JP2001129397A - Carbonate esterification catalyst and method for preparing cyclic carbonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a carbonate esperification catalyst with a high activity for a reaction between an epoxy compound and carbon dioxide and a method for preparing a cyclic carbonate using this. SOLUTION: An epoxy compound and carbon dioxide are reacted by using a composite metal oxide wherein Al:Mg=0.25:0.75-0.5:0.5 and the X-ray defraction pattern has the first peak at 34.5±2.5 deg. and the second peak at 42.5±2.5 deg. and the third peak at 62.5±2.5 deg. and the relative strength of the first peak to the second peak is 25-90% or a composite metal oxide comprising Al, Mg and the third metal of the 6A group, the 7A group or the 8 group in the periodic table of elements.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a carbonic acid esterification catalyst useful for reacting an epoxy compound with carbon dioxide, and a method for producing a cyclic carbonic ester using the same.

[0002]

2. Description of the Related Art The following general formula (2)

[0003]

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(Wherein R is a hydrogen atom, having 1 to 22 carbon atoms)
Linear saturated or unsaturated in the range of, branched or cyclic hydrocarbon group or a group represented by the general formula _{(3) -CH 2 (OR 2} ) n OR 1 ... (3) R 1 in the hydrogen atom, A saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 22 carbon atoms, wherein R ₂ is an alkylene group having 2 to 4 carbon atoms, and And n is a group representing an average number of moles of the OR ₂ group and an integer in the range of 0 to 30. ) Is used as an oil or a solvent, as well as various pharmaceuticals, agricultural chemicals, surfactants, cosmetics,
It is useful as an intermediate such as a functional material.

As one of the methods for producing the cyclic carbonate represented by the general formula (2), there is known a method of reacting an epoxy compound with carbon dioxide in the presence of a catalyst as shown in the following reaction formula (4). Have been.

[0006]

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Conventionally, a homogeneous catalyst has been mainly used as a catalyst for this reaction. However, when a homogeneous catalyst is used, a complicated process is required for separating a reaction product from a catalyst or a complicated by-product generated by decomposition of the catalyst, and there has been a problem that purification costs and the like are increased. Therefore, a method using a solid catalyst that can be easily separated by filtration was searched. An ion exchange resin is known as a solid catalyst used for this reaction. For example, Japanese Patent Application Laid-Open No. Hei 1-211579 uses an anion exchange resin containing a trimethylbenzylammonium halide group as a catalyst. Japanese Patent Application Laid-Open No. 3-120270 discloses that the water content is 0.5%.
A solid strong basic anion exchanger having up to wt.% Quaternary ammonium groups is used. Further, Japanese Unexamined Patent Publication No.
Japanese Patent No. 206846 uses a carboxylic acid type cation exchange resin having a metal cation or an unsubstituted or alkyl group-substituted ammonium cation as a counter cation.
However, these ion exchange resin-type catalysts are not practical because of problems such as complicated adjustment for increasing the activity and lack of heat resistance.

As a solid catalyst other than the ion exchange resin, Japanese Patent Application Laid-Open No. H11-226413 proposes a catalyst obtained by calcining a basic layered compound containing a divalent metal and a trivalent metal. This catalyst shows 2θ in the X-ray diffraction pattern.
[Deg.] Has one peak at each of the positions 40 to 45 and 60 to 65.

[0009]

Among the above-mentioned metal catalysts, alkali metal halides disclosed in Japanese Patent Publication No. 38-23175 have a low yield of cyclic carbonate and complicated post-treatment of the catalyst. Also, JP-A-11-2264
The catalyst obtained by calcining the basic layered compound of JP-A No. 13 is not suitable for industrialization because it has a low activity and requires a large amount of catalyst. The present invention has been made in order to solve the above-mentioned problems, and accordingly, has as its object to provide a carbonate esterification catalyst having high catalytic activity and easy post-treatment, and a method for producing a cyclic carbonate using the same. Is to do.

[0010]

According to the present invention, there is provided a composite metal oxide containing Al and Mg, wherein the atomic ratio between Al and Mg is Al: Mg = 0.25. :
0.75 to 0.5: within the range of 0.5 and CuΚ
The X-ray diffraction pattern using α radiation shows the first peak in the range of 34.5 ± 2.5 deg.
A second peak within the range of 2.5 ± 2.5 deg.
A third peak within a range of ± 2.5 deg., A relative intensity of the first peak to the second peak is in a range of 25% to 90%, and a relative intensity of the third peak to the second peak is Provide a carbonation esterification catalyst that is in the range of 30% to 100%. In the above, the atomic ratio of Al: Mg is:
It is preferably in the range of 0.35: 0.65 to 0.5: 0.5, particularly preferably in the range of 0.4: 0.6 to 0.5: 0.5.

In the X-ray diffraction pattern, the relative intensity of the first peak with respect to the second peak is in the range of 25% to 90%, and the third peak with respect to the second peak is included in the X-ray diffraction pattern. 30% to 100% relative strength
The composite metal oxide of the present invention within the range of
Catalyst ") has an extremely high catalytic activity for the reaction between the epoxy compound and carbon dioxide, and is easily recovered from the reaction product.

The first catalyst contains Al and Mg by coprecipitating a water-soluble Al salt and a water-soluble Mg salt in an aqueous solution whose pH is preferably adjusted to a range of 7 to 11. A composite metal hydroxide is formed, and the composite metal hydroxide is
It can be manufactured by firing at a temperature in the range of 0 ° C to 1000 ° C.

The present invention also provides a composite metal oxide containing Al, Mg, and at least one third metal selected from the group consisting of Groups 6A, 7A and 8 of the periodic table. (Hereinafter referred to as “the second catalyst”). The third metal is Cr, Mo, Mn,
It is preferably selected from the group consisting of Tc, Fe, Co, Ni and Ru.

The second catalyst also has a very high catalytic activity for the reaction between the epoxy compound and carbon dioxide, and is easy to recover from the reaction product.

The second catalyst comprises co-precipitating a water-soluble Al salt, a water-soluble Mg salt, and a water-soluble salt of the third metal in an aqueous solution to form Al, Mg and the third metal. And forming a composite metal hydroxide containing the composite metal hydroxide at 300 ° C.
It can be manufactured by firing at a temperature in the range of １０００1000 ° C.

In the above-mentioned manufacturing method, the firing temperature is 30
If the temperature is lower than 0 ° C., the catalytic activity is not sufficiently exhibited, and if the firing temperature exceeds 1000 ° C., the sintering proceeds excessively, the surface area decreases, and the catalytic activity also tends to decrease. From this viewpoint, the firing temperature is more preferably in the range of 600 ° C to 900 ° C.

The present invention further provides a method for producing a cyclic carbonate in which an epoxy compound is reacted with carbon dioxide in the presence of either the first catalyst or the second catalyst. The epoxy compound is preferably a compound represented by the following general formula (1), and the cyclic carbonate produced using this epoxy compound is represented by the following general formula (2)
It is a compound shown by these.

[0018]

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(Wherein R is a hydrogen atom, carbon number 1-22)
Linear saturated or unsaturated in the range of, branched or cyclic hydrocarbon group or a group represented by the general formula _{(3) -CH 2 (OR 2} ) n OR 1 ... (3) R 1 in the hydrogen atom, A saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 22 carbon atoms, wherein R ₂ is an alkylene group having 2 to 4 carbon atoms, and And n is a group representing an average number of moles of the OR ₂ group and an integer in the range of 0 to 30. )

[0020]

Embodiments of the present invention will be described below in detail. The First Catalyst The first catalyst is a composite metal oxide containing Al and Mg, and has an atomic ratio of Al: Mg of Al: Mg = 0.25:
0.75 to 0.5: within the range of 0.5 and CuΚ
The X-ray diffraction pattern using α radiation shows the first peak in the range of 34.5 ± 2.5 deg.
A second peak within the range of 2.5 ± 2.5 deg.
A third peak within a range of ± 2.5 deg., A relative intensity of the first peak to the second peak is in a range of 25% to 90%, and a relative intensity of the third peak to the second peak is It is in the range of 30% to 100%.

The first catalyst is prepared by mixing an aqueous solution of aluminum nitrate hydrate and an aqueous solution of magnesium nitrate hydrate, for example, in an environment having a pH preferably in the range of 7 to 11. 300 ° C under inert gas atmosphere
To 1000 ° C, more preferably 600 to 90 ° C.
It can be manufactured by firing at a temperature in the range of 0 ° C.
At this time, the mixing ratio of aluminum nitrate hydrate and magnesium nitrate hydrate was such that the atomic ratio of Al: Mg in the composite metal oxide obtained by firing was 0.25: 0.75
0.5: 0.5, preferably 0.35: 0.6
5: 0.5: 0.5, more preferably 0.5: 0.5.
Adjustment is made to be in the range of 4: 0.6 to 0.5: 0.5. As a result of the experiment, the atomic ratio of Al was less than 0.25,
Or, when it exceeds 0.5, it was found that sufficient catalytic activity as a carbonic acid esterification catalyst could not be obtained.

FIG. 1 shows an X-ray diffraction pattern (CuΚα radiation, 2θ [deg.]) Measured for an example of the first catalyst manufactured under the condition that the atomic ratio of Al is 0.444. As is clear from FIG. 1, in the X-ray diffraction pattern of the first catalyst, the first peak is in the range of 32 ° to 37 °, the second peak is in the range of 40 ° to 45 °, and 60 ° to 60 °. The third peak is remarkably observed within a range of 65 deg. Among them, the first catalyst has a relative intensity of the first peak with respect to the second peak in the range of 25% to 90% and a relative intensity of the third peak with respect to the second peak of 30%.
% Is within the range of 100%.

Referring to the literature for comparison, for example, JP-A-11-226413 discloses that hydrotalcite, which is a basic layered compound containing Al and Mg, is heated to 400 ° C.
Although a catalyst for carbonate ester production obtained by calcining within the range of 700 ° C. is described, the peak of about 34 deg. Observed in uncalcined hydrotalcite disappears by calcining, It is described that such a composite oxide having no peak around 34 deg. Exhibits extremely excellent performance as a catalyst for producing a carbonate ester (Japanese Patent Application Laid-Open No.
-226413, paragraph 0013 and FIG.
reference).

Referring to the above literature, 300 ° C. to 10 ° C.
34.5 ± 2.5 despite firing at 00 ° C
The first peak is in the range of deg.
g. the relative intensity of the first peak to the second peak within the range of 25% to 90%, and 62.5 ±
The first catalyst having a third peak within a range of 2.5 deg. And a relative intensity of the third peak with respect to the second peak within a range of 30% to 100% is disclosed in JP-A-11-226413. It is clear that the compound has a structure completely different from the compound described as a catalyst for producing a carbonate ester.

Although the reason why the first catalyst has a particularly high catalytic activity as compared with the conventional catalyst for producing a carbonate ester described in JP-A-11-226413 or the like is not necessarily clear, the present catalyst has a calcined property. This is considered to be due to the fact that the crystal structure of the previous composite metal oxide has a high irregularity, which results in formation of an extremely large active surface area after firing.
In the first catalyst, it is considered that Al activates the epoxy compound by providing an acid site, and Mg activates carbon dioxide by providing a base site from an adjacent oxygen atom, thereby promoting carbonation.

Second catalyst The second catalyst comprises Al, Mg, Group 6A of the periodic table,
A composite metal oxide containing at least one third metal selected from the group 7A and group 8 ranges. Preferred examples of the third metal include, for example, Cr, Mo, Mn, T
c, Fe, Co, Ni and Ru;
Of these, Cr, Mn, and Fe are more preferable, and in particular, Mn
Is preferred.

In the present second catalyst, the atomic ratio of Al to Mg is Al: Mg = 0.1: 0.9-0.7-0.3, more preferably 0.3: 0.7-0.3. 6: 0.4. The atomic ratio of the third metal to all metals is preferably 0.05 to 0.4, more preferably 0.1 to 0.4.
It is in the range of 0.25.

Both the first catalyst and the second catalyst are:
It can be produced by a conventionally known method for producing a composite metal oxide such as an impregnation method or a coprecipitation method. Here, a production method by a coprecipitation method will be described. The coprecipitation method is
First, mixed aqueous solutions containing metal compounds such as nitrates, sulfates, carbonates, acetates, and chlorides of the respective metals are prepared, and a precipitant is added to the mixed aqueous solutions and the pH is adjusted to a predetermined range.

The precipitating agent is a reagent added to form a precipitating hydroxide of the composite metal, and is, for example, an aqueous basic solution, particularly an aqueous solution containing a basic carbonate such as sodium carbonate, sodium hydroxide, potassium hydroxide. For example, an aqueous solution containing an alkali metal hydroxide, aqueous ammonia, or the like is preferable. It is preferable that the pH of the mixed solution is adjusted within the range of 7 to 11, particularly 8 to 10. If the pH is out of the above range, the metal may be eluted and an oxide catalyst having a desired composition or crystal structure may not be obtained.

The precipitate obtained by the addition of the precipitant is washed with water, dried and calcined to convert the composite metal hydroxide into a composite metal oxide.

Production of Cyclic Carbonate In the present invention, in the presence of either the first catalyst or the second catalyst, the epoxy compound represented by the general formula (1) and carbon dioxide are reacted with the reaction formula ( A method for producing a cyclic carbonate represented by the general formula (2) by reacting as shown in 4) is provided.

In the general formula (1), R represents a hydrogen atom, a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 22 carbon atoms, or the following general formula (3) ) -CH ₂ (OR ₂ ) _n OR ₁ (3) wherein R ₁ is a hydrogen atom, a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 22 carbon atoms. , R ₂ is a group representing the integer in the range of 0-30 with an average addition mole number of the alkylene group is and may be the same or different, n is OR ₂ group in the range of 2 to 4 carbon atoms.

Examples of R in the general formula (1) and the general formula R ₁ include a hydrogen atom, a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group,
Heptyl group, octyl group, nonyl group, decyl group, undecyl group, dodecyl group, myristyl group, pentadecyl group,
Palmityl, stearyl, behenyl, isopropyl, isobutyl, t-butyl, allyl, 1-methylheptyl, 2-ethylhexyl, hexenyl, heptenyl, octynyl, nonenyl, decenyl, undecenyl Group, dodecenyl group, myristenyl group, pentadecenyl group, palmitenyl group, oleyl group,
Examples include a linole group, a linolenyl group, an arachidyl group, a 2-ethylhexenyl group, a phenyl group, a 4-methylphenyl group, a benzyl group and a p-methoxybenzyl group.

In the group represented by the general formula (3),-(O
R ₂ ) — is generally called an alkylene oxide group, and examples of R ₂ include an ethylene group, a propylene group, and a butylene group. In the general formula (3), n is in the range of 0 to 30, and particularly preferably in the range of 0 to 20.

Examples of the epoxy compound represented by the general formula (1) include, for example, methyl glycidyl ether, ethyl glycidyl ether, propyl glycidyl ether, butyl glycidyl ether, isopropyl glycidyl ether, allyl glycidyl ether, octyl glycidyl ether, decyl glycidyl ether Benzyl glycidyl ether, glycidol, pentyl (oxyethylene) ₇ glycidyl ether, ethylene oxide, propylene oxide and the like.

The reaction shown in the reaction formula (4) is carried out in the presence of the first catalyst, the second catalyst or a mixed catalyst thereof. This reaction may be performed in a batch system or a continuous system, and any system generally used such as a fluidized bed system, a fixed bed system, and a stirring system may be employed.

The amount of the catalyst to be used is not particularly limited, but when a batch reaction is employed, the amount of the catalyst is 0.001% by weight to 10% by weight based on the epoxy compound as one raw material.
It is preferably used within the range of 0% by weight, and more preferably within the range of 0.01% by weight to 50% by weight.

This reaction can be carried out under normal pressure or under pressure, but it is preferable to carry out under pressure in order to increase the reaction rate. The reaction pressure at this time is 1 atm to 10 atm.
0 atm, preferably 3 to 50 atm. The molar ratio of carbon dioxide to epoxy compound is from 0.01 to 50.
Is preferably within the range, more preferably 0.1.
It is in the range of 05-40. Reaction temperature is 50 ° C to 200
The temperature is preferably in the range of 70 ° C, particularly preferably in the range of 70 ° C to 180 ° C.

In the reaction shown in the reaction formula (4), a reaction solvent is not necessarily required, but when used, an inert organic solvent is preferable. Examples of suitable inert organic solvents include cyclic carbonate derivatives and alkylene glycols,
Examples thereof include an alkylene glycol ether, dioxane, tetrahydrofuran, dimethylformamide, dimethylsulfoxide, and a mixture of any two or more thereof. In particular, considering the ease of separation, it is preferable to use the cyclic carbonate derivative as the target. The amount of the inert organic solvent to be used is preferably in the range of 5% by weight to 700% by weight, more preferably 10% by weight, based on the epoxy compound as one raw material.
５００500% by weight.

After completion of the reaction, the reaction mixture is filtered to separate the catalyst, and the filtrate is distilled, if necessary, to produce the desired cyclic carbonate derivative with high purity.

Examples of the cyclic carbonate derivative obtained by the production method of the present invention include 1,3-dioxolane-
2-one, 4-methyl-1,3-dioxolan-2-one, 4-ethyl-1,3-dioxolan-2-one,
-Propyl-1,3-dioxolan-2-one, 4-butyl-1,3-dioxolan-2-one, 4-methyloxymethyl-1,3-dioxolan-2-one, 4-ethyloxymethyl-1 , 3-dioxolan-2-one,
4-propyloxymethyl-1,3-dioxolan-2
-One, 4-butyloxymethyl-1,3-dioxolan-2-one, 4-isopropyloxymethyl-1,3
-Dioxolan-2-one, 4-allyloxymethyl-
1,3-dioxolan-2-one, 4-octyloxymethyl-1,3-dioxolan-2-one, 4-decyloxymethyl-1,3-dioxolan-2-one, 4-
Benzyloxymethyl-1,3-dioxolan-2-one, 4-hydroxymethyl-1,3-dioxolan-2
-One, 4-pentyloxy (ethoxy) ₇ methyl-
1,3-dioxolan-2-one and the like can be mentioned.

[0042]

The present invention will be described more specifically with reference to the following examples. (Example 1) The present first catalyst solution A: 66.8 g of aluminum nitrate 9 hydrate (0.1
78 mol) and 57.26 g of magnesium nitrate hexahydrate
(0.223 mol) was dissolved in 450 g of deionized water to obtain solution A. Solution B: 18.87 g (0.178 mol) of sodium carbonate
Was dissolved in 450 g of deionized water to obtain a solution B. The catalyst preparation tank was charged with 1800 g of deionized water, a 2N aqueous solution of NaOH was added to adjust the pH to 9 and the temperature in the tank to 4%.
While maintaining the temperature at 0 ° C., the solution A and the solution B were added dropwise over 1 hour, and after completion of the addition, the solution was aged for 1 hour. The mother liquor was removed by filtration, and the precipitate was washed with 6 liters of deionized water and spray-dried to obtain a composite metal hydroxide. This composite metal hydroxide is calcined at 700 ° C. for 3 hours in a nitrogen atmosphere,
17 g of the present first catalyst composed of a composite metal oxide having an atomic ratio of Al: Mg = 0.44: 0.56 between Mg and Mg was obtained.

The X-ray diffraction pattern (Cu
(Κα radiation, 2θ [deg.]) Is shown in FIG. In FIG. 1, the relative intensity of the first peak (within a range of 32 ° to 37 °) with respect to the second peak (within a range of 40 ° to 45 °) was 52%.

Example 2 This second catalyst (Al / Mg / Mn system) solution A: 47.69 g of aluminum nitrate nonahydrate (0.
127 mol) and 68.03 g of magnesium nitrate hexahydrate
(0.265 mol) and 24.33 g of manganese nitrate hexahydrate
(0.085 mol) was dissolved in 450 g of deionized water to obtain a solution A. Solution B: 13.47 g (0.127 mol) of sodium carbonate
Was dissolved in 450 g of deionized water to obtain a solution B. The catalyst preparation tank was charged with 1800 g of deionized water, a 2N aqueous NaOH solution was added to adjust the pH to 9, and the temperature in the tank to 40 ° C.
The solution A and the solution B were added dropwise over 1 hour while maintaining the temperature, and the mixture was aged for 1 hour after completion of the addition. The mother liquor was removed by filtration, and the precipitate was washed with 6 liters of deionized water and spray-dried to obtain a composite metal hydroxide. The composite metal hydroxide is fired at 800 ° C. for 3 hours in a nitrogen atmosphere, and the atomic ratio of Al, Mg, and Mn is Al: Mg: Mn = 0.26:
19 g of the present second catalyst comprising a composite metal oxide of 0.56: 0.18 was obtained.

Example 3 The present second catalyst (Al / Mg / Cr system) solution A: 50.06 g of aluminum nitrate nonahydrate (0.
133 mol) and 57.26 g of magnesium nitrate hexahydrate
(0.223 mol) and 35.60 g of chromium nitrate nonahydrate
(0.089 mol) was dissolved in 450 g of deionized water to obtain a solution A. Solution B: 23.57 g (0.222 mol) of sodium carbonate
Was dissolved in 450 g of deionized water to obtain a solution B. The catalyst preparation tank was charged with 1800 g of deionized water, a 2N aqueous solution of NaOH was added to adjust the pH to 9 and the temperature in the tank to 4%.
While maintaining the temperature at 0 ° C., the solution A and the solution B were added dropwise over 1 hour, and after completion of the addition, the solution was aged for 1 hour. The mother liquor was removed by filtration, and the precipitate was washed with 6 liters of deionized water and spray-dried to obtain a composite metal hydroxide. This composite metal hydroxide is calcined at 800 ° C. for 3 hours in a nitrogen atmosphere,
The atomic ratio of Al: Mg: Cr = 0.3
23 g of the present second catalyst consisting of a composite metal oxide of 0: 0.50: 0.20 was obtained.

Example 4 This second catalyst (Al / Mg / Fe system) solution A: 47.69 g of aluminum nitrate nonahydrate (0.
127 mol) and 68.03 g of magnesium nitrate hexahydrate
(0.265 mol) and ferrous chloride tetrahydrate 21.35 g
(0.085 mol) was dissolved in 450 g of deionized water to obtain a solution A. Solution B: 13.47 g (0.127 mol) of sodium carbonate
Was dissolved in 450 g of deionized water to obtain a solution B. The catalyst preparation tank was charged with 1800 g of deionized water, a 2N aqueous solution of NaOH was added to adjust the pH to 9 and the temperature in the tank to 4%.
While maintaining the temperature at 0 ° C., the solution A and the solution B were added dropwise over 1 hour, and after completion of the addition, the solution was aged for 1 hour. The mother liquor was removed by filtration, and the precipitate was washed with 6 liters of deionized water and spray-dried to obtain a composite metal hydroxide. This composite metal hydroxide is calcined at 800 ° C. for 3 hours in a nitrogen atmosphere,
The atomic ratio of Al: Mg: Fe = 0.2
18 g of the present second catalyst comprising a composite metal oxide of 6: 0.56: 0.18 was obtained.

Example 5 4-Isopropyloxymethyl-1,3-dioxolan
Production of -2-one In a stainless steel autoclave (volume: 300 ml), 1.5 g of the first catalyst of Example 1, 150 g of isopropyl glycidyl ether, and 4-isopropyloxymethyl-1,3-dioxolan-2 as a solvent were used. After charging 30 g of -ON and sealing, the system is replaced with carbon dioxide,
Carbon dioxide was injected to 4.0 atm. 24 at 135 ° C
The mixture was stirred for a period of time, and the carbon dioxide absorbed during this time was replenished from the outside to keep the pressure of the reaction system constant. After the reaction was completed, the reaction vessel was cooled and the reaction solution was analyzed. As a result, it was found that 4-isopropyloxymethyl-1,3-dioxolan-2-one was produced at a yield of 97%.

Example 6 4-Allyloxymethyl-1,3-dioxolan-2-
To-one stainless steel autoclave (volume 300 ml), of the second catalyst (Al / Mg / Mn system) Example 2 0.45 g
, 150 g of allyl glycidyl ether, and 4-allyloxymethyl-1,3-dioxolane-2- as a solvent.
After charging 30 g of ON, the inside of the system was replaced with carbon dioxide and carbon dioxide was injected to 4.0 atm. 13
The mixture was stirred at 5 ° C. for 18 hours. During this time, the carbon dioxide absorbed was supplied from the outside to keep the pressure of the reaction system constant. After the reaction was completed, the reaction vessel was cooled and the reaction solution was analyzed.
Allyloxymethyl-1,3-dioxolan-2-one was produced in a yield of 98%.

Example 7 4-butyloxymethyl-1,3-dioxolan-2-
0.45 g of the present second catalyst (Al / Mg / Cr system) of Example 3 was placed in a stainless steel autoclave (300 ml in volume) manufactured by ON.
And 150 g of butyl glycidyl ether and 30 g of dimethylformamide as a solvent, and after sealing,
The inside of the system was replaced with carbon dioxide, and carbon dioxide was injected to 4.0 atm. The mixture was stirred at 135 ° C. for 18 hours. During this time, the carbon dioxide absorbed was supplied from the outside to keep the pressure of the reaction system constant. After the completion of the reaction, the reaction vessel was cooled and the reaction solution was analyzed. As a result, it was found that 4-butyloxymethyl-1,3-dioxolan-2-one was produced at a yield of 98%.

Example 8 4-butyloxymethyl-1,3-dioxolan-2-
0.45 g of the second catalyst (Al / Mg / Fe system) of Example 4 was placed in a stainless steel autoclave (volume: 300 ml) manufactured by ON.
And 150 g of butyl glycidyl ether and 30 g of dimethylformamide as a solvent, and after sealing,
The inside of the system was replaced with carbon dioxide, and carbon dioxide was injected to 4.0 atm. The mixture was stirred at 135 ° C. for 18 hours. During this time, the carbon dioxide absorbed was supplied from the outside to keep the pressure of the reaction system constant. After the completion of the reaction, the reaction vessel was cooled and the reaction solution was analyzed. As a result, it was found that 4-butyloxymethyl-1,3-dioxolan-2-one was produced at a yield of 98%.

Example 9 4-Pentyloxy (ethoxy) ₇ methyl-1,3-di
Production of oxolan-2-one 0.5 g of the second catalyst (Al / Mg / Mn system) of Example 2 was placed in a stainless steel autoclave (volume: 300 ml).
And 150 g of pentyl (oxyethylene) ₇ glycidyl ether and 30 g of dimethylformamide as a solvent, and after sealing, the inside of the system was replaced with carbon dioxide.
Carbon dioxide was injected to 4.0 atm. 18 at 135 ° C
The mixture was stirred for a period of time, and the carbon dioxide absorbed during this time was replenished from the outside to keep the pressure of the reaction system constant. After the completion of the reaction, the reaction vessel was cooled and the reaction solution was analyzed. As a result, 4-pentyloxy (ethoxy) ₇ methyl-1,3-dioxolane-2 was obtained.
-One was formed in a yield of 96%.

Comparative Example 1 A stainless steel autoclave (300 ml in volume) was charged with 1.5 g of MgO powder as a comparative catalyst, 150 g of butyl glycidyl ether, and 30 g of dimethylformamide as a solvent. The system was replaced with, and carbon dioxide was injected to 4.0 atm. The mixture was stirred at 135 ° C. for 24 hours, and the carbon dioxide absorbed during this period was supplied from the outside to keep the pressure of the reaction system constant. After completion of the reaction, the reaction vessel was cooled and the reaction solution was analyzed. As a result, 4-butyloxymethyl-1,3
The yield of -dioxolan-2-one was 20%.

Comparative Example 2 As a solution A, 214.81 g (0.837 mol) of magnesium nitrate hexahydrate and 0.178 mol of aluminum nitrate nonahydrate were dissolved in 450 g of deionized water. did. Separately, as a solution B, 18.87 g (0.178 mol) of sodium carbonate was dissolved in 450 g of deionized water. A solution A and a solution B were added to a catalyst preparation tank previously charged with 1800 g of deionized water while maintaining the pH at 9 and the temperature at 40 ° C. with a 2N NaOH aqueous solution.
The mixture was added dropwise over a period of time, and after completion of the addition, the mixture was aged for 1 hour. The mother liquor was filtered off and the precipitate was washed with 6 liters of deionized water,
The composite metal hydroxide was obtained by spray drying. The composite metal hydroxide is calcined at 700 ° C. for 3 hours in a nitrogen atmosphere, and the atomic ratio of Al to Mg is Al: Mg = 0.18:
Catalyst 17 of Comparative Example 2 consisting of 0.82 composite metal oxide
g. In the catalyst of Comparative Example 2, the X-ray diffraction pattern hardly confirmed the first peak within the range of 34.5 ± 2.5 deg., And the relative intensity of the first peak to the second peak was 25%. Clearly less.

Comparative Example 3 In a stainless steel autoclave (300 ml in volume), 1.5 g of the powder of Comparative Example 2 and 150 g of butyl glycidyl ether were used as comparative catalysts.
And 30 g of dimethylformamide as a solvent, and after sealing, the inside of the system was replaced with carbon dioxide and carbon dioxide was injected to 4.0 atm. The mixture was stirred at 135 ° C. for 24 hours, and the carbon dioxide absorbed during this period was supplied from the outside to keep the pressure of the reaction system constant. After the reaction was completed, the reaction vessel was cooled and the reaction solution was analyzed. As a result, the yield of 4-butyloxymethyl-1,3-dioxolan-2-one was 5% or less.

As is clear from the above results, Example 1
When the corresponding cyclic carbonate derivative was produced from the epoxy compound using the catalysts of Example 4 to Example 4, a high yield of 97% or more was obtained in each case. On the other hand, when MgO which is a single metal oxide is used as a catalyst, or even when a composite metal oxide containing Al and Mg is used, Al /
Satisfactory yield when using the catalyst of Comparative Example 2 in which the atomic ratio of (Al + Mg) is less than 0.2 and the relative intensity of the first peak to the second peak in the X-ray diffraction pattern is less than 25%. Was not obtained.

[0056]

The first carbonic acid esterification catalyst of the present invention comprises:
The atomic ratio between Al and Mg is Al: Mg = 0.25: 0.7.
5: 0.5: 0.5, and the X-ray diffraction pattern has the first peak, the second peak, and the third peak.
Wherein the relative intensity of the first peak to the second peak is in the range of 25% to 90% and the relative intensity of the third peak to the second peak is in the range of 30% to 100%. It is a metal oxide, and when an epoxy compound is reacted with carbon dioxide in the presence of this catalyst, a cyclic carbonate can be produced in a high yield by a simple post-treatment. The second carbonic esterification catalyst of the present invention comprises Al
Is a composite metal oxide containing Mg and a third metal selected from Groups 6A, 7A and 8 of the Periodic Table of Elements, and reacting an epoxy compound with carbon dioxide in the presence of this catalyst. The cyclic carbonate can be produced in a high yield by a simple post-treatment.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction pattern of one embodiment of the carbonic acid esterification catalyst of the present invention.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) B01J 23/70 B01J 23/70 Z 23/745 C07D 317/36 C07D 317/36 C07B 61/00 300 // C07B 61/00 300 C07D 303/22 C07D 303/22 B01J 23/74 301Z (72) Inventor Masayuki Toda 1-3-7 Honjo, Sumida-ku, Tokyo Inside Lion Corporation (72) Inventor Kaoru Suzuki Tokyo 1-7-3 Honjo, Sumida-ku, Tokyo Inside Lion Corporation (72) Inventor Nobuyuki Yamamoto 3-7-7 Honsho, Sumida-ku, Tokyo Inside Rion Corporation F term (reference) 4C048 AA01 BB01 BB02 CC01 UU03 XX02 4G069 AA02 AA08 BB06A BB06B BB08B BB10B BB12B BB16B BC02B BC10A BC10B BC16A BC16B BC57A BC58A BC58B BC59A BC61A BC62A BC62B BC63A BC65A BC66A BC66B BC67A BC6 8A BC69A BC71A CB75 DA08 EC25 4H039 CA42 CA66 CF30

Claims (6)

[Claims] 1. A composite metal oxide containing Al and Mg, wherein the atomic ratio of Al and Mg is Al: Mg = 0.25:
0.75 to 0.5: within the range of 0.5 and CuΚ
The X-ray diffraction pattern using α radiation shows the first peak in the range of 34.5 ± 2.5 deg.
A second peak within the range of 2.5 ± 2.5 deg.
A third peak within a range of ± 2.5 deg., A relative intensity of the first peak to the second peak is in a range of 25% to 90%, and a relative intensity of the third peak to the second peak is A carbonic acid esterification catalyst characterized by being in the range of 30% to 100%. 2. Al, Mg, Group 6A of the Periodic Table of the Elements,
A carbonic acid esterification catalyst comprising a composite metal oxide containing at least one third metal selected from the group 7A and group 8 ranges. 3. The method according to claim 2, wherein the third metal is Cr, Mo, Mn, T
The carbonation esterification catalyst according to claim 2, wherein the catalyst is selected from the group consisting of c, Fe, Co, Ni, and Ru. 4. A composite metal hydroxide containing Al, Mg and the third metal by co-precipitating a water-soluble Al salt, a water-soluble Mg salt, and a water-soluble salt of the third metal in an aqueous solution. The method for producing a carbonic acid esterification catalyst according to claim 2 or 3, wherein the composite metal hydroxide is calcined at a temperature in the range of 300 ° C to 1000 ° C. 5. A method for producing a cyclic carbonate, comprising reacting an epoxy compound with carbon dioxide in the presence of the catalyst for esterification of carbon according to claim 1, 2, or 3. Production method. 6. The cyclic compound according to claim 5, wherein the epoxy compound is a compound represented by the following general formula (1), and the cyclic carbonate is a compound represented by the following general formula (2). Method for producing carbonate ester. Embedded image (R in the formula is a hydrogen atom, a saturated or unsaturated linear, branched or cyclic hydrocarbon group having a carbon number of 1 to 22, or a compound represented by the following general formula (3) -CH ₂ (OR ₂ ) _N OR ₁ ... (3) wherein R ₁ is a hydrogen atom, a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 22 carbon atoms, and R ₂ has ₂ carbon atoms. Alkylene groups in the range of 4 to 4, which may be the same or different, and n is a group representing an integer in the range of 0 to 30 by the average number of added moles of the OR ₂ group.)