JPH0232041A - Production of 4,4'-biphenyldicarboxylic acid - Google Patents

Abstract

PURPOSE:To obtain the subject substance by continuously or semicontinuously charging 4,4'-diethylbiphenyl or oxidized intermediate of said diethylbiphenyl and oxidizing with molecular oxygen-containing gas in solvent containing aliphatic monocarboxylic acid and in the presence of catalyst containing Co, Mn and Br. CONSTITUTION:4,4'-diethylbiphenyl or oxidized intermediate of said diethylbiphenyl is continuously or semi-continuously charged into reaction system and oxidized with molecular oxygen-containing gas in a solvent containing >=50wt.% <=3C aliphatic monocarboxylic acid (e.g., acetic acid) and in the presence of catalyst composed of Co and/or Mn in an amount of >=0.02wt.% (preferably >=0.05wt.%) of the solvent and Br of the same amount as said Co and/or Mn, at 130-250 deg.C and 0.1-20kg/cm<2>G partial pressure of oxygen (preferably at 150 deg.C and 0.5-5kg/cm<2>G) to obtain the subject substance in high-purity and high yield. The subject substance is useful for polymeric material, intermediate of dye or industrial chemicals.

Description

[Detailed Description of the Invention] [Industrial Application Field] The present invention relates to 4,4°-biphenyl dicarboxylic acid.
, 4°-BDCA).

[Prior Art 1 4,4'-BDCA is a compound useful as a polymer material, a dye intermediate, an industrial chemical, etc. Especially 4,4″-BD
Polyester containing CA has better heat resistance and rigidity than polyethylene terephthalate, and
It is attracting attention as a material for fibers, etc.

For this reason, it is desired to develop an advantageous method for producing 4,4°-BDCA.

The manufacturing method for this 4,4°-BDC is ■
Dechlorination and trimerization of p-chlorobenzoic acid using a palladium catalyst (USP 2,809,210); ■ 4,4°-bis(
Method of air oxidation with chloromethyl aqueous solution (Japanese Patent Publication No. 40-3, 774
), ■ A method of oxidizing dicyclohexylhinoenyl obtained by cyclohexylating biphenyl with air in an acetic acid solvent in the presence of a catalyst consisting of a halogen, an linker, and bromine (Japanese Patent Application Laid-Open No. 1983-16831). ■ 4-Alkyl biphenyl is reacted with carbon monoxide in the presence of a fluorine-boron fluoride catalyst to synthesize 4-alkyl 4"-formyl biphenyl, and oxidized with molecular oxygen-containing gas in the presence of a catalyst.
A method such as ``A method of ``(Japanese Unexamined Patent Publication No. 60174.745) is known.

However, method (2) requires the use of an expensive palladium catalyst, and is impractical due to the low purity of 4,4" in the product. 1. It is difficult to put it into practical use because harmful hischloromethyl ether is produced. Method 2 does not easily oxidize the cyclohexyl group, and the yield of oxidized T culm and I4 degree are low. Pre-process 4-
Considering the production of alkyl biphenyl, both methods are industrially unsuitable due to the fact that they are not economical, etc.
- Convenient and easily practicable preparation to 4, 4°-8 DC) 1
Even though it is the b method, it is only 4! , -1[Invention tries to solve 1
- Problem 1 The present invention has been devised in view of this point of view.
The purpose of this invention is to provide a method for producing qru4,4°-BDCA. That is, by using raw materials that are relatively easily obtained industrially and oxidizing air (oxygen-containing gas) in the liquid phase,
．． The purpose is to produce 4'4DCA.

[Means for Solving the Problems 1] In other words, the present invention provides 4,4'-di-1[-chirpidinyl or an oxidized intermediate thereof, an aliphatic monocarboxylic acid having 3 or less carbon atoms, and an aliphatic monocarboxylic acid having at least 50,000 carbon atoms. When oxidizing from molecular oxygen-containing gas 1 in a solvent containing star%, 0.0 per solvent.
A catalyst consisting of a heavy metal consisting of cobalt and/or manganese of 22 times or more and bromine of 0602 times or more per solvent is used, and 4,4゛-diT-delbiphenyl, its oxidized intermediate and 4.4゛-Use at least twice as much solvent as biphenyl dicarboxylic acid, and reduce the reaction temperature to 1.
30-=-250"C1 oxygen fraction 0.1"-2ONf
This is a method for producing 4,4°-biphinyldicarboxylic acid, which is oxidized under f/ci·G reaction conditions.

The raw material 4,4'-diethylbinyl (hereinafter abbreviated as 4,4'-[)[BP]) used in the present invention can be obtained by ethylating biphenyl or monoethylvinyl with ethylene, or by translating poly]nitylbenzene (with It is obtained by ethylation, isomerization of ethyl biphenyl, for example, by passing ethyl biphenyl into ethylene in the presence of an alkylation catalyst such as aluminum chloride or a solid acid catalyst.

The 13'''C of the alkylation reaction T culm varies depending on the type of catalyst, but for example, in the case of aluminum chloride, it is usually 50~
At a temperature of 200°C, preferably 80-150°C, several Nf
It is carried out under a pressure of f/ci-G"f & 1/cirt.G, preferably 5 to 108!J/ci-G.

(The alkylation reaction product q is obtained by distillation after removing the catalyst (including 4,4' and 4'4).
One leaf BP distillate is collected. In addition, unreacted hyphenyl, monoethyl hyphenyl, etc. are recovered and sent to the cylindrical culm for recycling.

Furthermore, the residual components such as 1- and 1-isomers can be sent to an isomerization step and used for recycling.

In the isomerization step C, such as 1 Herans Y delation and disproportionation, the sent ethylhyphenyls are isomerized in the presence of an isomerization catalyst. In this process, 1) EB other than 4, 4° integral
P, triethyl biphinyl, didirubinyl, etc. are monoethyl biphinyl, DEBP.

1-ethyl diphenyl is converted to detora-o-purubino-1-niphenyl. In this isomerization step, the same catalyst as in the T-chill process can be used, and it is also possible to carry out the reaction in the same reactor. The pressure may be C' or higher than the pressure necessary to keep the reactants in a liquid phase at the reaction temperature.

The jelly BP fraction is sent to a crystallization step for 4,4-integral separation, and crystals are precipitated by cooling.

The crystallization temperature depends on the composition of the Kano BP swamp, but is usually 15~-
The temperature is preferably 30°C. In this case, by using an appropriate solvent, the crystallization temperature can be lowered and the overall recovery rate can be improved by 4.4%. Alcohols such as isopropyl alcohol are suitable as the solvent.

Moreover, 4,4-integrated can be separated using zeolite as an adsorbent, and mordenite is suitable as the zeolite used in this case.

The obtained crystals of 4,4'' are highly pure 4.4''-BP as they are, but if washed or recrystallized with a suitable solvent such as isopropyl alcohol, even higher purity 4,4'' can be obtained. 1q of 4'-diethylbiphenyl is obtained.

Next, 4,4°-DEBP is sent to an oxidation step where it is contacted with molecular oxygen-containing gas in the presence of an oxidation catalyst in an aliphatic monocarboxylic acid-containing solvent and oxidized to 4,4′-BDCA. Ru.

The solvent used here contains an aliphatic monocarboxylic acid having 3 or less carbon atoms in an amount of 50% or more, preferably 70% by weight.
Use a solvent containing the above. As the aliphatic monocarboxylic acid, acetic acid is economically suitable. The amount of the solvent used is at least 2 times the weight of the raw materials 4,4°-KoBP, its oxidized intermediate and 4,4°-BDCA present in the reaction system, preferably 3 times or more by weight, More preferably, it is used in an amount of about 5 to 10 times the weight. In addition, it is desirable that the water content in the solvent is 50% or less, preferably 30% or less; if the water content is excessive, reaction intermediates will increase,
The yield of 4,4°-BDCA decreases.

As the oxidation catalyst, a catalyst system consisting of a small metal consisting of cobalt and/or manganese and bromine is used. As cobalt and manganese, any compound soluble in a solvent can be used, but acetate and bromide are preferred.

As bromine, hydrogen bromide, cobalt bromide, manganese bromide, ammonium bromide, alkali metal bromide or tetrabromoethane are preferred. The amount of heavy metals, ie, cobalt compounds and manganese compounds used, is such that the total metal concentration of cobalt and manganese is 0.02% or more, preferably 0.05% or more, based on the solvent. The amount of the bromine compound to be used is such that the bromine concentration is 0.02% by weight or more, preferably 0.05% by weight or more, based on the solvent.

If the catalyst is insufficient, the yield of BDCA will be low.

The reaction temperature is in the range of 130 to 250°C, preferably 150°C.
~200°C. When the reaction temperature is low, the yield of 4,4°-BDCA decreases due to a decrease in the reaction rate, whereas when it is high, on the other hand, side reaction products increase and the yield of 4,4°-BDCA is reduced.
-8 [) The purity of CA crystal decreases. Further, the oxygen partial pressure is in the range of 0.1 to 2 ONff10yf, preferably 0.
1 to 10KFi/car-G, more preferably 0.5 to
5Kg/cd-G. The reaction pressure is set so that the solvent is kept in the liquid phase at the reaction temperature, but
Usually 9/c on 10-30! -G level is appropriate.

Pure oxygen gas can also be used as the molecular oxygen-containing gas, but from an industrial perspective, normal air is most suitable.

Generally speaking, the reaction method may be either a batch method or a semi-continuous method, but in order to control side reactions and obtain products of good quality with a high yield, it is necessary to use the raw material 4,4°-DEBP and other methods. Particularly preferred is a semi-continuous or continuous method in which raw materials are continuously or semi-continuously charged into the reaction system.

4,4'-BDCA produced by the oxidation reaction is poorly soluble even in hot acetic acid, and by solid-liquid separation of the reaction mixture, the solvent, catalyst, unreacted substances, by-products, etc. can be separated. . The obtained 4,4-BDCA can be further purified as necessary to obtain highly pure 4.4'-8D.
It can be C8.

[Examples] Hereinafter, the present invention will be specifically explained based on Examples. In the Examples, parts and % indicate parts by weight and % by weight, respectively.

Example 1 Biphenyl 11,
000 parts of diethylbenzene, 19.000 parts of diethylbenzene, and 600 parts of aluminum chloride were charged, and the mixture was reacted at 130° C. for 3 hours with stirring. After the reaction was completed, the catalyst was removed by washing with water, and the reaction mixture was distilled to remove the alkylbenzenes to obtain a mixture of alkylbiphenyls. The composition of the resulting alkyl biphenyl mixture was 39% biphenyl, 40% monoethyl biphenyl, 13% diethylbiphenyl, 2% triedyl biphenyl, and 6% others, and the proportion of 4,4゛ in diethylbiphenyl was It was 9%.

4. further distilling this alkyl biphenyls mixture;
3°50 of Kano BP fraction containing 25% 4'-BDCA
I got 0 copies.

3,000 parts of DEBP fraction and 3.00 parts of isopropanol
0 parts was added, crystallized at -25°C for solid-liquid separation, and the crystals were washed with cold isopropanol to give 4.4°-4.4°C with a purity of 99%.
Obtained 640 copies of DEBP.

In addition, in a glass column filled with 600 parts of ■-mordenite, 10 parts of DEBP fraction 1 and 1.0 parts of n-heptane were added.
After supplying and adsorbing 0.00 parts, 1.000 parts of toluene was used for development. 4.4°-DEB in the second half of the developing solution
A fractionated solution containing only P and solvent was obtained, and when toluene was distilled off from this fractionated solution, 4,4°-DEBPh<0.
I got 5 copies.

4,4°-DE with a purity of 99% produced by the above method in a 50011dl titanium autoclave equipped with a magnetic stirrer.
30 parts of BP and 300 parts of acetic acid were charged, and cobalt acetate, manganese acetate, and sodium bromide were used as catalysts, and Co and HnlBr were 0°2% and 0%, respectively, based on the solvent.
．． 2% and 0.6%, and after raising the temperature to 180°C, 1. While maintaining the pressure at 20Kg/cIi・G, the reaction air is pumped at 2.1 times per minute! The mixture was supplied to the reaction vessel at a rate of 1 hour for reaction.

After the reaction was completed, the slurry of the reaction mixture was cooled and separated by filtration, the obtained crystals were dried, and the purity of the dried crystals was measured by an internal standard method using high-performance liquid chromatography. The result was 82.3%, and the 4.4'-BDC^ yield was 79.5%.

Examples 2 to 7 and Comparative Examples 1 and 2 Reactions were carried out in the same manner as in Example 1. The reaction conditions and results are shown in Table 1.

Example 8 200 parts of acetic acid was charged in a 300-titanium autoclave equipped with a magnetic stirrer, and cobalt acetate, manganese acetate, and sodium bromide were added as catalysts to the solvent, respectively.
n and 8r were added so that they were 0.2%, 0°2%, and 0.6%, respectively, and after raising the temperature to 180°C, the pressure was lowered to 2.
While supplying reaction air to the reaction vessel at a rate of 2 g/min while maintaining the temperature at 0KI/ci-G, 4,4°-KoBP30
1 hour to react.

After the reaction was completed, the slurry of the reaction mixture was cooled and separated by filtration, and the resulting crystals were dried, and the purity of the dried crystals was measured by an internal standard method using high-performance liquid chromatography.Results is 97.0% and 4,4°-BDC^
The yield was 85.0%.

Example 9 A reaction was carried out in the same manner as in Example 8. The reaction conditions and results are shown in Table 1.

[Effects of the Invention] According to the method of the present invention, 4,4゛-diethylbiphenyl, which can be obtained 1q relatively easily and with high purity by means such as crystallization, is used as a raw material and oxidized with an oxygen-containing gas such as air. As a result, 4,4゛-biphenyl dicarboxylic acid can be obtained in high yield, so it is not only possible to produce it industrially advantageously, but also has the potential to be used in polymeric materials such as polyester and polyamide. can be increased.

Moreover, if the method of the present invention is carried out in a continuous or semi-continuous manner, 4,4°-biphenyldicarboxylic acid can be produced with higher yield and purity.

Patent applicant: Nippon Steel Chemical Co., Ltd.

Claims (2)

[Claims] (1) When oxidizing 4,4'-diethylbiphenyl or its oxidized intermediate with a molecular oxygen-containing gas in a solvent containing at least 50% by weight of an aliphatic monocarboxylic acid having 3 or less carbon atoms, 0 per heavy metal and solvent consisting of 0.02% by weight or more of cobalt and/or manganese
．． using a catalyst consisting of 0.02% by weight or more of bromine, and
4,4'-diethylbiphenyl, its oxidized intermediates and 4
, 4'-biphenyldicarboxylic acid at least 2
Production of 4,4'-biphenyldicarboxylic acid, characterized by oxidation using twice the weight of solvent, reaction temperature of 130 to 250°C, and oxygen partial pressure of 0.1 to 20 Kg/cm^2.G. Method. (2) The method for producing 4,4'-diviphenyldicarboxylic acid according to claim 1, wherein 4,4'-diethylbiphenyl is continuously or semi-continuously charged into the reaction system.