JPH0889810A - Method for producing aromatic carbonic acid ester - Google Patents

Abstract

PURPOSE: To provide a method for producing an arom. carbonate in a high yield by using a catalytic system being simpler than before and recyclable when the arom. carbonate is produced by reacting an arom. hydroxyl compd. with carbon monoxide and oxygen. CONSTITUTION: A catalytic system consisting of at least one selected from palladium and palladium compd., at least one of compd. contg. a metal ion of cerium, cobalt or manganese as a redox agent, at least one of inorg. halide selected from among alkali metal halides and alkaline earth metal halides and an active carbon, is used.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an aromatic carbonic acid ester using a specific catalyst system. Aromatic carbonic acid esters, especially diphenyl carbonate, are useful as raw materials for polycarbonate and the like.

[0002]

2. Description of the Related Art Conventionally, a method of reacting an aromatic hydroxy compound with phosgene has been used as a method for producing an aromatic carbonic acid ester. However, this method is not preferable because phosgene is highly toxic. Therefore, as a method that does not use phosgene, a method of producing an aromatic carbonic acid ester from an aromatic hydroxy compound and carbon monoxide and oxygen has been proposed.

As a catalyst in this method, Japanese Examined Patent Publication No. 56-3
No. 8144 discloses a palladium compound and III of the periodic table.
Methods of using compounds and bases containing metals of group A, IVA, VA, VIA, IB, IIB, VIB or VIIB are described. Further, JP-B-56-38145 discloses a method using a palladium compound, a manganese complex or cobalt complex, a base and a desiccant; JP-A-1-165551 discloses a method using a palladium compound, iodine and zeolites; JP-A-2-104564 discloses a method using a palladium compound, a divalent or trivalent manganese compound, a tetraalkylammonium halide and quinones; JP-A-2-142754 discloses a palladium compound, a divalent or trivalent compound. -Valent cobalt compounds, tetraalkylammonium halides and quinones; JP-A-525095 discloses a method using palladium compounds, cobalt compounds, organic or inorganic halides and basic compounds; JP-A-5-58961. The publication describes a method using a palladium compound, a cobalt compound and an alkali metal halide. Has been.
Further, in JP-A-5-97775, a palladium compound, cobalt, iron, cerium, manganese, molybdenum,
Mixture of a cocatalyst of an inorganic compound selected from samarium, vanadium, chromium and copper, an organic cocatalyst selected from an aromatic ketone, an aliphatic ketone and an aromatic polycyclic hydrocarbon, and a quaternary ammonium salt. Is described.

[0004]

The conventional catalyst system for producing an aromatic carbonic acid ester requires a quaternary ammonium salt, a base and an organic co-catalyst in order to obtain the target compound in a high yield. Which makes the catalyst complex,
In addition, quaternary ammonium salts and the like are unstable under the reaction conditions, and there is a problem that a large amount of brominated phenol and the like is produced, and it is difficult to recycle the catalyst. On the other hand, the yield is low if these compounds are not used,
It wasn't practical. An object of the present invention is to provide a method for producing a target aromatic carbonic acid ester in a high yield with a simple catalyst system which can be recycled.

[0005]

The present inventors have completed the present invention by finding that the production efficiency of aromatic carbonic acid ester is improved by using the following specific catalyst system as a catalyst. That is, the present invention relates to a method for producing an aromatic carbonic acid ester by reacting an aromatic hydroxy compound with carbon monoxide and oxygen, and (A) one or more selected from palladium and a palladium compound, and (B) a redox agent. As one or more compounds containing a metal ion of cerium, cobalt or manganese, one or more inorganic halides selected from (C) alkali metal halides and alkaline earth metal halides, and (D) activated carbon are present. Then, the reaction is carried out to produce an aromatic carbonic acid ester.

[Detailed Description of the Invention] 1. Reaction Raw Materials (1) Aromatic Hydroxy Compound The aromatic hydroxy compound used in the present invention is an aromatic mono- or polyhydroxy compound, for example, phenol; cresol, xylenol, trimethylphenol, tetramethylphenol, ethylphenol, propylphenol, Substituted phenols such as methoxyphenol, ethoxyphenol, chlorophenol, dichlorophenol, bromophenol, dibromophenol and their isomers; substituted naphthols such as naphthol, methylnaphthol, ethylnaphthol, chloronaphthol, bromonaphthol and their isomers body;
Various bisphenols such as 2,2-bis (4-hydroxyphenyl) propane; various biphenols; various heteroaromatic hydroxy compounds and their isomers, and their substitution products with alkyl, halogen and the like. Of these, phenol is particularly preferred.

(2) Carbon monoxide Carbon monoxide used in the present invention is not only highly pure, but also diluted with other gases such as nitrogen, argon, carbon dioxide and hydrogen, which do not adversely affect the reaction. You can use it even if there is.

(3) Oxygen The oxygen used in the present invention is not only high-purity oxygen,
It is also possible to use one diluted with air or another gas that does not adversely influence the reaction, such as nitrogen, argon, carbon dioxide, or hydrogen.

2. Catalyst The catalyst used in the reaction of the present invention is (A) to
It contains three components (D). (A) Palladium or palladium compound Palladium or palladium compound used in the present invention is palladium black; supported palladium such as palladium / carbon, palladium / alumina, palladium / silica; palladium chloride, palladium bromide, palladium iodide, palladium sulfate. Inorganic salts of palladium such as palladium nitrate; organic acid salts of palladium such as palladium acetate, palladium oxalate, palladium formate and palladium benzoate. Palladium (II) acetylacetonate, palladium on carbon monoxide, nitriles,
Palladium complex compounds coordinated with amines, phosphines, olefins, etc., such as PdCl ₂ (PhC
N) ₂ , PdCl ₂ (PPh ₃ ) ₂ , Pd (CO) (PPh
₃ ) ₃ , [Pd (NH ₃ ) ₄ ] Cl ₂ , Pd (C ₂ H ₄ ) (P
It is also possible to use a mixture of palladium with Ph ₃ ) ₂ or the like, or a compound such that a complex compound thereof is formed in the reaction system. Of these, organic acid salts of palladium are preferred, and palladium acetate is most preferred. The amount of the palladium component used in the reaction is preferably in the range of 10 ^-6 to 1 with respect to the aromatic hydroxy compound, and particularly preferably in the range of 10 ^-5 to 10 ^-1 .

(B) Redox agent The redox agent used in the present invention is cerium,
Compounds containing metal ions of cobalt or manganese are included. Examples of the compound containing a cerium ion include trivalent or tetravalent cerium compounds, for example, inorganic salts such as cerium chloride, cerium bromide, cerium sulfate and cerium nitrate; organic acids such as cerium acetate and cerium oxalate. It is salt. In addition, cerium acetylacetonate, a cerium complex compound in which carbon monoxide, nitriles, amines, phosphines, olefins and the like are coordinated to cerium, or a compound such that these complex compounds are formed in the reaction system A mixture of a class and cerium may be used. Examples of the compound containing cobalt ions include divalent or trivalent cobalt compounds. For example, inorganic salts such as cobalt chloride and cobalt bromide; organic acid salts such as cobalt acetate, cobalt formate and cobalt oxalate;
Examples thereof include amines, ketones, and complexes with carbon monoxide. Examples of compounds containing manganese ions include divalent or trivalent manganese compounds, for example, inorganic salts such as manganese chloride and manganese bromide; manganese acetate,
Organic acid salts such as manganese formate and manganese oxalate; amines, ketones, complexes with carbon monoxide and the like.

The amount of the redox agent used in the reaction is not particularly limited, but it is preferably in the range of 10 ⁻³ to 10 ² in terms of molar ratio with respect to the palladium component (A),
In particular, the range of 10 ⁻² to 10 is particularly preferable.

(C) Inorganic Halide The inorganic halide used in the present invention is an alkali metal or alkaline earth metal halide. As the halide, chloride and bromide are preferable, and examples thereof include lithium chloride, cesium chloride, sodium bromide, potassium bromide, rubidium bromide, cesium bromide, barium bromide, and the like. Among these, cesium chloride is particularly preferable. Cesium bromide is preferred. The amount of the inorganic halide used in the reaction is not particularly limited, but it is preferably in the range of 10 ^-2 to 10 ³ with respect to the palladium component (A), and particularly in the range of 10 ^-1 to 10 ² . Is particularly preferable.

(D) Activated carbon The activated carbon used in the present invention may be any commercially available one, and the raw material may be wood-based, coconut shell-based, coal-based or pitch-based. The amount of activated carbon used in the reaction is 20 times or more by weight, preferably 50 times the weight of palladium metal.
The range is up to 150 times.

3. Reaction conditions In the reaction, the above-mentioned aromatic hydroxy compound and the catalyst comprising the above-mentioned components (A), (B), (C) and (D) are charged into a reaction apparatus, pressurized with carbon monoxide and oxygen, and heated. To be done. Reaction pressure is 10 ^{-2 to} 50MP
a, preferably in the range of 10 ^{-1 to} 25 MPa. From the viewpoint of safety, the composition ratio of carbon monoxide and oxygen is preferably outside the combustion range. The reaction temperature is in the range of 20 to 300 ° C, preferably 60 to 250 ° C, more preferably 80 to 130 ° C. The reaction time is a few minutes to a few hours. It is also effective to add a desiccant such as molecular sieve to the reaction system or carry out the reaction while removing water generated from the reaction system. In the reaction, as a solvent, for example, an inert solvent such as hexane, heptane, cyclohexane, benzene, toluene, xylene, methylene chloride, chloroform, chlorobenzene, diethyl ether, diphenyl ether, tetrahydrofuran, dioxane, ethyl acetate, methyl formate, acetonitrile and the like. Can be used. Since the starting aromatic hydroxy compound may serve as the reaction solvent, it is not necessary to use another solvent at this time.

[0015]

The present invention will be described in detail below with reference to examples and comparative examples. Example 1 3.0 g (32 mmol) of phenol and 2.7 mg (0.01 of palladium acetate) were placed in a Hastelloy autoclave having a volume of 30 ml.
2mmol Pd), cesium (III) chloride monohydrate 4.1mg
(0.012 mmol), cesium chloride 40 mg (0.238 mm)
ol), activated carbon ["Taiko P" manufactured by Nimura Chemical Co., Ltd.] 100 mg
(C / Pd = 77 weight ratio) was charged, and after the system was replaced with carbon monoxide, carbon monoxide 6 MPa and dry air 3 MPa were introduced, and the reaction was carried out at 100 ° C. for 3 hours, and the reaction solution was analyzed by gas chromatography. analyzed. As a result, diphenyl carbonate was obtained in a yield of 16.46% (2.63 mmol). In addition, phenyl salicylate as a by-product is 0.35%
(0.056 mmol), p-phenoxyphenol is 0.2
9% (0.046 mmol) was produced.

Example 2 The amount of activated carbon used was 130 mg (C / Pd = 100 weight ratio).
As a result of carrying out the reaction in the same manner as in Example 1 except that
Diphenyl carbonate was obtained with a yield of 17.43% (2.79 mmol).

Example 3 The reaction was carried out in the same manner as in Example 1 except that the type of activated carbon was changed to "Dia Hope" crushed product manufactured by Mitsubishi Kasei Co., Ltd. As a result, the yield of diphenyl carbonate was 13.64% (2.18 mmol). ) Was obtained.

Comparative Example 1 Phenol (3.0 g, 32 mmol) and palladium acetate (2.76 mg, 0.0) were added to a Hastelloy autoclave having a volume of 30 ml.
12 mmol Pd), cerium (III) acetate monohydrate 4.1 mg
(0.012 mmol), 40 mg of cesium chloride (0.238 m)
mol) was added and the inside of the system was replaced with carbon monoxide, then carbon monoxide 6 MPa and dry air 3 MPa were introduced, the reaction was carried out at 100 ° C. for 3 hours, and the reaction liquid was analyzed by gas chromatography. As a result, the yield of diphenyl carbonate was 4.22.
% (0.68 mmol). In addition, phenyl salicylate as a by-product is 0.26% (0.042 mmol), p
-Phenoxyphenol is 0.46% (0.074 mmol)
Generated.

[0019]

As is clear from the above results, in the catalyst system of the present invention, the production of by-products which are difficult to separate by distillation is suppressed, and therefore it can be said to be a method of high industrial value.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification number Internal reference number FI Technical indication location C07C 69/96 Z 9546-4H // C07B 61/00 300 (72) Inventor Hideto Hayashi Ibaraki Prefecture 8-3-1 Chuo, Ami-cho, Inashiki-gun Tsukuba Research Institute, Mitsubishi Petrochemical Co., Ltd. (72) Inventor Yuji Ogaki 8-3-1, Chuo, Ami-cho, Inashiki-gun, Ibaraki Mitsubishi Petrochemical Co., Ltd.

Claims (6)

[Claims] 1. A method for producing an aromatic carbonic acid ester by reacting an aromatic hydroxy compound with carbon monoxide and oxygen, wherein the reaction system comprises (A) one or more selected from palladium and a palladium compound, and (B) redox. As an agent, one or more compounds containing a metal ion of cerium, cobalt or manganese, (C) one or more inorganic halides selected from alkali metal halides and alkaline earth metal halides (D) in the presence of activated carbon And a method for producing an aromatic carbonic acid ester, which comprises carrying out the reaction. 2. The method according to claim 1, wherein the palladium compound is an organic acid salt of palladium. 3. The method according to claim 1, wherein the component (B) is a trivalent or tetravalent cerium compound, divalent or trivalent cobalt or manganese. 4. The method according to claim 1, wherein the inorganic halide is chloride or bromide. 5. The method according to claim 1, wherein the inorganic halide is cesium chloride or cesium bromide. 6. The method according to claim 1, wherein the amount of the activated carbon used is 20 times or more the amount of palladium metal.