JPH08198817A - Production of aryl carbonate and catalyst used therefor - Google Patents

Abstract

PURPOSE: To facilitate the separation of a catalyst after reaction and industrially and advantageously obtain the subject ester useful as a raw material, etc., for resins in high yield and selectivity by using a specific microporous material as the catalyst. CONSTITUTION: (B) An arylcarboxylic acid ester of formula II [R<3> is a (cyclo) alkyl or an arylalkyl; R<4> is same as R<1> ] and (C) an alkyl carbonate of formula III (R<5> is same as R<3> ; R<6> is same as R<2> ) are passed through a step for carrying out the transesterification in the liquid phase in the presence of (A) a heterogeneous catalyst of a microporous material containing a group IV metallic element to afford the objective compound of formula I [R<1> is a (substituted) aryl; R<2> is a (cyclo)alkyl, an arylalkyl or a (substituted)aryl]. Furthermore, the component (A) is preferably a metallosilicate, especially a mesoporouse titanosilicate having the 30-1000 atomic ratio of Si to Ti, >=500m<2> /g specific surface area and >=0.2cm<3> /g volume of pores having 1.3-20nm diameter.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing an aryl carbonate and a catalyst used therefor, and more particularly to a method for producing an aryl carbonate using a transesterification reaction and a catalyst used therein.

[0002]

2. Description of the Related Art Various methods for producing aryl carbonates are known, for example, a method based on a transesterification reaction between a carbonate ester and an aromatic hydroxy compound, and a method based on a transesterification reaction between an alkylaryl carbonate ester. Leveling method. A catalyst is required for these transesterification reactions, and various catalysts have been proposed. For example, a Lewis acid or a compound that generates a Lewis acid, a Ti-based compound, an Al-based compound, a lead compound,
It has been proposed to use an organotin compound or the like as a catalyst. However, all of the catalysts used in these methods are homogeneous catalysts in which the catalyst dissolves in the raw materials and reacts.
It is difficult to separate the catalyst after the reaction, and it is a problematic catalyst for industrial implementation.

In order to solve such a problem of separation, Japanese Patent Publication No. 61-5467 proposes using a silica-titania composite oxide as a heterogeneous catalyst. It has been proposed to use high surface area titanium oxide as a catalyst. However, since silica-titania composite oxide has a strong acid property, a decarboxylation reaction which is a side reaction is likely to occur. Further, there is a problem that the high surface area titanium oxide has a low catalytic activity. Further, both catalysts are heterogeneous at the start of the reaction, but as the reaction proceeds, the catalyst components are considerably dissolved in the raw materials, and are substantially the same as the homogeneous system.

[0004]

The problem to be solved by the present invention is to produce aryl carbonates with high yield, high selectivity and industrial advantage. Another problem to be solved by the present invention is to provide a catalyst for producing an aryl carbonate ester, which is easy to separate the catalyst after the reaction, and which has high yield, high selectivity and is industrially advantageous. Is.

[0005]

[Means for Solving the Problems]

 (1) Method for producing aryl carbonate according to the present invention
Is represented by the following general formula (I) (R¹O) CO (OR²) (I) (wherein, R¹Represents an aryl group which may have a substituent
Represent, R²Is an alkyl group, cycloalkyl group, aryl
Alkyl group or aryl group which may have a substituent
Represents To produce the aryl carbonate represented by
A method for producing a microporous material containing a group IV metal element
In the liquid phase in the presence of a heterogeneous material catalyst, the following general formula
(II) R³COOR^Four (II) (wherein R³Represents an alkyl group, a cycloalkyl group or
Represents a reel alkyl group;^FourHas a substituent
Represents a good aryl group. Aryl carboxy represented by)
Acid ester and the following general formula (III) (R^FiveO) CO (OR⁶) (III) (wherein, R^FiveIs an alkyl group, cycloalkyl group, aryl
Represents an alkyl group; ⁶Is an alkyl group, cycloalkyl
Even if it has an aryl group, an arylalkyl group or a substituent.
Represents a good aryl group. ) Represented by alkyl carbonate
And a reaction step of transesterifying with ter.

(2) Aryl carbonate according to the present invention
The catalyst for production is represented by the following general formula (II):³COOR^Four (II) (wherein R³Represents an alkyl group, a cycloalkyl group or
Represents a reel alkyl group;^FourHas a substituent
Represents a good aryl group. Aryl carboxy represented by)
Acid ester and the following general formula (III) (R^FiveO) CO (OR⁶) (III) (wherein, R^FiveIs an alkyl group, cycloalkyl group, aryl
Represents an alkyl group; ⁶Is an alkyl group, cycloalkyl
Even if it has an aryl group, an arylalkyl group or a substituent.
Represents a good aryl group. ) Represented by alkyl carbonate
Is transesterified in the liquid phase with the following general formula (I) (R¹O) CO (OR²) (I) (wherein, R¹Represents an aryl group which may have a substituent
Represent, R²Is an alkyl group, cycloalkyl group, aryl
Alkyl group or aryl group which may have a substituent
Represents To produce the aryl carbonate represented by
A catalyst for use in the case, which contains a group IV metal element
Containing a porous material.

[0007] The microporous material containing a group IV metal element is preferably a metallosilicate or a metalloaluminophosphate. Preferably, the metallosilicate is mesopore titanosilicate. It is preferable that the mesopore titanosilicate has an atomic ratio of silicon to titanium 1 of 30 to 1,000.

The mesopore titanosilicate has a specific surface area of not less than 500 m ² / g, and 1.3 nm to 20 nm.
The volume of pores having a diameter within the range is preferably 0.2 cm ³ / g or more. The mesopore titanosilicate preferably has at least one peak of the powder X-ray diffraction pattern after the heat treatment having a plane interval larger than 1.8 nm.

Preferably, the metalloaluminophosphate is crystalline titanoaluminophosphate. Hereinafter, the present invention will be described in detail. Production Method The method for producing an aryl carbonate according to the present invention comprises the steps of IV
A reaction step of transesterifying the arylcarboxylic acid ester and the carbonic acid ester in a liquid phase in the presence of a microporous material heterogeneous catalyst containing a group metal element is included.

The aryl carboxylic acid ester is not particularly limited as long as it is represented by the general formula (VIII), but it is phenyl acetate, methyl phenyl acetate (each isomer), ethyl phenyl acetate (each isomer). , Chlorophenyl acetate (each isomer), isopropylphenyl acetate (each isomer), paramethoxyphenyl acetate (each isomer), dimethylphenyl acetate (each isomer), naphthyl acetate (each isomer), phenyl propionate, propion Examples thereof include methyl phenyl acid (each isomer), phenyl butyrate, methyl phenyl isobutyrate (each isomer), methyl phenyl valerate (each isomer), phenyl isovalerate, phenyl hexanoate, and phenyl heptanoate.

The carbonic acid ester is not particularly limited as long as it is a carbonic acid ester represented by the general formula (III). Specifically, dimethyl carbonate, diethyl carbonate,
Normal propyl carbonate, isopropyl carbonate, dibutyl carbonate (each isomer), dipentyl carbonate (each isomer), dihexyl carbonate (each isomer), diheptyl carbonate (each isomer),
Dioctyl carbonate (each isomer), dinonyl carbonate (each isomer), didecyl carbonate (each isomer), dicyclohexyl carbonate (each isomer), dibenzyl carbonate (each isomer), diphenethyl carbonate (each isomer), dicarbonate -Aliphatic carbonates such as methylbenzyl (each isomer); alkylaryl carbonates such as methylphenyl carbonate and ethylphenyl carbonate, and a mixture thereof may be used. Dimethyl carbonate is particularly preferably used industrially.

In the method of the present invention, the lower limit of the molar ratio of the carbonic acid ester to the starting arylcarboxylic acid ester is 1/50, preferably 1/10, more preferably 1 /.
5, the upper limit is 50, preferably 10, more preferably 5
Is. Since this reaction is an equilibrium reaction having an equilibrium constant of about 0.2 to 5, by using one of the raw materials in a large excess, the conversion of the smaller raw material can be increased. Since it must be recycled, it is industrially disadvantageous to make the molar ratio too large or small. For example, when the carbonic acid ester is a dialkyl carbonic acid ester, if the carbonic acid ester is used in excess, the conversion rate of the arylcarboxylic acid ester increases, but the alkylaryl carbonic acid ester becomes the main product, and the target product diaryl carbonic acid ester is not formed. It gets harder. Conversely, when the amount of the aryl carboxylate is excessive, the conversion of the carbonate becomes high, and the diaryl carbonate becomes the main product.

The production method according to the present invention comprises a batch reactor,
It can be carried out in any of flow-through reactors and is not particularly limited. Furthermore, it can also be carried out in a reactive distillation format. The lower limit of the reaction temperature is 100 ° C, preferably 140 ° C, more preferably 160 ° C. The upper limit of reaction temperature is 35
The temperature is 0 ° C, preferably 300 ° C, more preferably 280 ° C. If the reaction temperature is too low, the catalyst activity is low and the reaction time and contact time are too long, resulting in low productivity. On the other hand, if the reaction temperature is too high, side reactions such as decarboxylation reaction are likely to occur, or the pressure inside the reactor is too high, which is disadvantageous.

When a batch reactor is used, the lower limit of the amount of the catalyst used is 0.1% by weight, preferably 0.5% by weight, more preferably 1% by weight, based on the raw materials. The upper limit is 40% by weight, preferably 30% by weight, more preferably 20% by weight. A predetermined amount of the catalyst and the raw material of the present invention is charged into a batch reactor, and a transesterification reaction is performed with stirring at a predetermined temperature to obtain a mixture containing the desired aryl ester. The reaction pressure is a pressure generated by the vapor pressure of the raw material. At that time, the reaction time varies depending on the reaction temperature and the amount of the catalyst, but generally 0.1 to
The period is 100 hours, preferably 1 to 30 hours. The catalyst can be easily removed from the thus obtained reaction liquid containing the catalyst by a method such as centrifugation or filtration.

The target aryl ester, by-product and unreacted starting material can be recovered from the reaction solution after the catalyst is separated, generally by distillation, and in some cases by extraction or recrystallization. it can. When a flow reaction type reactor is used, it can be carried out in any of a fluidized bed type, a fixed bed type, and a stirred tank type. The reaction conditions at this time vary depending on the raw material composition and the reaction temperature, but the liquid hourly space velocity (LHSV) obtained by dividing the volume flow rate of the flowing raw material by the volume of the reactor.
And the lower limit is 0.05 hr ^-1 , preferably 0.1 hr
r ^-1 , more preferably 0.2 hr ^-1 , and the upper limit is 5
It is 0 hr ^-1 , preferably 20 hr ^-1 .

[0016]catalyst The catalyst according to the present invention comprises a microporous material containing a group IV metal element.
Contains the glass material and is mostly dissolved in the raw material
None (heterogeneous system). Included in the catalyst of the present invention
Microporous materials are extremely regular
Very crystalline with pores in the micropore to mesopore range
It is a solid substance with high specificity and a large specific surface area. Specifically
Has a pore size of 0.4 to 10 nm and a crystal structure of MFI
(ZSM-5, TS-1, etc.), MEL (ZSM-11,
TS-2, etc.), AFI (ALPO _Four-5), BEA
(Β-type zeolite, etc.), VFI (VPI-5, etc.), MC
It has a structure such as M-41 and a specific surface area of 100m.²/ G ~
1500m²/ G is a large substance.

Examples of those having micropores include metallosilicate and metalloaluminophosphate. In addition, examples of those having mesopores include mesopoitatanosilicate and the like, and they are preferably used in the reaction for obtaining a product having a large molecular diameter as in the present invention. The metallosilicate is a compound in which another metal element enters a crystal lattice in place of the aluminum atom of zeolite, which is an aluminosilicate. In the present invention, the metal element includes a group IV metal element, and examples of the group IV metal element include elements such as titanium, zirconium, tin, and lead. Particularly, when the metal element is titanium, titanosilicate having a structure similar to that of ZSM-5 having an MFI type structure or ZSM-11 having a MEL type structure or β may be used.
Type titanoaluminosilicate and the like are known.

The composition of the crystalline metallosilicate containing a Group IV metal element is, in terms of the atomic ratio of silicon to Group IV metal element 1, a lower limit of 10, preferably 20, more preferably 25, and an upper limit of 25. At 500, preferably 2
00, more preferably 100. If the atomic ratio of silicon to the group IV metal element is too small, the amount of the group IV metal element will be too large and not all the group IV metal elements will be incorporated into the crystal lattice but will exist outside the crystal lattice as an oxide. On the other hand, if the atomic ratio of silicon to the group IV metal element is too large, the density of the group IV metal element in the crystal will decrease, and the catalytic activity will decrease.

The metalloaluminophosphate is
Aluminum phosphate type molecular sieves (AlPO ₄
-N: n is a number indicating a crystal structure) and a part of aluminum or phosphorus is replaced by another metal element. Aluminum phosphate type molecular sieves (AlPO ₄ ) is a substance composed of AlPO ₄ and having a structure in which AlO ₄ tetrahedra and PO ₄ tetrahedra are alternately and regularly arranged. There are various kinds of crystal structures of aluminophosphate, and n of AlPO ₄ -n is given as a number for distinguishing them. For example, AlPO
₄ -5 is a substance consisting of oxygen 12-membered ring structure having a pore size of about 8 nm, also AlPO ₄ -11 is pore size 5-6
It is a substance composed of a 10-membered oxygen ring structure having nm. The metalloaluminophosphate referred to in the present invention is a substance in which a part of the aluminum or phosphorus is replaced with a Group IV metal element such as titanium, zirconium, tin or lead as described above.

With respect to the composition of the crystalline metalloaluminophosphate containing a group IV metal element, the lower limit of the total sum of Al and P relative to group IV metal element 1 is 1, preferably 5, and more preferably. Is 10 and the upper limit is 500, preferably 100, and more preferably 50. If the lower limit is less than the lower limit, the Group IV metal element is too large and all the Group IV metal elements are not taken into the crystal lattice, and exist outside the crystal lattice as oxides. The density of the group metal atom in the crystal decreases, and the catalytic activity decreases. The atomic ratio of P to Al in the crystalline metalloaluminophosphate containing a Group IV metal element is preferably from 0.9 to 1.1. Since trivalent Al and pentavalent P partially replace the tetravalent group IV metal element, P
If the atomic ratio is outside the range of 0.9 to 1.1, the overall charge balance may be disturbed and catalytic acid sites may be generated. As a result, when producing an aryl carbonate, a side reaction such as a decarboxylation reaction proceeds, and a by-product tends to be generated.

The above-mentioned mesopore titanosilicate is a compound in which part of silicon atoms of mesopore silicalite is replaced by titanium atoms. The specific surface area of the mesopoitatanosilicate is 500 m ² / g or more and 700 m ²
/ G or more is preferable. Specific surface area is 500m ²
If it is smaller than / g, the catalyst activity will be reduced.

The mesopoitatanosilicate is 1.3 n
The volume of pores having a diameter in the range of m to 20 nm is 0.2 c
m ³ / g or more, and preferably 0.3 cm ³ / g or more. If the volume of the pores having a diameter in the range of 1.3 nm to 20 nm is less than 0.2 cm ³ / g, the diffusion of the reaction raw materials into the pores of the catalyst becomes insufficient, so that the catalytic activity decreases. .

The composition of the mesopore titanosilicate is titanosilicate having an atomic ratio of silicon to titanium 1 of 30 to 1,000. At this time, the atomic ratio of silicon to titanium 1 is 30 at the lower limit, preferably 60,
The upper limit is 1000, preferably 500, more preferably 300. If the silicon / titanium atomic ratio is too small,
Since there is too much titanium, not all of the titanium is taken into the crystal lattice and exists as an oxide outside the crystal lattice. On the other hand, if the silicon / titanium atomic ratio is too large, the density of titanium in the crystal will decrease, and the catalytic activity will decrease.

Regarding the crystal structure of the mesopore titanosilicate, at least one peak of the powder X-ray diffraction pattern after heat treatment has a plane spacing larger than 1.8 nm;
Preferably, it has a plane spacing larger than 2.0 nm. When the interplanar spacing is 1.8 nm or less, the pore diameter is not sufficient for the size of the product, and the reaction rate is reduced and the product is not easily desorbed. The crystal structure of the mesopore titanosilicate does not need to be a clear hexagonal system such as so-called MCM-41, but may be a cubic system or a layered lamellar structure.

The crystallinity of the microporous material can be determined by powder X-ray diffraction (XRD) analysis. For example, non-crystalline silica-titania does not show a distinct XRD diffraction peak, but only an amorphous broad peak. On the other hand, in the case of crystalline metallosilicate, metalloaluminophosphate, etc., a clear XRD diffraction peak corresponding to each crystal structure is observed.

Method for producing aryl ester according to the present invention
The method includes microstructures containing Group IV metal elements of these structures.
Porous materials are effective, and specifically,
Crystalline metallosilicate containing metal element, Group IV metal element
Particularly, crystalline metalloaluminophosphates containing
It is effective. Titanium is particularly preferred as the IV group metal element.
New Among the crystalline titano aluminophosphates, T
APO-5 (AlPO _Four-5 type) is relatively
It is suitable for use because it is easy, has good crystallinity, and has high catalytic activity.
Can be used.

As the method for preparing the catalyst of the present invention, a method generally used for preparing a microporous material can be applied. Among them, the hydrothermal synthesis method is preferably used, and this method is a method in which the raw material of the microporous material, the template agent and water are mixed and heated to a predetermined temperature for crystallization. According to the present invention, a transesterification reaction or a disproportionation reaction due to a transesterification reaction for obtaining target aryl esters rapidly progresses.
In addition, since the microporous material catalyst containing a group IV metal element hardly dissolves in the reaction raw material (it is a heterogeneous system), the reaction solution and the catalyst can be easily separated, and the distillation step in the homogeneous reaction can be easily performed. Reverse reaction with residual catalyst,
A decrease in yield due to decomposition, polymerization reaction, etc. can be prevented. Therefore, industrially important aryl esters can be efficiently produced.

The aryl esters obtained by the production method according to the present invention are industrially useful substances as resin raw materials and intermediate raw materials for various resin raw materials. Further, the group IV metal element-containing microporous material according to the present invention is a substance useful as a heterogeneous catalyst used in a method for producing an alkylaryl carbonate, a diaryl carbonate or an aryl carboxylate.

[0029]

EXAMPLES The present invention will be described in more detail below with reference to examples and comparative examples, but the present invention is not limited to these examples. The conversion and the yield in the examples are calculated by the following formulas. -Conversion ratio of aryl carboxylic acid ester (mol%) = 100-(number of moles of recovered unreacted aryl carboxylic acid ester / number of moles of raw material aryl carboxylic acid ester supplied) x 100-Yield of alkyl aryl carbonate ( (Mol%) = (mol number of alkylaryl carbonate generated / mol number of raw material aryl carboxylate supplied × 100) Yield of diaryl carbonate (mol%) = (mol number of generated diaryl carbonate / supplied) (Mole number of raw material aromatic carboxylic acid ester) × 200 <Preparation of catalyst> Example 1 (Preparation of catalyst A-1) 81.1 g of tetraethyl orthosilicate under a nitrogen stream
(0.39 mol) titanium tetrabutoxide 1.
3 g was slowly added dropwise with stirring, then the temperature was raised to about 80 ° C., and the mixture was stirred for about 5 hours. This is cooled to room temperature and then dodecyltrimethylammonium chloride 0.1.
A solution obtained by dissolving 29 mol in 231.3 g of 2-propanol was added, and the mixture was stirred for 30 minutes. Next, tetramethylammonium hydroxide (15% aqueous solution) 17.7
g in 35.4 g of 2-propanol.
The mixture was slowly added dropwise over a period of minutes, and stirring was continued for about 12 hours. Further, 42.9 g of tetramethylammonium hydroxide (15% aqueous solution) and 590 g of ion-exchanged water were added, the temperature was raised to about 90 ° C., and the alcohol was distilled off for about 5 hours. Then, it was transferred to a Teflon container and hydrothermally synthesized at 100 ° C. for 240 hours. The obtained solid was filtered, washed, dried, and heat-treated in the air at 540 ° C. for 6 hours to obtain mesopore titanosilicate. This catalyst is designated as A-1.

The molar ratio of the raw materials used is Si: Ti: dodecyltrimethylammonium chloride: water = 1: 1 /
It was 100: 0.75: 85.5. The powder X-ray diffraction pattern is shown in FIG. The peak with the largest spacing is 2
The surface spacing was 3.32 nm with a peak of 2.66 ° at θ. FIG. 2 shows the pore size distribution obtained by the nitrogen adsorption method.
It was shown to. The pore diameter determined from this was about 2.5 nm. The specific surface area by the BET method was 1319 m ² / g,
The Si / Ti atomic ratio determined from CP emission analysis was 89.9.

Example 2 (Preparation of Catalyst A-2) 34.6 g of phosphoric acid (85% by weight aqueous solution) was charged with an internal volume of 500
Into a beaker of ml, 73.6 g of tetraethylammonium hydroxide (20% by weight aqueous solution) was added, stirred for a while, and then cooled to room temperature. 18.0 g of ion-exchanged water and pseudo-boehmite (Cat) were added to this mixed solution.
alloid-AP; Catalysis Co., Ltd., 70 wt% Al ₂
0 ₃ content) 21.9 g was added and stirred for 2 hours further added titanium tetraisopropoxide 15.8 g. This mixed solution was transferred to an autoclave to perform hydrothermal synthesis.
In hydrothermal synthesis, the temperature is raised from room temperature to 160 ° C in 90 minutes, then from 160 ° C to 200 ° C in 3 hours, and then 20
The test was carried out at 0 ° C. for 4 hours. The generated solid is filtered off,
Further, after washing with pure water three times, drying and firing were performed by the following methods. First, the temperature is raised from room temperature to 120 ° C at 10 ° C per minute,
Hold at 120 ° C. for 180 minutes, and again at 10 ° C. every 2 minutes
After the temperature was raised to 30 ° C., the temperature was maintained at 230 ° C. for 480 minutes, further raised to 600 ° C. at 3 ° C. per minute, and maintained at 600 ° C. for 180 minutes to obtain crystalline titanoaluminophosphate. This catalyst is designated as A-2.

According to ICP analysis, the atomic ratios of aluminum and phosphorus to titanium 1 are 6.25 and 6.
27. Specific surface area by BET method is 269 m ² /
g. Data of powder X-ray diffraction using CuKα ray is in shown in Table 1, was AlPO ₄ -5 type structure.

[0033]

[Table 1]

<Production of Aryl Carbonic Acid Ester> Example 3 33.6 g of dimethyl carbonate in a dry box in an autoclave having an internal volume of 200 ml equipped with a stirrer, a pressure gauge, a sampling nozzle, a thermometer, and an external heater for heating. 66.4 g of phenyl herbate and 2.0 g of catalyst A-1 were charged and pressurized to 200 kPa with nitrogen. This was heated to 200 ° C. and reacted for 5 hours. The molar ratio of raw material dimethyl carbonate: phenyl valerate is 1: 1, and the catalyst is 2% by weight. The reaction solution was analyzed by gas chromatography to determine the conversion rate and yield. The results are shown in Table 2.

The concentration of eluted Ti in the reaction solution was analyzed by an ICP emission spectrometer. The concentration of Ti detected in the reaction solution was only 3 ppm, and almost no elution was observed. Since this reaction is an equilibrium reaction and the conversion rate and yield hardly change even if the reaction time is extended, it can be said that the reaction proceeded to near equilibrium in this example. Example 4 A reaction was carried out in the same manner as in Example 3 except that the raw materials used were changed to 45.2 g of dimethyl carbonate and 54.8 g of phenyl butyrate instead of phenyl valerate. The molar ratio of dimethyl carbonate: phenyl butyrate is 3: 2 and the catalyst is 2% by weight.
The reaction results are shown in Table 2.

Example 5 The starting material used was diethyl carbonate 6 instead of dimethyl carbonate.
7.0 g, phenyl acetate 3 instead of phenyl valerate
The reaction was carried out in the same manner as in Example 3 except that the amount was changed to 3.0 g. The dimethyl carbonate: phenyl acetate molar ratio is 7:
3, the catalyst is 2% by weight. The reaction results are shown in Table 2.

Example 6 A reaction was carried out in the same manner as in Example 3 except that the raw materials used were changed to 41.7 g of dimethyl carbonate and 58.3 g of phenyl propionate instead of phenyl valerate, and containing aryl carbonates. A reaction solution was obtained. This reaction solution was stirred for 20 minutes with an internal diameter of 20 mm, a condenser / reflux distributor, and a distillation column of 10 stages provided with an inner volume of 200 ml.
And heated to 200 ° C. to cause a reaction. The generated steam was distilled at a reflux ratio of 2 to extract the light-boiling components from the distillation column. One hour after the start of the reaction, the pressure in the system was gradually reduced to 100 mmHg, and the generated light boiling components were sufficiently distilled off. The reaction was carried out for 5 hours to obtain 69.0 g of a distillate and 31.0 g of a residue, which were analyzed and the conversion and yield were determined. The results are shown in Table 2.

Example 7 A reaction was carried out in the same manner as in Example 3 except that the catalyst A-2 was used instead of the catalyst A-1. The results are shown in Table 2. Almost no Ti was detected in the reaction solution. Although the reaction rate was slower than when using the catalyst A-1, methylphenyl carbonate and diphenyl carbonate were produced.

[0039]

[Table 2]

[0040]

According to the method for producing an aryl carbonate according to the present invention, since a microporous material containing a Group IV metal element is used as a catalyst, the aryl carbonate is transesterified with an alkyl carbonate to form an aryl ester. The carbonic acid ester formation reaction proceeds quickly. In addition, since a catalyst that hardly dissolves in the reaction raw material (is a heterogeneous system) is used, it is possible to prevent a reduction in yield due to a reverse reaction, a decomposition, a polymerization reaction, or the like due to a residual catalyst in a distillation step, which is observed in a homogeneous reaction. Therefore, an aryl carbonate can be produced industrially advantageously with high yield and high selectivity.

The catalyst for producing an aryl carbonate according to the present invention contains a microporous material containing a Group IV metal element and is hardly soluble in the reaction raw material (is a heterogeneous system). Is easy,
It is possible to prevent a reduction in yield due to a reverse reaction, decomposition, polymerization reaction, or the like due to a residual catalyst in a distillation step, which is observed in a homogeneous reaction.
Therefore, an aryl carbonate can be produced industrially advantageously with high yield and high selectivity.

Among the microporous materials containing the group IV metal elements, metallosilicate or metalloaluminophosphate exhibits particularly excellent effects. Among the above metallosilicates, mesopoitatanosilicate exhibits a particularly excellent effect. Among the metalloaluminophosphates, crystalline titanoaluminophosphate exhibits particularly excellent effects.

[Procedure amendment]

[Submission date] May 2, 1995

[Procedure Amendment 1]

[Document name to be amended] Statement

[Name of item to be corrected] Brief description of the drawing

[Correction method] Added

[Correction content]

[Brief description of drawings]

FIG. 1 is a view showing an X-ray diffraction pattern of a catalyst A-1 prepared in Example 1.

FIG. 2 is a view showing a pore size distribution of a catalyst A-1 prepared in Example 1.

Claims (9)

[Claims] (1) The following general formula (I) (R¹O) CO (OR²) (I) (wherein, R¹Represents an aryl group which may have a substituent
Represent, R²Is an alkyl group, cycloalkyl group, aryl
Alkyl group or aryl group which may have a substituent
Represents To produce the aryl carbonate represented by
A method for producing a microporous material containing a group IV metal element
In the liquid phase in the presence of a heterogeneous material catalyst, the following general formula
(II) R³COOR^Four (II) (wherein R³Represents an alkyl group, a cycloalkyl group or
Represents a reel alkyl group;^FourHas a substituent
Represents a good aryl group. Aryl carboxy represented by)
And an acid ester represented by the following general formula (III) (R^FiveO) CO (OR⁶) (III) (wherein, R^FiveIs an alkyl group, cycloalkyl group, aryl
Represents an alkyl group; ⁶Is an alkyl group, cycloalkyl
Even if it has an aryl group, an arylalkyl group or a substituent.
Represents a good aryl group. ) Represented by alkyl carbonate
Aryl carbon including a reaction step of transesterification with ter
A method for producing an acid ester. 2. The method for producing an aryl carbonate ester according to claim 1, wherein the microporous material containing a Group IV metal element is a metallosilicate. 3. The method for producing an aryl carbonate ester according to claim 2, wherein the metallosilicate is mesopoitatanosilicate. 4. The mesopore titanosilicate is titanium 1
The method for producing an aryl carbonate according to any one of claims 1 to 3, wherein an atomic ratio of silicon to the carbon is 30 to 1,000. 5. The mesopoitatanosilicate has a specific surface area of 500 m ² / g or more and 1.3 nm to 20 nm.
Pore volume having a size in the range of is is 0.2 cm ³ / g or more, a manufacturing method of an aryl carbonic acid ester according to claim 1. 6. The aryl carbonate according to claim 1, wherein the mesopore titanosilicate has at least one of peaks in a powder X-ray diffraction pattern after heat treatment having an interplanar spacing larger than 1.8 nm. Manufacturing method. 7. The microporous material containing a Group IV metal element is metalloaluminophosphate,
The method for producing an aryl carbonate according to claim 1. 8. The method for producing an aryl carbonate according to claim 7, wherein the metalloaluminophosphate is crystalline titanoaluminophosphate. 9. The following general formula (II) R³COOR^Four (II) (wherein R³Represents an alkyl group, a cycloalkyl group or
Represents a reel alkyl group;^FourHas a substituent
Represents a good aryl group. Aryl carboxy represented by)
And an acid ester represented by the following general formula (III) (R^FiveO) CO (OR⁶) (III) (wherein, R^FiveIs an alkyl group, cycloalkyl group, aryl
Represents an alkyl group; ⁶Is an alkyl group, cycloalkyl
Even if it has an aryl group, an arylalkyl group or a substituent.
Represents a good aryl group. ) Represented by alkyl carbonate
Is transesterified in the liquid phase with the following general formula (I) (R¹O) CO (OR²) (I) (wherein, R¹Represents an aryl group which may have a substituent
Represent, R²Is an alkyl group, cycloalkyl group, aryl
Alkyl group or aryl group which may have a substituent
Represents To produce the aryl carbonate represented by
The catalyst used in the process includes a microporous material containing a group IV metal element.
Contact for producing aryl carbonate characterized by having
Medium.