JPH05339204A - Production of aromatic dicarboxylic acid - Google Patents

Abstract

PURPOSE:To obtain an aromatic dicarboxylic acid in high purity and yield by oxidizing an aromatic dialkyl compound with oxygen or an oxygen-contg. gas in the presence of a specific catalytic system. CONSTITUTION:The objective aromatic dicarboxylic acid of formula VII can be obtained by oxidizing (I) a compound of formula I [R<1> and R<2> are each alkyl; A is of formula II-VI (m and n are each 0-4); X, Y<1>, Y<2> and Z are each halogen, NO2 or CN] with (II) oxygen or an oxygen-contg. gas (industrially, air is optimal) in (III) a 2-10C aliphatic monocarboxylic acid (pref. acetic acid) in the presence of (IV) a catalyst composed of (A) cobalt, (B) bromine or bromine plus chlorine, and (C) at least one kind selected from manganese, cerium, zirconium and nickel (e.g. cobalt bromide-manganese acetate, cobalt naphthenate- manganese naphthenate-tetrabromoethane).

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing an aromatic dicarboxylic acid by oxidizing an aromatic dialkyl compound. Aromatic dicarboxylic acids have a wide range of applications as raw materials for various resins such as polyamide, polyester, polyamideimide, and polyesterimide, modifiers, liquid crystal materials, epoxy resin curing agents, and raw materials for agricultural chemicals and dyes.

[0002]

2. Description of the Related Art Conventionally, as a method for producing an aromatic dicarboxylic acid, for example, ω-decachloro-4 ', obtained by chlorinating 4', 4 "-dimethyl-1,4-dibenzylbenzene,
Method for decomposing 4 "-dimethyl-1,4-dibenzylbenzene in acetic acid in the presence of zinc chloride (USSR21224
8) is known.

[0003]

However, this method is
Since it is extremely toxic and uses a stoichiometric amount of dangerous chlorine that explosively reacts with heating, direct sunlight, ultraviolet rays, etc., and produces a large amount of waste, it is a serious problem as an industrial manufacturing method. Therefore, in producing an aromatic dicarboxylic acid, it has been desired to establish an advantageous method which is inexpensive and can be industrially carried out.

[0004]

[Means for Solving the Problems] As a result of intensive studies to develop a method for producing an aromatic dicarboxylic acid that is inexpensive and does not cause environmental damage, as an alternative to the known method, the present inventors have found that the aromatic dialkyl compound should be oxygenated. Alternatively, when oxidizing with an oxygen-containing gas, by using a catalyst system containing specific heavy metals and bromine or bromine and chlorine as essential components, it is possible to oxidize easily and in high yield, and achieve the intended purpose. Found. The present invention has been completed based on such findings, and an object thereof is to provide an industrially advantageous method for efficiently producing an aromatic dicarboxylic acid by using an inexpensive oxidizing agent.

The method for producing an aromatic dicarboxylic acid according to the present invention is a method in which an aromatic dialkyl compound represented by the general formula (1) is added to oxygen or oxygen in an aliphatic monocarboxylic acid having 2 to 10 carbon atoms in the presence of a catalyst. In the method for producing an aromatic dicarboxylic acid represented by the general formula (2) by oxidizing with a contained gas, the catalyst comprises (A) cobalt, (B) bromine or bromine and chlorine, (C) manganese as its constituent elements. , A catalyst containing at least three elements selected from the respective groups of one or more heavy metals selected from cerium, zirconium and nickel.

[Chemical 8] [In the formula, R ¹ and R ² are the same or different and each represents an alkyl group, and A is

[Chemical 9] ,

[Chemical 10] ,

[Chemical 11] ,

[Chemical formula 12] Or

[Chemical 13] Represents. X, Y ¹ , Y ² and Z are the same or different and each represents a halogen group, a nitro group or a nitrile group. m and n each independently represent an integer of 0-4. ]

[Chemical 14] [In the formula, A, X, Y ¹ , Y ² , Z, m and n have the same meanings as in formula (1). ]

The aromatic dialkyl compound used as a raw material in the present invention can be synthesized, for example, by the Friedel-Crafts reaction of toluene and phthalic acid dichloride or alkyl-substituted benzoyl chloride and a predetermined aromatic compound.

The carbon number of the alkyl group is, for example, 1 to 5, and a methyl group, an ethyl group and an isopropyl group are particularly preferable.

Specific examples of the aromatic dialkyl compound include 1,3-bis (3-methylbenzoyl) benzene,
1,3-bis (4-methylbenzoyl) benzene, 1,3
-Bis (3-ethylbenzoyl) benzene, 1,3-bis (4-ethylbenzoyl) benzene, 1,3-bis (3-isopropylbenzoyl) benzene, 1,3-bis (4-isopropylbenzoyl) benzene, 1 , 4-
Bis (3-methylbenzoyl) benzene, 1,4-bis (4-methylbenzoyl) benzene, 1,3-bis (3
-Ethylbenzoyl) benzene, 1,4-bis (3-isopropylbenzoyl) benzene, 1,4-bis (4-
Isopropylbenzoyl) benzene, 1,3-bis (4
-Methyl-2-fluorobenzoyl) benzene, 1,3
Benzenes such as -bis (4-methylbenzoyl) -5-fluorobenzene,

4,4'-bis (4-methylbenzoyl) biphenyl, 4,4'-bis (3-methylbenzoyl) biphenyl, 3,3'-bis (4-methylbenzoyl) biphenyl, 3,3'- Bis (4-methylbenzoyl) biphenyl, 2-chloro-4,4'-bis (4-methylbenzoyl) biphenyl, 2-fluoro-4,4'-bis (4-methylbenzoyl) biphenyl, 2,2 ', Biphenyls such as 6,6′-tetrafluoro-4,4′-bis (4-methylbenzoyl) biphenyl,

4,4'-bis (4-methylbenzoyl) diphenylether, 4,4'-bis (3-methylbenzoyl) diphenylether, 3,3'-bis (4-methylbenzoyl) diphenyl Diphenyl ethers such as ether, 3,3′-bis (4-methylbenzoyl) diphenyl ether,

4,4'-bis (4-methylbenzoyl) diphenyl sulfone, 4,4'-bis (3-methylbenzoyl) diphenyl sulfone, 3,3'-bis (4-methylbenzoyl) diphenyl sulfone, 3,3 ' Diphenyl sulfones such as 3′-bis (4-methylbenzoyl) diphenyl sulfone,

4,4'-bis (4-methylbenzoyl) benzophenone, 4,4'-bis (3-methylbenzoyl)
Benzophenones such as benzophenone, 3,3′-bis (4-methylbenzoyl) benzophenone and 3,3′-bis (4-methylbenzoyl) benzophenone can be mentioned.

The catalyst used in the present invention contains, as its constituent elements, at least three kinds of elements selected from the following groups (A) to (C). (A) Cobalt (B) Bromine or bromine and chlorine (C) One or more heavy metals selected from manganese, cerium, zirconium and nickel

Cobalt may be in any form such as elemental form, oxide, salt, complex and the like, but especially a salt which is at least partially dissolved in the reaction system, for example, cobalt acetate, cobalt bromide,
Cobalt naphthenate and cobalt hydroxide are preferred.

The amount of cobalt used is 0.1 in terms of metal conversion.
01 to 10 g / l is suitable. If it is less than 0.01 g / l, a sufficient reaction rate cannot be obtained, and if it is more than 10 g / l, the burden of the catalyst cost increases and it becomes difficult to produce the desired product.

As bromine, any of bromine molecules, acids, salts, oxygenates or organic bromine compounds can be used. Particularly, hydrogen bromide, ammonium bromide, manganese bromide, cerium bromide, cobalt bromide, tetrabromoethane, tribromoethane and the like are preferable. The same applies to chlorine.

The amount of bromine used is 0.1 to 10 in terms of bromine atom per atom of (A) cobalt and (C) heavy metal.
0 equivalent is suitable. If the amount is less than 0.1 equivalent, a sufficient reaction rate cannot be obtained. If the amount is more than 100 equivalents, the contamination of the target substance with bromine and the burden of the catalyst cost increase, which is not preferable.

When bromine and chlorine are used in combination, the total amount thereof is suitably 0.1 to 100 equivalents in terms of atoms, and the ratio of chlorine to bromine is preferably 0.7 or less.

The one or more heavy metals selected from manganese, cerium, zirconium and nickel may be in any form such as elemental form, oxide, salt and complex.

The amount of the heavy metal used is appropriately 0.0001 to 100 by weight, preferably 0.005 to 0.5, relative to the cobalt metal. 0.0
If it is added in an amount of 001 or less, a large effect of promoting the reaction is not recognized, and if it is added in an amount of 100 or more, the catalyst cost is increased and it is economically disadvantageous.

As the catalyst system according to the present invention, specifically,
Cobalt bromide and manganese bromide, cobalt bromide and manganese acetate, cobalt acetate and manganese bromide, manganese acetate and cobalt acetate and ammonium bromide, cobalt acetate and manganese acetate and hydrogen bromide, cobalt bromide and cerium acetate,
Manganese bromide and cerium acetate, cobalt acetate and manganese acetate and cerium acetate and hydrogen bromide, cobalt bromide and zirconium acetate, cobalt acetate and nickel bromide, cobalt naphthenate and manganese naphthenate and tetrabromoethane, cobalt acetylacetonate And manganese acetylacetonate and hydrogen bromide, cobalt acetate and manganese acetate and cerium acetate and hydrogen bromide, and cobalt acetate and manganese acetate and hydrogen bromide and hydrogen chloride.

The aliphatic monocarboxylic acid having 2 to 10 carbon atoms used as the reaction solvent in the present reaction method has the advantage that it is relatively stable against oxidation and can be easily separated from the reaction product. However, acetic acid is particularly preferable.

Although the amount of the reaction solvent used varies depending on the type of raw material and the reaction conditions, it is usually preferably 50 to 900 g / l.

The oxygen or oxygen-containing gas used as the oxidant may be pure oxygen or industrial exhaust gas, but is not limited to these and any gas containing oxygen may be used. Industrially, normal air is most suitable. is there.

The reaction temperature is usually about 100 to 250 ° C., preferably 150 to 220 ° C. 100
If the temperature is lower than 0 ° C, the reaction rate is slow, while if the temperature is higher than 250 ° C, decomposition of the solvent or the product occurs, which is not preferable.

The reaction pressure is such that the total reaction pressure is 1 to 30 kg / cm ²
G, especially 3 to 20 kg / cm ² G, and oxygen partial pressure of 0.01 to
2.4 kg / cm ² is preferred. Further, from the viewpoint of safety, it is desirable to operate so that the oxygen concentration in the exhaust gas is 8% by volume or less.

The method of the present invention is generally carried out as follows. That is, a raw material, a catalyst and a solvent are charged into a reactor equipped with a stirrer equipped with a gas inlet and a gas outlet, replaced with or pressurized with a gas containing nitrogen or oxygen, and heated to a predetermined temperature. Stirring and gas blowing are not always necessary in this temperature rising process. The absorption of oxygen generally starts at 100 to 150 ° C, though it depends on the type of catalyst. When the absorption of oxygen starts, oxygen or an oxygen-containing gas is introduced, and the reaction is performed while maintaining the oxygen partial pressure and temperature in a predetermined range. The exhaust gas is cooled and the condensate is returned to the reactor. After the reaction for a predetermined time, it is cooled, the reaction product is taken out, and the solvent is distilled off as it is or a part of the solvent. Then, a high-purity aromatic dicarboxylic acid is obtained through steps such as evaporation of the solvent and recrystallization.

A bubble column type reactor can be used in addition to the above-mentioned one equipped with a stirrer. Further, the reaction method is not limited to the batch reaction, and a continuous or semi-continuous method is also possible. Specifically, the raw material, the catalyst and the solvent are continuously supplied to the reactor, the reaction is performed while blowing oxygen or an oxygen-containing gas, and the reaction product is continuously extracted, or the catalyst and the solvent are supplied to the reactor. An example is a method in which the materials are charged, and then, only the raw materials or the raw materials and the solvent are reacted for a certain period of time, and then the charging is stopped to continue the reaction to complete the reaction.

[0029]

EXAMPLES The present invention will be described in detail below with reference to examples. Example 1 50 equipped with gas inlet and gas outlet with reflux condenser
Electromagnetic equipped with a stirrer autoclave 0 ml, 1,3-bis (4-methylbenzoyl) benzene 31.5 g, cobalt bromide [CoBr ₂ · 6H ₂ O, the same applies hereinafter] 5.80 g,
Manganese acetate _{[Mn (OAc) 2 · 4H} 2 O, forth]
Charge 0.65g and 300g acetic acid, nitrogen 10kg / cm
^The pressure was increased to ² G, and the mixture was heated and stirred. Starting to introduce air from 150 ° C, reflux acetic acid and release exhaust gas,
The amount of introduced air was adjusted so that the oxygen concentration in the exhaust gas was in the range of 1 to 6% at 55 to 165 ° C and a pressure of 20 kg / cm ² G (oxygen partial pressure was 0.1 to 0.8 kg / cm ² ). .. When the reaction was carried out under these conditions for about 1 hour, no oxygen absorption was observed, at which point the introduction of air was stopped and the reaction was continued for another 30 minutes. Then, the reactor was cooled and the contents were taken out, and the precipitate was separated by filtration, washed with water and dried to obtain 33.5 g of a colorless solid. Its neutralization number was 298, and as a result of IR, NMR and GLC analysis, the purity of the desired 4,4′-isophthaloyldibenzoic acid (IDBA) was 99.3%, and its yield was 89.6%. Met.

Example 2 In the same reactor as in Example 1, 31.4 g of 1,3-bis (4-methylbenzoyl) benzene and 2.80 of cobalt bromide were added.
g, 0.02 g of manganese acetate and 300 g of acetic acid were charged, the pressure was increased to 10 kg / cm ² G with nitrogen, and the mixture was heated and stirred. 1
Starting to introduce air from 60 ° C, reflux acetic acid and releasing exhaust gas, 175 to 185 ° C, pressure 20 kg / cm ² G
The amount of introduced air was adjusted so that the oxygen concentration in the exhaust gas was in the range of 1 to 6% (oxygen partial pressure of 0.1 to 0.8 kg / c).
m ² ). After reacting for about 2 hours under these conditions, absorption of oxygen is no longer observed, at which point the introduction of air is stopped
The reaction was continued for 0 minutes. Then, the reactor was cooled, the contents were taken out, and acetic acid and generated water were distilled off under reduced pressure to obtain 39.8 g of crude oxidation reaction product. The neutralization value of this product is 279
As a result of IR, NMR and GLC analysis,
DBA was 93.0% and the yield was 99.0%.

[0031] Example 3 Example 1 and the same reactor 1,3-bis (4-methylbenzoyl) benzene 31.5 g, acetate 300g and cobalt acetate _{[Co (OAc) 2 · 4H} 2 O] - manganese acetate -Preparing a predetermined amount of ammonium bromide-based catalyst, 155 to 1
65 ℃, 15kg / cm ² G (Oxygen partial pressure 0.01-0.6kg / c
IDBA was produced under the conditions of m ² ). The results obtained are shown in Table 1.

Example 4 The same as Example 3 except that a cobalt bromide-manganese acetate-cerium acetate [Co (OAc) ₃ .H ₂ O] -47% hydrobromic acid catalyst was used as the catalyst. IDBA was prepared. The results obtained are shown in Table 1.

Example 5 IDBA was carried out in the same manner as in Example 3 except that a cobalt bromide-cerium acetate-sodium bromide catalyst was used as the catalyst.
Was prepared. The results obtained are shown in Table 1.

Example 6 An IDBA was prepared in the same manner as in Example 3 except that a cobalt naphthenate-manganese naphthenate-tetrabromoethane catalyst was used as the catalyst. The results obtained are shown in Table 1.

[Table 1]

Example 7 In the same reactor as in Example 1, 31.7 g of 1,4-bis (4-methylbenzoyl) benzene and 5.16 of cobalt bromide were added.
g, manganese acetate 0.45 g and acetic acid 300 g were charged and reacted for 1 hour at 175 to 185 ° C. and 10 kg / cm ² G to obtain 4,4′-terephthaloyldibenzoic acid (purity 9
7.2%) was obtained in a yield of 94.8%.

Example 8 In the same reactor as in Example 1, 31.5 g of 1,4-bis (4-methylbenzoyl) benzene and 2.40 of cobalt acetate were added.
g, manganese acetate 0.24 g, hydrobromic acid 6.00 g and acetic acid 300 g were charged, and the temperature was 185 to 195 ° C. and 20 kg / cm ^2.
The reaction was carried out for 1 hour under the condition of G to obtain 4,4′-terephthaloyldibenzoic acid (purity 98.8%) in a yield of 95.3%.

Example 9 As in Example 1, 4,4'-bis (4-methylbenzoyl) diphenyl ether 40.6 g, cobalt bromide 5.1
6 g, 0.45 g of manganese acetate and 300 g of acetic acid were charged and reacted for 1 hour under the conditions of 175 to 185 ° C. and 20 kg / cm ² G to obtain 4,4′-bis (4-hydroxycarbonylbenzoyl) diphenyl ether ( Purity 98.5%) 92.
Obtained in a yield of 7%.

Example 10 As in Example 1, 4,4'-bis (4-methylbenzoyl) diphenyl sulfone 45.4 g, cobalt bromide 5.8
0 g, manganese acetate 0.65 g and acetic acid 300 g were charged and reacted for 1 hour under the conditions of 185 to 195 ° C. and 20 kg / cm ² G to obtain 4,4′-bis (4-hydroxycarbonylbenzoyl) diphenyl sulfone (purity 97 2.9%) to 92.
Obtained in a yield of 1%.

[0039]

By applying the method of the present invention, the desired aromatic dicarboxylic acid can be produced in high purity and high yield under industrially advantageous conditions.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI Technical indication C07C 65/40 8930-4H 201/12 205/61 6917-4H 253/30 255/57 6917-4H 315/04 317/44 7419-4H // C07B 61/00 300 (72) Inventor Akihiro Nishiuchi, 13 Yakura-cho, Yashimajima Fushimi-ku, Kyoto City, Kyoto Prefecture Nihon Rika Co., Ltd. (72) Inventor Hitoshi Yagi Kyoto Prefecture, Kyoto Prefecture Shinya Rika Co., Ltd. 13 Yagura-cho, Hyoshima, Fushimi-ku

Claims (1)

[Claims] 1. An aromatic dialkyl compound represented by the general formula (1) is oxidized with oxygen or an oxygen-containing gas in an aliphatic monocarboxylic acid having 2 to 10 carbon atoms in the presence of a catalyst to obtain the general formula (2). In the method for producing an aromatic dicarboxylic acid represented by, the catalyst comprises (A) cobalt, (B) bromine or bromine and chlorine, (C) manganese, as its constituent elements.
A process for producing an aromatic dicarboxylic acid, which is a catalyst containing at least three elements selected from the group consisting of one or more heavy metals selected from cerium, zirconium and nickel. [Chemical 1] [Wherein R ¹ and R ² are the same or different and each represents an alkyl group, and A is , , , Or Represents. X, Y ¹ , Y ² and Z are the same or different and each represents a halogen group, a nitro group or a nitrile group. m and n each independently represent an integer of 0-4. ] [Chemical 7] [In the formula, A, X, Y ¹ , Y ² , Z, m and n have the same meanings as in formula (1). ]