyl group, and n is 0 to 40)

[0012]

Embedded image (Wherein, R ¹ represents a hydrogen atom or a methyl group, and m is 0 to 40)

Among these, bisphenol A type epoxy resin represented by the formula (I) and polyglycidyl ether of orthocresol novolak resin represented by the formula (II) are preferred. Among them, diglycidyl ether of bisphenol A ( Particular preference is given to n = 1) of the formula (I) and its oligomers. The diglycidyl ether of bisphenol A is used, for example, as Epicoat 827, 828, its oligomer is used as Epicoat 834, and the compound of formula (II) is used as Epicoat 152, 154, 180S6.
No. 5 is commercially available from Yuka Shell Epoxy Co., Ltd.

The hydrogenation catalyst used in the present invention is a catalyst comprising a noble metal supported on zeolite. The zeolite used in the present invention is not particularly limited as long as it is a zeolite that can be used as a carrier. Known zeolites such as zeolites containing foreign elements such as silicate and ferroaluminosilicate are exemplified. Among these, crystalline aluminosilicate is preferable, and those having a maximum pore diameter of zeolite of 5 mm or more are preferable. Among the zeolites, Y-type zeolites, mordenite-type zeolites and L-type zeolites are more preferable. In the present invention, when such a zeolite having a maximum pore diameter of a specific value or more is used, the reaction substrate can sufficiently diffuse in the pores, and only the unsaturated bond is selectively hydrogenated. It is thought that good results can be obtained because the reaction substrate is immobilized in an optimal state for the reaction.

The cations constituting the zeolite are nonmetallic cations such as protons and ammonium or metal ions. In the case of metal ions, alkali metal ions such as sodium and potassium and alkali metal ions such as calcium and magnesium are usually used. Examples thereof include earth metal ions, rare earth ions such as lanthanum and cerium, and among them, the proton type is preferable. If the acidity of the zeolite is high, the loss of epoxy groups is large. Therefore, the silica / alumina (Si / 2Al) molar ratio of the crystalline aluminosilicate is preferably 6 or more, more preferably 10 or more, and still more preferably 30 or more.
That is all. The upper limit is usually 1000 or less, preferably 800 or less, particularly preferably 600 or less. In the present invention, a zeolite as a noble metal catalyst carrier, in particular, a crystalline aluminosilicate having a maximum pore diameter of a specific value or more and a silica / alumina (Si / 2Al) ratio within a predetermined range and a desired acidity range is used. By using
The loss of the epoxy group is relatively small, and the carbon of the aromatic ring is
It is possible to form a catalyst in which the activity of the selective hydrogenation reaction for carbon unsaturated bonds is extremely high.

The noble metal of the catalyst component includes gold, silver and platinum group metals (Ru, Rh, Pd, Os, Ir, Pt). Among them, platinum group metals are preferable, and Ru or R
h is preferred, and Rh is particularly preferred. The rhodium compound and ruthenium compound used in the present invention are not particularly limited as long as they can be thermally decomposed. Examples of the rhodium compound include inorganic salts such as rhodium chloride, rhodium nitrate, and rhodium sulfate; organic compounds such as rhodium acetylacetonate; and coordination compounds such as tetrarhodium dodecacarbonyl. Examples of the ruthenium compound include inorganic salts such as ruthenium chloride and ruthenium nitrosyl nitrate, organic compounds such as ruthenium acetylacetonate, and coordination compounds such as triruthenium dodecacarbonyl. Among these, the use of a rhodium compound is particularly preferred because of its higher activity. There is no particular limitation on the amount of the metal component to be supported, but if the amount is small, the effect of the catalyst is reduced, and if the amount is large, the cost is disadvantageous.
Preferably, it contains 10% by weight, more preferably 2 to 8% by weight of metal.

The method of supporting the rhodium or ruthenium component on the zeolite carrier is not particularly limited, but in general, the dipping method is used. For example, the metal component of the catalyst component is dissolved in a solvent capable of dissolving the same, for example, water to form a solution, and zeolite is immersed in the solution to be impregnated and supported. Thereafter, the solvent is distilled off under reduced pressure, and a reduction treatment is performed if necessary. The reduction treatment can be performed by either a gas phase reduction method or a liquid phase reduction method.

In the case of a gas phase reduction method, for example, when reducing in the gas phase using hydrogen gas, 100 to 600 ° C., preferably 15 to 60 ° C.
The reaction is performed at a temperature of 0 to 500C. Examples of the reducing agent used here include carbon monoxide in addition to hydrogen. Further, it may be used after being diluted with an inert gas such as nitrogen or argon. In the case of reduction in the liquid phase, it is preferable to first carry a rhodium compound or a ruthenium compound, then treat with an alkaline aqueous solution to insolubilize and immobilize the noble metal as a hydroxide, and reduce it. As the kind of alkali of the aqueous alkali solution used for insoluble / immobilization, ammonia water or an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide can be preferably used, but it is easy to wash with water after insoluble / immobilization. It is most preferable to use aqueous ammonia in consideration of the influence of the residual alkali metal cations.

The amount of the alkali used is preferably 3 to 100 equivalents relative to rhodium or ruthenium.
6 to 50 equivalents are preferred. The temperature of the treatment with the alkaline aqueous solution is preferably from 20 ° C. to 90 ° C., and particularly in the case of using ammonia water, if the temperature is higher than 50 ° C., the desorption of ammonia becomes remarkable, so the temperature is preferably from 20 ° C. to 50 ° C.

After insolubilization and immobilization with an alkaline aqueous solution, the noble metal-carrying catalyst is filtered, and sufficiently washed with ion exchanged water or the like.
Particularly when an aqueous solution of an alkali metal hydroxide is used, Na
^If the alkali metal cations such as ⁺ and K ⁺ remain, the hydrogenation activity decreases, so that it is necessary to sufficiently wash them. The insoluble and immobilized catalyst is preferably reduced in a liquid phase using formalin, formic acid, or methanol. The amount of the reducing agent used is 3 to 10 based on rhodium or ruthenium.
It is 0 molar equivalent, preferably 6 to 50 molar equivalent. The reduction temperature is from 20 ° C to 120 ° C, preferably from 50 to 100 ° C
It is. The catalyst reduced in the liquid phase can be filtered, washed sufficiently with ion-exchanged water, etc., dried and used for the hydrogenation reaction.

The amount of the catalyst used in the hydrogenation reaction is desirably 0.1 to 100 parts by weight, preferably 5 to 50 parts by weight, based on 100 parts by weight of the reaction raw material. Depending on various conditions such as the above, it can be arbitrarily selected as long as a practical reaction rate can be obtained.

When the reaction temperature in the hydrogenation reaction of the present invention is too low, the reaction rate decreases, and when it is too high, hydrogenolysis of the epoxy group proceeds. ° C. The reaction pressure is usually 1
-30 MPa, preferably 3-10 MPa. As a reaction method, either a liquid phase suspension reaction or a fixed bed reaction can be adopted. As the reaction solvent, ethers such as THF and dioxane are preferably used in view of the solubility of the starting materials. After carrying out the hydrogenation reaction according to the method of the present invention, the catalyst is filtered off and then the volatile components are removed by distillation to obtain the desired product.

[0023]

EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited to these examples unless it exceeds the gist. In the examples, the amount of the metal carried on the catalyst is indicated by weight% of the metal in the catalyst. Further, the maximum pore diameter of the zeolites (Y type, mordenite type, L type) used in Examples 1 to 5 below is all 5.7 ° or more.

Example 1 Zeolite (Y-type zeolite manufactured by Tosoh Corporation) was dissolved in 312 mg of 40 wt% rhodium chloride in 5 ml of water.
(390 HUA) 2.37 g was added for impregnation. Thereafter, the solvent was removed under reduced pressure. After raising the temperature from room temperature to 150 ° C. in 15 minutes under argon gas flow,
Dry at 150 ° C. for 2 hours. After cooling, the temperature was raised from room temperature to 200 ° C. in 25 minutes under flowing hydrogen gas,
A reduction treatment was performed at 0 ° C. for 2 hours to prepare a 5% rhodium-supported catalyst.

In a 70 ml spinner-stirring autoclave, 5 g of THF, 5 g of 2,2-di- (p-glycidoxyphenyl) -propane (Epicoat 828, epoxy equivalent 186, manufactured by Yuka Shell Epoxy Co.), and 0.1 g of the above reduction catalyst Was added, 10 MPa of hydrogen was injected at room temperature, the temperature was raised to 100 ° C., and the reaction was performed for 2 hours. After the reaction, the catalyst was filtered off, the volatile components were distilled off under reduced pressure, the hydrogenation rate of the aromatic ring was determined by ¹ H-NMR spectrum, and the perchloric acid titration method (J
The epoxy equivalent was determined by IS K7236). Here, the hydrogenation rate is determined by 1H-NMR from the integral values of the protons of the aromatic ring and the methyl group, and the epoxy equivalent indicates the number of grams of an epoxy resin containing 1 mol of epoxy group. Table 1 shows the aromatic ring hydrogenation rate. Epoxy equivalent was 197.

Example 2 Zeolite (Y-type zeolite 330HU manufactured by Tosoh Corporation)
A catalyst was prepared and reacted in the same manner as in Example 1 except that A) was used. Table 1 shows the results.

Example 3 Zeolite (Mordenite type zeolite 6 manufactured by Tosoh Corporation)
A catalyst was prepared and reacted in the same manner as in Example 1 except that 60HOA) was used. Table 1 shows the results.

Example 4 Zeolite (Mordenite type zeolite 6 manufactured by Tosoh Corporation)
A catalyst was prepared and reacted in the same manner as in Example 1 except that 20HOA) was used. Table 1 shows the results.

Example 5 Zeolite (L-type zeolite 500KO manufactured by Tosoh Corporation)
A catalyst was prepared and reacted in the same manner as in Example 1 except that A) was used. Table 1 shows the results.

Comparative Example 1 Instead of zeolite, silica (D-Daikai Chemical Co., Ltd.
A catalyst was prepared and reacted in the same manner as in Example 1 except that 150-300A) was used. Table 1 shows the results.

Comparative Example 2 Instead of zeolite, γ-alumina (N, manufactured by Mizusawa Chemical Co., Ltd.)
A catalyst was prepared and reacted in the same manner as in Example 1 except that eobad GB-08) was used. Table 1 shows the results.

Comparative Example 3 An α-alumina (Spheralite 512A manufactured by Rhone-Poulenc) was used instead of zeolite.
A catalyst was prepared and reacted in the same manner as in Example 1.
Table 1 shows the results.

Comparative Example 4 Activated carbon instead of zeolite (CX-2 manufactured by Mitsubishi Chemical Corporation)
A catalyst was prepared in the same manner as in Example 1 except for using. The reaction used 0.25 g of catalyst, and 15M of hydrogen at room temperature.
The procedure was performed in the same manner as in Example 1, except that the press-fitting was performed.

[0034]

[Table 1]

[0035]

According to the present invention, when a catalyst in which a noble metal, particularly rhodium or ruthenium is supported on zeolite, is used, the carbon-carbon unsaturated bond of the epoxy-containing compound can be selectively hydrogenated and the catalyst can be easily separated. In addition, it is easy to regenerate a catalyst whose activity has been reduced due to the attachment of an organic substance. Further, the epoxy compound obtained by the method of the present invention is a compound having a low content of a chlorinated component which has a bad effect in various applications, a high purity, and a high industrial value.

Claims (11)

[Claims] 1. A method for producing an epoxy compound by selectively hydrogenating a carbon-carbon unsaturated bond of a compound having at least one carbon-carbon unsaturated bond and at least one epoxy group, wherein the noble metal is converted into a zeolite. A method for producing an epoxy compound, comprising using a supported catalyst. 2. The method for producing an epoxy compound according to claim 1, wherein the noble metal is rhodium or ruthenium. 3. The method for producing an epoxy compound according to claim 1, wherein at least one carbon-carbon unsaturated bond forms an aromatic ring. 4. The method for producing an epoxy compound according to claim 1, wherein the zeolite is crystalline aluminosilicate. 5. The method for producing an epoxy compound according to claim 4, wherein the maximum pore diameter of the zeolite is 5 ° or more. 6. The method for producing an epoxy compound according to claim 4, wherein the crystalline aluminosilicate is a Y-type zeolite, a mordenite-type zeolite or an L-type zeolite. 7. The method for producing an epoxy compound according to claim 4, wherein the cation of the crystalline aluminosilicate is a proton. 8. The method for producing an epoxy compound according to claim 4, wherein the molar ratio of silica / alumina (Si / 2Al) of the crystalline aluminosilicate is 6 or more. 9. The method for producing an epoxy compound according to claim 1, wherein an ether is used as a hydrogenation reaction solvent. 10. The hydrogenation reaction is carried out at a reaction temperature of 30 to 150 ° C.
The method for producing an epoxy compound according to any one of claims 1 to 9, wherein the method is performed at a hydrogen pressure of 1 to 30 MPa. 11. The compound having at least one carbon-carbon unsaturated bond and at least one epoxy group is a compound obtained by reacting epichlorohydrin with a polyhydric phenol. 11. The method for producing an epoxy compound according to any one of 1 to 10.