JPH10158221A - Production of aromatic carbonate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain an aromatic carbonate efficiently while preventing formation of by-product halogenized aromatic hydroxy compounds and maintaining high activity of catalysts by using a specific catalytic system. SOLUTION: This aromatic carbonate, for example, diphenyl carbonate, which is useful as a material for production of polycarbonate, is produced by carrying out a reaction of an aromatic hydroxy compound (for example, phenol) with carbon monoxide and oxygen in the presence of one or more compounds of each group of (A) palladium (compounds) (e.g. palladium acetate, palladium bromide, palladium/carbon), (B) lead compounds [lead oxides, Pb(OR)2 (R is an acyl of a 1-4C alkyl, 6-10 aryl, etc.)], (C) manganese compounds (manganese salts of organic acids, manganese complexes with lead, etc.), and (E) halides [chlorides, bromides (e.g., quaternary ammonium bromide)]. In this reaction system a solvent inactive to the reaction system, such as hexane, may be used.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

[0001] The present invention relates to a method for producing an aromatic carbonate. More specifically, the present invention relates to a method for producing an aromatic carbonate by reacting an aromatic hydroxy compound with carbon monoxide and oxygen using a specific catalyst system. Aromatic carbonates, especially diphenyl carbonate, are useful as raw materials for polycarbonate and the like.

[0002]

2. Description of the Related Art Conventionally, as a method for producing an aromatic carbonate, a method of reacting an aromatic hydroxy compound with phosgene has been used. However, this method is not preferred because phosgene is highly toxic. For this reason, as a method not using phosgene, a method of producing an aromatic carbonate by reacting an aromatic hydroxy compound with carbon monoxide and oxygen has been proposed.

As the catalyst used in this method, for example, Japanese Patent Publication No. 56-38144 discloses a palladium compound, IIIA, IVA, VA, VIA, IB, IIB, VIB of the periodic table.
Or a method using a compound containing a metal of Group VIIB and a base; Japanese Patent Publication No. 56-38145 discloses a method using a palladium compound, a manganese complex or a cobalt complex, a base and a drying agent; Is a method using a palladium compound, a divalent or trivalent manganese compound, a tetraalkylammonium halide and quinones; Japanese Patent Application Laid-Open No. 2-142754 uses a palladium compound, a cobalt compound, a tetraalkylammonium halide and quinones. Method: JP-A-5-392
No. 47 discloses a method using a palladium compound, a copper compound, quinones and an onium halide;
JP-A-8961 discloses a method using a palladium compound, a cobalt compound and an alkali metal halide; JP-A-5-97775 discloses (a) a palladium compound;
(B) a quaternary ammonium salt, (c) one metal promoter selected from cobalt, iron, cerium, manganese, molybdenum, samarium, vanadium, chromium and copper, and (d) an aromatic ketone, an aliphatic ketone and A method using an organic promoter selected from aromatic polycyclic hydrocarbons;
No. 9505 discloses a method using a palladium compound, a cerium compound and a quaternary ammonium salt;
No. 41020 discloses (a) a palladium compound,
(B) a method using a metal promoter selected from manganese, cobalt and copper and (c) a nitrile compound;
JP-A-271506 discloses a method using a palladium compound, a manganese compound, a cobalt compound and an inorganic halide; JP-A-7-145107 discloses a method using a palladium compound, a manganese compound and an inorganic halide; JP-A-8-134022 discloses a method using a palladium compound, an inorganic halide and activated carbon; JP-A-8-99935 discloses a method using a palladium compound, a lead compound and a halide, and optionally a copper compound; In the publication, a number of catalyst systems are proposed, such as a method using a palladium compound and an iodine compound.

As an operation method of the present catalyst reaction, for example, a method using a continuous multi-stage distillation column is disclosed in Japanese Patent Application Laid-Open No. 4-257546; a method using a noble metal catalyst in a carbon monoxide atmosphere is disclosed in Japanese Patent Application Laid-Open No. 7-188116. JP-A-7-247243 discloses a method of performing the present reaction while distilling off water produced as a by-product in the reaction;
Japanese Patent Publication No. -501501 describes a method for carrying out a reaction while maintaining a constant molar ratio and partial pressure of carbon monoxide and oxygen in a reactor.

[0005]

The present inventors have conducted additional tests using phenol as a substrate and a conventional catalyst, and found that halogenated aromatic hydroxy compounds as by-products in many catalyst systems. , For example, o, p-bromophenol. In general, by-products of halogenated aromatic hydroxy compounds are extremely difficult to separate and purify aromatic carbonates by distillation or the like, or to consume catalyst components and cause a reduction in reaction activity. In addition, in a catalyst system in which a halogenated aromatic hydroxy compound is not produced as a by-product, satisfactory catalytic activity has not been achieved at present, judging from the molar ratio of aromatic carbonate formed to palladium catalyst and the space-time yield. is there. Therefore, an object of the present invention is to provide a method for efficiently producing an aromatic carbonate, which has high catalytic activity while preventing by-produced halogenated aromatic hydroxy compounds.

[0006]

Means for Solving the Problems The present inventors have made intensive studies to solve the above-mentioned problems, and as a result, have found that an aromatic hydroxy compound is reacted with carbon monoxide and oxygen in the presence of a specific catalyst. It has been found that aromatic carbonates can be obtained efficiently and that by-products of halogenated aromatic hydroxy compounds are prevented, and the present invention has been completed.

That is, the present invention relates to a method for producing an aromatic carbonate by reacting an aromatic hydroxy compound with carbon monoxide and oxygen, wherein at least one selected from the following components, (A) palladium and a palladium compound: , (B) one or more lead compounds, (C) one or more manganese compounds,
A method for producing an aromatic carbonate, wherein the reaction is carried out in the presence of (D) one or more cobalt compounds and (E) one or more halides. Hereinafter, the present invention will be described in detail.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION

1. Reaction raw materials (1) Aromatic hydroxy compound As the aromatic hydroxy compound, aromatic mono- or polyhydroxy compounds such as phenol; cresol, xylenol, trimethylphenol, tetramethylphenol, ethylphenol, propylphenol, methoxyphenol, ethoxyphenol, Substituted phenols such as chlorophenol, dichlorophenol, bromophenol and dibromophenol and their isomers; substituted naphthols such as naphthol, methylnaphthol, ethylnaphthol, chloronaphthol and bromonaphthol and their isomers; Various bisphenols such as bis (4-hydroxyphenyl) propane; various biphenols; various heteroaromatic hydroxy compounds and isomers thereof, and furthermore Alkyl, substitution products with a halogen or the like is used. Of these, phenol is particularly preferred.

(2) Carbon monoxide As carbon monoxide, not only high-purity carbon monoxide but also air,
Those diluted with another gas that does not adversely affect the reaction, such as argon, carbon dioxide, and hydrogen, can also be used.

(3) Oxygen As oxygen, not only high-purity oxygen but also air diluted with other gases that do not adversely affect the reaction, such as air, nitrogen, argon, carbon dioxide and hydrogen, may be used. Can be.

2. Catalyst The catalyst used in the present invention includes the following (A), (B),
In each of the components listed in (C), (D) and (E),
Including at least one selected and combined system
Have (A) Palladium and palladium compound As palladium and palladium compound, palladium
Black; palladium / carbon, palladium / alumina and
Supported palladium such as palladium / silica; palladium chloride
Palladium bromide, palladium iodide, palladium sulfate
And inorganic salts of palladium such as palladium nitrate;
Organic palladium such as radium and palladium oxalate
Acid salts are used. Also, palladium (II) acetyl
Settonate, palladium to carbon monoxide, nitriles,
Amines, phosphines or olefins coordinated
Complex compounds of palladium, for example PdCl_Two(PhCN)
_Two, PdCl_Two(PPh_Three)_Two, Pd (CO) (PPh
_Three)_Three, [Pd (NH_Three) _Four] Cl_Two, Pd (C
_TwoH_Four) (PPh_Three)_Two, [(Η^Three-C_ThreeH_Five) PdC
l]_Two, Pd (DBA)_Two, Pd_Two(DBA)_Three・ CH
Cl_ThreeWherein Ph is a phenyl group, DBA is dibenzyl
Or the complex compound reacts.
A coordinating species such as that produced in the system and palladium or para
Mixtures with the indium compounds can also be used. Inside
Also palladium acetate, palladium bromide and palladium /
Carbon is preferred. Palladium component used in the reaction
Is in a molar ratio of 10 to the aromatic hydroxy compound.
^-7-10^-2Preferably in the range of 10^-6-10
^-3It is particularly preferable that it is in the range of

(B) Lead compound As the lead compound, those which are soluble in the liquid phase under the reaction conditions are preferable. For example, PbO, Pb ₃ O ₄ and PbO ₂
Lead oxides such as lead (II) acetate, lead tetraacetate, lead oxalate (II) and lead (II) propionate; organic acid salts of lead; lead (II) sulfate and lead (II) nitrate Inorganic lead salt; Pb (O
Examples include alkoxy lead and aryloxy lead such as Me) ₂ and Pb (OPh) ₂ ; and complex compounds of lead such as lead phthalocyanine. Among them, lead oxide or Pb
A lead compound represented by (OR) ₂ (R represents an acyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms in the alkyl group) is preferable. The amount of the lead compound used in the reaction is not particularly limited, but is preferably in a range of 10 ^-5 to 10 ^{-1 in} a molar ratio with respect to the aromatic hydroxy compound,
It is particularly preferred that it be in the range of 10 ^-5 to 10 ^-2 .

(C) Manganese compound As the manganese compound, divalent, trivalent or tetravalent manganese is used.
Compound is used. Specifically, manganese oxide (I
I) and manganese oxides such as manganese dioxide; man chloride
Cancer (II), manganese (II) bromide, manganese sulfate (II)
And inorganic salts of manganese such as manganese (II) nitrate;
Ngan (II), manganese acetate (III), manganese oxalate
Organic manganese such as (II) and manganese (II) benzoate
Acid salt: manganese (II) acetylacetonate, manganese
(III) acetylacetonate, phthalocyanine manga
, N, N'-bis (salicylidene) ethylenediamine
Manganese (II) and bis (tropolonate) manganese
A manganese complex compound such as (II) is mentioned as an example.
Among them, manganese organic acid salts and manganese complex compounds
preferable. The amount of manganese compound used in the reaction is particularly limited
Is not present but in a molar ratio of 1 to the aromatic hydroxy compound
0^-7-10^-2Preferably in the range of 10^-6~ 1
0 ^-3It is particularly preferable that it is in the range of

(D) Cobalt compound As the cobalt compound, divalent, trivalent or tetravalent cobalt is used.
Compound is used. Specifically, cobalt oxide (I
I) and cobalt oxides such as cobalt dioxide;
Lt (II), cobalt (II) bromide, cobalt (II) sulfate
And inorganic salts of cobalt such as cobalt (II) nitrate;
Baltic (II), cobalt acetate (III), cobalt oxalate
Organic cobalt such as cobalt (II) and cobalt (II) benzoate
Acid salt: cobalt (II) acetylacetonate, cobalt
(III) acetylacetonate, phthalocyanine koval
G, N, N'-bis (salicylidene) ethylenediamine
Cobalt (II) and bis (tropolonate) cobalt
An example is a complex compound of cobalt such as (II).
Among them, organic acid salts of cobalt and complex compounds of cobalt are
preferable. The amount of cobalt compound used in the reaction is particularly limited
Is not present but in a molar ratio of 1 to the aromatic hydroxy compound
0^-7-10^-1Preferably in the range of 10^-6~ 1
0 ^-2It is particularly preferable that it is in the range of

(E) Halide As the halide, those which are soluble in the liquid phase under the reaction conditions are preferable, and chlorides and bromides are particularly preferable. Specifically, inorganic halides such as cesium chloride, sodium bromide, potassium bromide, rubidium bromide, cesium bromide and barium bromide; halogens such as tetra-n-butylammonium bromide and tetramethylammonium bromide Quaternary ammonium salts; halogenated quaternary phosphonium salts such as tetraphenylphosphonium bromide and methyltriphenylphosphonium bromide. Among them, quaternary ammonium bromide is more preferable.
The amount of the halide used in the reaction is not particularly limited, but may be in a molar ratio of ^10-5 to the aromatic hydroxy compound.
It is preferably in the range of ¹ , particularly preferably in the range of 10 ^-4 to 10 ^-1 .

3. Reaction Conditions As the reaction vessel, a gas-phase and / or liquid-phase flow-type or batch-type vessel can be used according to a normal gas-liquid high-pressure reaction. However, it is preferable that the material is hardly corroded by halogen ions such as Hastelloy C. In the reaction, the aromatic hydroxy compound and a catalyst obtained by combining at least one selected from each of the components (A), (B), (C), (D) and (E) are charged into a reactor. It is usually carried out under pressure and heating with the above-mentioned carbon monoxide and oxygen.

The absolute pressure during the reaction ranges from 1 to 500 atm, preferably from 1 to 150 atm in total pressure. The mixing ratio of carbon monoxide and oxygen is preferably a value outside the explosion range from the viewpoint of safety. The partial pressures of carbon monoxide and oxygen are 10 to 100 atm and 0.2 to 1 respectively.
It is preferably 0 atm. Reaction temperature is 20-300
° C, preferably in the range of 80 to 130 ° C. The reaction time varies depending on the reaction conditions, but is usually several minutes to several hours.

At the time of the reaction, organic additives such as aromatic diols such as hydroquinone used in conventional catalysts and oxidized products thereof such as quinones and amines may be added to the reaction system. Further, as a solvent, for example, inert to a reaction system such as hexane, heptane, cyclohexane, benzene, nitrobenzene, toluene, xylene, methylene chloride, chloroform, chlorobenzene, ethyl ether, phenyl ether, tetrahydrofuran, dioxane, diglyme or acetonitrile. Solvents can be used. In this case, since the aromatic hydroxy compound as the raw material may be used as the reaction solvent, it is not necessary to use another solvent in this case.

[0019]

EXAMPLES Hereinafter, the present invention will be described specifically with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples as long as the gist of the present invention is not exceeded. Example 1 12.6 g (133 mmol) of phenol, 0.44 mg (2.0 μmol) of palladium acetate, and 6.6 of lead oxide (II) were placed in a Hastelloy autoclave having an internal volume of 66 ml.
mg (30 μmol), manganese (II) acetate tetrahydrate 1.8 mg (7.3 μmol), cobalt acetate (II) tetrahydrate 3.8 mg (15 μmol) and tetramethylammonium bromide 38.5 mg (0.5 μm). 25 mmol), and the inside of the system was replaced with carbon monoxide. Then, 40 atm of carbon monoxide was introduced, followed by introduction of dry air to bring the total pressure to 60 atm.
The mixture was stirred and mixed at 00 ° C. for 2 hours. After the reaction was completed, quantitative analysis by gas chromatography was performed using the reaction solution. As a result, diphenyl carbonate was obtained in a yield of 3.8% (2.5 mmol) based on phenol. Note that no by-product of bromophenol was observed on the chromatogram.

Examples 2 to 4 Example 1 was repeated except that 7.5 μmol of various manganese compounds were used instead of manganese (II) acetate tetrahydrate.
An experiment was performed in the same manner as in the above. Table 1 shows the manganese compound used and the yield of the generated diphenyl carbonate relative to phenol. In addition, no by-product of bromophenol was observed in any of the examples.

[0021]

[Table 1]

Examples 5 to 6 Experiments were carried out in the same manner as in Example 1 except that 15 μmol of each of various cobalt compounds was used instead of cobalt (II) acetate tetrahydrate. Table 2 shows the yield of the cobalt compound used and the yield of diphenyl carbonate with respect to phenol. In addition, no by-product of bromophenol was observed in any of the examples.

[0023]

[Table 2]

Example 7 Instead of lead (II) oxide, lead (II) acetate trihydrate 11m
The reaction was carried out in the same manner as in Example 1 except that g (30 μmol) was used. As a result, the yield of diphenyl carbonate was 4.0.
% (2.7 mmol). In addition, by-product of bromophenol was not recognized.

Example 8 Instead of palladium acetate, 4.3 mg (2.0 μm) of 5% palladium / carbon (manufactured by NE Chemcat) was used.
The reaction was carried out in the same manner as in Example 1 except that mol Pd) was used. As a result, the yield of diphenyl carbonate was 3.5%.
(2.3 mmol). In addition, by-product of bromophenol was not recognized.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 except that cobalt (II) acetate tetrahydrate was not used. As a result, diphenyl carbonate was obtained in a yield of 3.4% (2.3 mmol). However, bromophenol was by-produced at a molar ratio of 79% to the bromide used.

Comparative Example 2 A reaction was carried out in the same manner as in Example 1 except that manganese (II) acetate tetrahydrate was not used. As a result, the yield of diphenyl carbonate remained at 0.1% (0.08 mmol).
In addition, by-product of bromophenol was not recognized.

Comparative Example 3 A reaction was carried out in the same manner as in Example 1 except that lead (II) acetate was not used. As a result, the yield of diphenyl carbonate was 0.1.
It remained at 1% (0.1 mmol). In addition, by-product of bromophenol was not recognized.

Example 9 In a Hastelloy-made autoclave having an internal volume of 66 ml, 6.3 g (67 mmol) of phenol and 0.1 ml of palladium acetate were added.
46 mg (2.0 μmol), 6.7 mg of lead (II) oxide
(30 μmol), manganese (II) acetate tetrahydrate 1.8
mg (7.3 μmol), 3.7 mg (15 μmol) of cobalt (II) acetate tetrahydrate, 38 mg (0.25 mmol) of tetramethylammonium bromide and 7.0 g (57 mmol, the same volume as phenol) of nitrobenzene as a solvent. After the atmosphere was replaced with carbon monoxide, 40 atm of carbon monoxide and then dry air were introduced to bring the total pressure to 60 atm, and the mixture was stirred and mixed at 100 ° C. for 2 hours. After the reaction,
Quantitative analysis by gas chromatography was performed using the reaction solution. As a result, diphenyl carbonate was obtained in a yield of 7.0% (2.3 mmol) based on phenol. In addition, by-product of bromophenol was not recognized.

[0030]

As is evident from the above results, according to the present invention, an aromatic carbonate is efficiently produced and a by-product which makes separation and purification difficult is prevented. Accordingly, the present invention provides a method for producing an aromatic carbonate having high industrial value.

Continued on the front page (72) Inventor Yuji Ogome 3-3-1, Chuo, Ami-cho, Inashiki-gun, Ibaraki Pref.

Claims (7)

[Claims] 1. A method for producing an aromatic carbonate by reacting an aromatic hydroxy compound with carbon monoxide and oxygen, comprising: (A) at least one selected from the group consisting of palladium and a palladium compound; An aromatic carbonate characterized in that the reaction is carried out in the presence of one or more lead compounds, (C) one or more manganese compounds, (D) one or more cobalt compounds, and (E) one or more halides. Manufacturing method. 2. The method according to claim 1, wherein component (A) is palladium acetate, palladium bromide or palladium / carbon. 3. Component (B) is lead oxide or Pb (OR)
The method according to claim 1, wherein the compound is a lead compound represented by ₂ (R represents an alkyl group having 1 to 4 carbon atoms or an aryl group having 6 to 10 carbon atoms). 4. The method according to claim 1, wherein component (C) is an organic acid salt of manganese or a complex compound of manganese. 5. The method according to claim 1, wherein component (D) is an organic acid salt of cobalt or a complex compound of cobalt. 6. The method according to claim 1, wherein component (E) is chloride or bromide. 7. The method according to claim 6, wherein component (E) is a quaternary ammonium bromide salt.