JPH0768247B2 - Method for producing diallyl dicarboxylic acid - Google Patents

Description

TECHNICAL FIELD The present invention relates to a method for producing a corresponding diarylcadylbonic acid by oxidizing a dialkyl-substituted diaryl compound.

The diaryldicarboxylic acid obtained by the method of the present invention is
It is a compound useful as a raw material for polyester resins and polyamide resins having excellent heat resistance and mechanical properties.

[Prior Art and its Problems] Conventionally, dialkyl-substituted diaryl compounds in organic solvents,
As a method for producing a corresponding diaryldicarboxylic acid by oxidation with molecular oxygen, a method using cobalt as a catalyst and methyl ethyl ketone as a promoter (US Pat.
676,488, U.S. Pat. No. 3,641,135, etc.) or a method of using cobalt and bromine as catalysts (JP-A-61-6064).
No. 5, JP-A-61-63634, etc.) are known. But,
The former has drawbacks such that the reaction time is long, a large amount of expensive promoter is required, and the yield is not so good. In addition, the latter has the drawbacks that an induction period occurs at the start of the reaction, the rate decreases remarkably during the reaction, and the yield decreases.
Therefore, these known methods are not satisfactory as methods for industrially inexpensively producing diaryldicarboxylic acids.

Further, as an oxidation catalyst of ditolylethane, a cobalt-bromine-copper catalyst, a cobalt-manganese-bromine-copper catalyst (JP-A-52-77022) and (vanadium, niobium and / or molybdenum) -cobalt-bromine catalyst. , (Vanadium, niobium and / or molybdenum) -cobalt-manganese-bromine catalysts (JP-A-51-127034).

[Problems to be Solved by the Invention] In producing a diaryldicarboxylic acid by oxidizing a dialkyl-substituted diaryl compound, establishment of an industrially advantageous method that can be oxidized at a low cost and in a high yield at an economical rate Is desired.

As a result of intensive studies on the method of oxidizing a dialkyl-substituted diaryl compound with molecular oxygen in an organic solvent, the present inventors have found that by applying a specific compound as a catalyst for an oxidation reaction, the intended purpose can be obtained. They have found the present invention and have completed the present invention based on this finding.

That is, the object of the present invention is to provide a novel method for producing a diaryldicarboxylic acid, which is characterized by an oxidation reaction catalyst.

[Means for Solving Problems] The method for producing a diaryldicarboxylic acid according to the present invention comprises a compound represented by the general formula (I): [In the formula, A is —O—, —SO ₂ —, Represents ] The dimethyl-substituted diaryl compound represented by the general formula (II) is oxidized with molecular oxygen in an organic solvent. [In the formula, A ′ is —O—, —SO ₂ —, Represents ] In producing the diarylcarboxylic acid represented by, at least one kind or two or more kinds selected from the group consisting of (A) cobalt, (B) bromine or bromine and chlorine, (C) manganese, cerium and nickel It is characterized by using a catalyst containing three components of heavy metals. However, in the above general formula, when A is -O- A 'is -O-, and when A is -SO ₂ A' is -SO _2, A is Is.

In the method according to the present invention, as the dimethyl-substituted aryl compound represented by the general formula (I) used as a raw material, 3,3′-dimethyldiphenyl ether, 3,4′-dimethyldiphenyl ether, 4,4′-dimethyldiphenyl ether, 3,3'-Dimethyldiphenyl sulfone, 3,4'-Dimethyldiphenyl sulfone, 4,4'-Dimethyldiphenyl sulfone, 1,1-Bis (3-methylphenyl) ethane, 1,1-Bis (4-methylphenyl) ) Ethane, bis (3-methylphenyl) dimethylsilane, bis (4-methylphenyl) dimethylsilane, and other dimethyl-substituted compounds of each of the above diaryl compounds.

The catalyst used in the present invention contains at least three components of one or more heavy metals selected from the group consisting of (A) cobalt, (B) bromine or bromine and chlorine and (C) manganese, cerium and nickel. contains.

(A) Cobalt may be added to the reaction system in any form such as a simple substance, an oxide, a hydroxide, an organic acid salt, an inorganic acid salt and a complex, but a salt which is at least partially dissolved in the reaction system,
For example, cobalt acetate, cobalt naphthenate, cobalt bromide, cobalt hydroxide and the like are preferable.

The appropriate amount of cobalt used is 0.01 to 10 g / in terms of metal concentration. If it is less than 0.01 g /, a sufficient reaction rate cannot be obtained, and if it is more than 10 g /, the burden of catalyst cost increases and side reactions tend to increase.

As (B) bromine, any of bromine molecule, its acid, salt, oxyacid salt, organic bromine compound and the like can be used, and in particular, hydrogen bromide, ammonium bromide, sodium bromide, cobalt bromide, bromide Manganese, cerium bromide, tetrabromoethane, tribromoethane and the like are preferable. The same applies to chlorine.

The appropriate amount of bromine used is 0.1 to 100 equivalents in terms of bromine atom per atom of cobalt (A) and heavy metal (C). 0.
If it is less than 1 equivalent, a sufficient speed cannot be obtained, and if it is more than 100 equivalents, product contamination due to bromine and the burden of catalyst cost are large, which is not preferable.

When using bromine and chlorine together, the total is 0 in atomic conversion.
A suitable amount is 1 to 100 equivalents, and the ratio of chlorine to bromine is preferably 0.7 or less.

The heavy metal (C) selected from the group consisting of manganese, cerium and nickel may be in any form such as a simple substance, an oxide, a hydroxide, an organic acid salt, an inorganic acid salt or a complex.

The amount of the heavy metal used is a weight ratio to the cobalt metal.
A ratio of 0.01 to 100 is suitable. If it is added in an amount of 0.01 or less, no significant effect of accelerating the reaction is observed, and if it is added in an amount of 100 or more, the burden of the catalyst cost increases and it is economically disadvantageous.

Specific examples of the catalyst system according to the present invention include the following catalyst systems. That is, cobalt bromide and manganese bromide, cobalt acetate and manganese acetate and ammonium bromide, cobalt bromide and manganese acetate, cobalt naphthenate and manganese acetate and tetrabromoethane, cobalt bromide and cerium acetate, cobalt acetate and cerium acetate. And, hydrogen bromide, cobalt acetate and nickel bromide, cobalt acetate and manganese acetate and cerium acetate and hydrogen bromide, cobalt acetate and manganese acetate and hydrogen bromide, and hydrogen chloride are fried. The present invention is not limited to this example.

As the molecular oxygen used as the oxidant, pure oxygen or industrial exhaust gas can be used, but industrially air is most suitable.

The reaction solvent may be any medium that is inert or relatively stable under the oxidation reaction conditions of the present invention, and preferably a polar organic compound is used. For example, a saturated monocarboxylic acid having about 2 to 10 carbon atoms is preferable, and acetic acid is particularly suitable.

The reaction pressure is preferably such that the total reaction pressure is in the range of 1 to 100 atm, particularly 2 to 50 atm, and the oxygen partial pressure is 0.1 to 10 atm.

Further, from the viewpoint of safety, it is desirable to operate so that the oxygen concentration in the gas discharged from the reactor is 8% by volume or less.

The reaction temperature is in the range of 80 to 250 ° C, preferably 120 to 200 ° C. The reaction rate is slower at temperatures lower than 80 ℃, 250 ℃
If the temperature exceeds 1, the decomposition of the solvent or the product into carbon dioxide becomes severe, which is not preferable.

The reaction time depends on the amount of the catalyst, the kind of the dialkyl-substituted diaryl compound and various reaction conditions, but is usually 0.5 to 50 hours.

When the reaction is carried out under the above conditions, the intended product, diaryldicarphonic acid, is precipitated outside the reaction system. Therefore, the desired product can be easily isolated only by allowing the reaction to proceed sufficiently, separating the precipitated solid from the reaction solution by filtration, and washing. The reaction solution after isolation of the desired product can be subjected to repeated oxidation reaction by adding a dialkyl-substituted diaryl compound as it is or after adjusting the water content or adding a new catalyst as necessary.

[Examples] Hereinafter, the present invention will be described in more detail with reference to Examples.

Example 1 246 g (1.0 mol) of 4,4'-dimethyldiphenyl sulfone,
Cobalt bromide _{[CoBr 2 · 6H 2 O]} 16g (49 mmol), manganese acetate _{[Mn (OAc) 2 · 4H} 2 O] a 3 g (12 mmol) and 2.5 was dissolved in acetic acid were charged into an autoclave, stirred While raising the temperature to 150 ° C. The pressure was increased to 20 kg / cm ² · G with air, the air was continuously sucked at 5.0 to 0.5 ml / min, and oxidation was performed for 1.5 hours. Then, the reaction mixture was extracted, cooled to room temperature, and the precipitated solid was filtered off. The solid was thoroughly washed with acetic acid and then with cold water, and dried under reduced pressure to give 294 g of colorless powder.
(Yield 96%) was obtained.

This product was identified as diphenylsulfone-4,4'dicarboxylic acid by NMR and IR spectra, and its neutralization number was 361.
(Purity 98.4%).

Comparative Example 1 Oxidation was performed in the same manner as in Example 1 without using manganese acetate.
An induction period of about 0.25 hours occurred in the early stage of the reaction, and 267 g (yield 87%) of the solid obtained after the reaction was slightly yellow.

Example 2 4,4'-dimethyl ether 198 g (1.0 mol), cobalt acetate _{[Co (OAc) 2 · 4H} 2 O] 7g (28 mmol), manganese acetate 7 g (28 mmol) and ammonium bromide 11g (112 mmol ) In acetic acid to 2.5,
In the same manner as in Example 1, 240 g (yield 93%) of colorless powder of diphenyl ether-4,4'-dicarboxylic acid was obtained. The neutralization value of this product was 426 (purity 98.2%).

Example 3 1,1-bis (4-methylphenyl) ethane 210g (1.0 mole), cobalt bromide 9 g (28 mmol) and nickel acetate _{[Ni (OAc) 2 · 4H} 2 O] 3g (12 mmol) acetic acid It was dissolved in the solution to give 2.5 and was oxidized in the same manner as in Example 2. The solid precipitated from the reaction mixture is filtered off, washed and dried to give a colorless powder.
259 g (yield 96%) was obtained.

This product was identified as benzophenone-4,4'-dicarboxylic acid by NMR and IR spectra, and its neutralization value was 412.
(Purity 99.3%).

Example 4 210 g (1.0 mol) of 1,1-bis (3-methylphenyl) ethane, 6 g (24 mmol) of cobalt acetate, 3 g of manganese acetate
(12 mmol), 3 g (10 mmol) of cerium acetate and 16 g (93 mmol) of hydrobromic acid (d = 1.48) were dissolved in acetic acid to 2.5 and oxidized in the same manner as in Example 2. The solid precipitated from the reaction mixture is filtered off, washed and dried to give a colorless powder.
265 g (yield 98%) was obtained.

This product was identified as benzophenone-3,3'-dicarboxylic acid by NMR and IR spectra, and its neutralization value was 410
(Purity 98.8%).

Example 5 240 g of bis (4-methylphenyl) dimethylsilane (1.0
Mol), cobalt acetate 12 g (48 mmol), manganese acetate 1 g (4 mmol), hydrobromic acid 8 g (46 mmol) and concentrated hydrochloric acid 5 g (48 mmol) in acetic acid to 2.5.
It was oxidized in the same manner as in Example 1. The solid precipitated from the reaction mixture was filtered off, washed and dried to give 284 g of colorless powder (yield 95%).
Got

This product was fixed to bis (4-carboxyphenyl) dimethylsilane by NMR and IR spectra, and its neutralization number was 370 (purity 99.0%).

[Effects of the Invention] According to the method of the present invention, when various dialkyl-substituted diaryl compounds are oxidized by molecular oxygen in an organic solvent, the reaction time is shortened as compared with the conventional method, and high yield and high purity are industrially advantageous. Further, diaryldicarboxylic acids can be produced.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical indication C07C 65/34 315/04 317/44 // C07B 61/00 300

Claims (1)

[Claims] 1. A general formula (I) [In the formula, A is —O—, —SO ₂ —, Represents ] The dimethyl-substituted diaryl compound represented by the general formula (II) is oxidized with molecular oxygen in an organic solvent. [In the formula, A ′ represents —O—, —SO ₂ —, Represents ] In producing the diarylcarboxylic acid represented by, at least one kind or two or more kinds selected from the group consisting of (A) cobalt, (B) bromine or bromine and chlorine, (C) manganese, cerium and nickel A method for producing a diarylcarboxylic acid, which comprises using a catalyst containing three components of a heavy metal. However, in the above general formula, when A is -O- A 'is -O-, and when A is -SO ₂ A' is -SO _2, A is Is. ]