JP2011162488A - Method for producing asymmetric biphenyltetracarboxylic acid tetraester - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an asymmetric biphenyltetracarboxylic acid tetraester, comprising oxidation-coupling a phthalic acid diester in the presence of molecular oxygen using a palladium-bearing catalyst and the phthalic acid diester to continuously produce the asymmetric biphenyltetracarboxylic acid tetraester, which can be performed with a simple apparatus in simple operations in high productivity at a low cost, while holding high catalyst efficiency (catalyst turnover frequency). <P>SOLUTION: The method for producing the asymmetric biphenyltetracarboxylic acid tetraester includes continuously or intermittently supplying a phthalic acid diester, a catalyst component comprising at least a palladium compound and a copper salt in an amount of 2 to 20 times (in mole) the palladium compound, and molecular oxygen, to the first reaction region, in a reaction apparatus whose liquid phase portion has one or more reaction regions, continuously or intermittently taking out a part of the reaction mixture solution from the first reaction region, and simultaneously performing the oxidation dimerization reaction of the phthalic acid diester. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to biphenyltetracarboxylic acid tetraester, particularly 2,3,3 ′, 4′-biphenyltetracarboxylic acid, by oxidative coupling of phthalic acid diester using a catalyst containing palladium in the presence of molecular oxygen. The present invention relates to a production method for continuously producing asymmetric biphenyltetracarboxylic acid tetraesters such as tetraesters.

  Asymmetric 2,3,3 ′, 4′-biphenyltetracarboxylic acid tetraester (hereinafter abbreviated as a-BPTT) by oxidative coupling of phthalic diester with a catalyst containing palladium in the presence of molecular oxygen. There are already some examples of the production method for selectively producing the same.

  For example, Patent Document 1 discloses a production method for producing a-BPTT by causing an organic palladium salt and an organic copper salt to be present in a reaction solution in an atmosphere in which molecular oxygen exists, and oxidatively coupling a phthalic acid diester. It is disclosed.

  In Patent Document 2, a phthalic acid diester is oxidized while continuously or intermittently replenishing β-diketone to the reaction system using palladium salt and copper salt at high temperature in the presence of molecular oxygen. A method for producing a-BPTT characterized by coupling is disclosed.

  However, all of the production methods of the above-mentioned patent documents are based on batch operations. When this method is carried out particularly on an industrial scale, operations such as preparation and removal at the start and end of the reaction are complicated. In addition, there is room for improvement in terms of large loss of energy in order to perform heating and cooling operations each time, and difficulty in improving productivity because of the time required for operations other than reactions. . In addition, the said patent document did not show at all about the concrete means and method for the manufacturing method manufactured continuously.

  On the other hand, Patent Document 3 discloses a method for producing biphenyltetracarboxylic acid tetraester by continuous operation. That is, a step of continuously or intermittently feeding a phthalic diester and a catalyst containing a palladium compound as a uniformly stirred mixture to the reactor, and a phthalic diester oxidation dioxide while supplying molecular oxygen to the reactor. Biphenyl, wherein the step of performing the quantification reaction in a temperature range of 140 ° C. or higher and lower than 250 ° C. and the step of continuously or intermittently removing a part of the reaction mixture from the reactor are performed in parallel. A method for producing tetracarboxylic acid tetraesters is disclosed. Here, focusing on the catalyst rotation speed (hereinafter sometimes abbreviated as TON) represented by [product (mole number) / catalyst palladium (mole number)] with respect to the production of a-BPTT, TON has a TON of about 33 in a reaction with an apparent reaction time of 10 hours, and the utilization efficiency of palladium is not sufficient, and there is room for improvement in the utilization efficiency of palladium, which is an expensive noble metal. .

  In Patent Document 3, the catalyst component (particularly β-dicarbonyl compound) is introduced only into the first reactor, and the catalyst component is newly replenished to the reactor after the second reactor. Is not mentioned.

JP 55-141417 A JP 61-106541 A JP 2004-131470 A

  The present invention relates to biphenyltetracarboxylic acid tetraester, particularly 2,3,3 ′, 4′-biphenyltetracarboxylic acid, by oxidative coupling of phthalic acid diester using a catalyst containing palladium in the presence of molecular oxygen. A production method for continuously producing asymmetric biphenyltetracarboxylic acid tetraesters such as tetraesters, which can be carried out with simple equipment, simple operation, and high productivity, and catalyst efficiency (catalyst rotation speed) ) Is kept high and a manufacturing method that can be carried out more economically is proposed.

The present invention relates to the inventions of the following items.
(1) In a reactor having a liquid phase part having one or a plurality of reaction zones, from the phthalic acid diester and at least a palladium compound and a copper salt of 2 to 20 moles relative to the palladium compound to the first reaction zone The catalyst component is continuously or intermittently supplied, molecular oxygen is supplied to the first reaction zone, and a part of the reaction mixture is continuously or intermittently removed from the first reaction zone. A process for producing an asymmetric biphenyltetracarboxylic acid tetraester, characterized by carrying out an oxidative dimerization reaction of a phthalic acid diester.
(2) In a reaction apparatus having a plurality of reaction zones in the liquid phase part, in the reaction zone after the second reaction zone, a part of the reaction mixture is continuously or intermittently removed from the previous reaction zone, and the next Introduce sequentially into the reaction zone, supply molecular oxygen to the reaction zone, and carry out an oxidative dimerization reaction of phthalic acid diester while continuously or intermittently removing a part of the reaction mixture from the last reaction zone. Item 2. The method for producing an asymmetric biphenyltetracarboxylic acid tetraester according to Item 1 above.
(3) The method for producing an asymmetric biphenyltetracarboxylic acid tetraester as described in (1) or (2) above, wherein a β-dicarbonyl compound is further continuously or intermittently supplied as a catalyst component.
(4) In a reaction apparatus having a plurality of reaction zones in the liquid phase part, a catalyst component comprising at least a β-dicarbonyl compound is continuously or intermittently supplied to the reaction zones after the second reaction zone. Item 4. The method for producing an asymmetric biphenyltetracarboxylic acid tetraester according to any one of Items 1 to 3.

  According to the present invention, a phthalic acid diester is oxidatively coupled with a catalyst containing palladium in the presence of molecular oxygen to form a biphenyltetracarboxylic acid tetraester, particularly 2,3,3 ′, 4′-biphenyltetracarboxylic acid. A production method for continuously producing asymmetric biphenyltetracarboxylic acid tetraesters such as tetraesters, which can be carried out with simple equipment, simple operation, and high productivity, and catalyst efficiency (catalyst rotation speed) ) Can be kept high and a production method that can be carried out more economically can be obtained.

FIG. 1 is a schematic view of the reaction apparatus used in Examples 1, 2, 3, and 6. FIG. 2 is a schematic view of the reaction apparatus used in Examples 4 and 5. FIG. 3 is a schematic view showing an example of the embodiment of the present invention. FIG. 4 is a schematic view showing another example of the embodiment of the present invention.

Hereinafter, the present invention will be described in detail.
In the production method of the present invention, in a reactor having a liquid phase part having one or a plurality of reaction zones, the phthalic acid diester, at least a palladium compound and a palladium compound at 2 to 10 times mol to the first reaction zone. A catalyst component comprising a copper salt is supplied continuously or intermittently, molecular oxygen is supplied to the first reaction zone, and a part of the reaction mixture is continuously or partially supplied from the first reaction zone. A process for producing an asymmetric biphenyltetracarboxylic acid tetraester, characterized in that an oxidative dimerization reaction of a phthalic acid diester is carried out while intermittently taking out.

  Further, in the production method of the present invention, in a reaction apparatus having a plurality of reaction zones in the liquid phase part, a part of the reaction mixture is continuously or intermittently passed from the previous reaction zone in the reaction zone after the second reaction zone. And then sequentially introduced into the next reaction zone, supplying molecular oxygen to the reaction zone, and continuously or intermittently removing a portion of the reaction mixture from the last reaction zone, A method for producing an asymmetric biphenyltetracarboxylic acid tetraester, characterized by performing a quantification reaction.

  Specific examples of the phthalic diester used in the present invention preferably include dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dibutyl phthalate, dioctyl phthalate, diphenyl phthalate, and the like. Can do. These phthalic acid diesters can be easily obtained by reacting phthalic acid, phthalic anhydride, phthalic acid halide, and the like with a compound having a hydroxyl group, such as lower aliphatic alcohols, aromatic alcohols, and phenols. it can.

  Examples of the palladium compound used in the present invention include palladium chloride, palladium bromide, palladium nitrate, palladium sulfate, palladium hydroxide, palladium acetate, palladium trifluoroacetate, palladium propionate, palladium pivalate, palladium trifluoromethanesulfonate, Specific examples include bis (acetylacetonato) palladium and bis (1,1,1-5,5,5-hexafluoroacetylacetonato) palladium. In particular, palladium acetate, palladium propionate, palladium pivalate, palladium trifluoroacetate, palladium hydroxide, and palladium nitrate are preferable because they exhibit high catalytic activity.

The amount of the palladium compound used is 1 × 10 ⁻⁵ to 1 × 10 ⁻² times mol, preferably 5 × 10 ^{−5 to} 5 × 10 ⁻⁴ times mol, with respect to 1 mol of phthalic acid diester as a reaction raw material. The amount is preferably 8 × 10 ^{−5 to} 3 × 10 ⁻⁴ times mol, more preferably 1 × 10 ⁻⁴ to 2 × 10 ⁻⁴ times mol. If palladium is used in an amount greater than the specified range, the TON improvement effect may not be sufficient. On the other hand, if palladium less than the specified range is used, the yield may be low and impractical.

  Examples of the copper salt used in the present invention include copper acetate, copper propionate, copper normal butyrate, copper 2-methylpropionate, copper pivalate, copper lactate, copper butyrate, copper benzoate, copper trifluoroacetate, bis (Acetylacetonato) copper, bis (1,1,1-5,5,5-hexafluoroacetylacetonato) copper, copper chloride, copper bromide, copper iodide, copper nitrate, copper nitrite, copper sulfate, Preferred examples include copper phosphate, copper oxide, copper hydroxide, copper trifluoromethanesulfonate, copper paratoluenesulfonate, and copper cyanide. In particular, copper acetate, copper propionate, normal butyrate, copper pivalate, and bis (acetylacetonato) copper are preferable because they have a high effect of promoting the oxidative coupling reaction. These copper salts can be suitably used in the form of anhydrides or hydrates.

  The amount of copper salt used is 2 to 20 times mol, preferably more than 2 times mol to 20 times mol, more preferably 3 to 20 times mol, more preferably in the first reaction zone, relative to the palladium compound. The amount is 3 to 10 times mol, particularly preferably 4 to 6 times mol. If the amount of copper salt used is less than 2 times mol, it is difficult to maintain high catalyst efficiency (catalyst rotation speed), and it is not economical to use a large amount of copper salt of 20 times mol. However, when using the reaction apparatus whose liquid phase part consists of a plurality of reaction zones, the amount of copper salt used after the second reaction zone is not limited to the above range.

  Depending on the solubility of the copper salt used in the present invention in the phthalic acid diester, the copper salt cannot be completely dissolved in the phthalic acid diester when used in the above concentration range, and may become a slurry. In such a case, the copper salt may be used in a slurry state.

In the present invention, a phthalic acid diester and a catalyst component composed of at least a palladium compound and a copper salt of 2 to 20 moles relative to the palladium compound are continuously or intermittently supplied to the first reaction zone.
Here, “continuously or intermittently supplied” means continuous supply or intermittent supply with a predetermined interval between supply stop periods. And in this invention, it is preferable that it is intermittent supply from a continuous supply (a supply stop period is 0 minute) to a supply stop period of less than 2 hours, preferably less than 1 hour, more preferably less than 30 minutes.

In the present invention, it is preferable to continuously or intermittently supply a β-dicarbonyl compound as a catalyst component.
As the β-dicarbonyl compound, both aliphatic and aromatic β-dicarbonyl compounds can be suitably used. Specific examples of β-dicarbonyl compounds include acetylacetone, benzoylacetone, trifluoroacetylacetone, 2,4-pentanedione, 2,4-hexanedione, 2,4-heptanedione, 1,3-diphenyl-1,3. -1,3-diketones such as propanedione, 1,1,1-trifluoro-2,4-hexanedione, acylacetates such as methyl acetoacetate, ethyl acetoacetate and methyl 3-oxovalerate, benzoyl Preferable examples include alcoyl acetates such as ethyl acetate, and malonates such as diethyl malonate and meltrum acid. Among these, 1,3-diketones are preferable.

When the β-dicarbonyl compound is continuously or intermittently supplied to the first reaction zone as the catalyst component, it is preferable to supply continuously or intermittently at intervals of less than 30 minutes, preferably at intervals of less than 10 minutes.
When the supply interval of β-dicarbonyl compound (supply stop period) is 30 minutes or more, it becomes difficult to suppress the consumption of palladium, which is an expensive noble metal, and [product (number of moles) / catalyst palladium ( The TON indicated by the number of moles)] becomes low, making it difficult to obtain an economical production method.

In supplying the β-dicarbonyl compound to each reaction zone in the apparatus, a reaction mixture consisting of phthalic acid diester, molecular oxygen, palladium compound, copper salt, etc., already contained in the reaction zone in the apparatus receiving the supply. The temperature is preferably 130 ° C. or higher. For example, when starting up a continuous reaction operation from a new state or a pause state, in the process of raising the temperature of the reaction mixture contained in the reaction zone to a target temperature, the temperature of the mixture does not reach 130 ° C. If the β-dicarbonyl compound is supplied or charged in advance together with other catalyst components in the reaction zone, the β-dicarbonyl compound is unlikely to evaporate or decompose, so the amount of β-dicarbonyl compound in the mixture May become an obstacle to the reaction, and at least in the initial stage of the continuous reaction, there may be a case where the steady operation cannot be performed stably, such as a decrease in the reaction result.
Therefore, in the present invention, the supply of the β-dicarbonyl compound is preferably started when the temperature of each reaction zone is 130 ° C. or higher, preferably 140 ° C. or higher, more preferably 150 ° C. or higher.

  In the present invention, when a reaction apparatus having a plurality of reaction zones in the liquid phase portion is used, in the reaction zone after the second reaction zone, a part of the reaction mixture in the previous reaction zone is introduced into the reaction zone. However, in addition to this, phthalic acid diester as a raw material for the reaction and a catalyst component may be additionally supplied. In particular, a catalyst component consisting of at least a β-dicarbonyl compound may be additionally supplied continuously or intermittently. Is preferred. Since the β-dicarbonyl compound is easily lost from the reaction mixture due to decomposition, evaporation, etc., not only the first reaction zone but also the second reaction zone and beyond can be supplied separately. This is suitable for keeping the catalyst efficiency (catalyst rotation speed) high in the zone. It should be noted that the β-dicarbonyl compound additionally supplied to the reaction zone after the second reaction zone is not necessarily supplied together with the phthalic acid diester as the reaction raw material and the palladium compound or copper salt as other catalyst components. Absent. Even when supplying together with phthalic acid diester as a reaction raw material or palladium compound or copper salt as a catalyst component, the type and composition ratio need not be the same as those supplied to the first reaction zone.

  The state or form of the β-dicarbonyl compound when supplying the β-dicarbonyl compound to the reaction zone is not particularly limited. If the β-dicarbonyl compound is liquid, it may be supplied intermittently and continuously by a liquid feed pump or the like, and the β-dicarbonyl compound dissolved in, for example, a phthalate ester as a reaction raw material or a suspended suspension As an alternative, it may be supplied intermittently and continuously by a liquid feed pump or the like.

  In the production method of the present invention, the supply amount of the β-dicarbonyl compound needs to be appropriately determined in consideration of the influence of the reaction pressure, reaction temperature, etc., but usually, relative to the palladium compound supplied to the reaction zone. The reaction time is intermittently or continuously in the reaction zone at a rate of 0.1 to 50 times mol, preferably 1 to 10 times mol, more preferably 2 to 9 times mol, further preferably 3 to 8 times mol per hour. It is preferable to supply them automatically. When the residence time is long, it is preferable to increase the supply amount in proportion to the residence time.

  If the β-dicarbonyl compound is intermittently or continuously supplied at the above rate relative to the palladium compound supplied per unit time to the reaction zone, other catalyst components such as palladium compound and copper salt are added. The β-dicarbonyl compound may be additionally supplied to the reaction zones after the second reaction zone. That is, when additionally supplying together with the palladium compound, β− with respect to the total amount of the palladium compound contained in the reaction mixture supplied from the previous reaction zone and the additional palladium compound supplied to the reaction zone. It is preferable to additionally supply the dicarbonyl compound so that the supply amount thereof becomes the above-mentioned preferable ratio. On the other hand, when the copper salt is additionally supplied, it is not necessary that the copper salt is 2 to 20 times mol based on the total amount of the palladium compound supplied to the reaction zone, and it may be less than 2 times mol. Absent.

  In the production method of the present invention, a reaction solvent may be used, but may not be used when the reaction raw material is liquid under the reaction conditions. Industrially, it is preferable to carry out the reaction substantially without using a reaction solvent. In the case of using a reaction solvent, although not limited, organic ester compounds such as ethylene glycol diacetate and dimethyl adipate, and ketone compounds such as n-butyl methyl ketone, methyl ethyl ketone, and isopropyl ethyl ketone are preferably exemplified. be able to.

  In the production method of the present invention, molecular oxygen is supplied to each reaction zone to carry out the reaction. The molecular oxygen may be pure oxygen gas, but considering the risk of explosion, the oxygen content is diluted to about 5% to 50% by volume with an inert gas such as nitrogen gas or carbon dioxide. It is preferable to use a mixed gas or air. For example, when air is used, it is preferable to supply the reaction mixture uniformly in the reaction mixture at a supply rate of about 1 to 20000 ml / min, particularly 10 to 10000 ml / min per 1000 ml of the reaction solution. . Specific supply methods include, for example, a method in which a molecular oxygen-containing gas is circulated along the liquid surface of the reaction mixture and brought into gas-liquid contact, and the gas is ejected from a nozzle provided at the top of the reaction mixture. A method in which the gas is supplied in the form of bubbles from a nozzle provided at the bottom of the reaction mixture, and the bubbles are caused to flow into the reaction mixture to be in gas-liquid contact, and a porous is provided at the bottom of the reaction mixture. Preferred examples include a method of supplying the gas in the form of bubbles from a plate, or a method of causing the reaction mixture to flow into the conduit and jetting the gas into the reaction mixture from the side of the conduit. .

  The reaction pressure of the production method of the present invention is not particularly limited. If the catalyst, molecular oxygen, and β-dicarbonyl compound can stay in the reaction system within the specified concentration range, the reaction pressure can be reduced, normal, or pressurized. There is no problem. Usually, normal pressure is preferred because facilities and operations become simple.

  The reaction temperature in the production method of the present invention is preferably 140 to 250 ° C, more preferably 170 to 240 ° C, still more preferably 180 to 220 ° C. The reaction time, that is, the average residence time of the raw material mixture in the entire reaction zone is not limited and may be appropriately determined, but is usually about 1 to 20 hours, preferably about 5 to 10 hours.

  In the present invention, when a reaction apparatus having a liquid phase part composed of a plurality of reaction zones is used, the reaction temperature in each reaction zone may be the same or different. In particular, it is preferable that the reaction temperature of each reaction zone is a temperature range of 140 ° C. or more and less than 250 ° C., and the reaction temperature of the (n + 1) th reaction zone is higher than the reaction temperature of the nth reaction zone. . (Here, n is an integer of 1 or more.)

  In the present invention, as long as the oxidative dimerization reaction can be carried out by continuous operation, the method for continuously or intermittently supplying the reaction raw material phthalic acid diester and the catalyst component to each reaction zone is not particularly limited. Specifically, palladium compounds and copper salts as catalyst components may be supplied in a uniform slurry form with phthalic diester, or phthalic diester is supplied with a pump or the like, and the catalyst component reacts as a separate powder. It may be supplied to the area. In particular, if the catalyst component is completely dissolved to form a uniform solution, or if the solid component is made into a sufficiently fine slurry, it can be supplied with a simple liquid pump without requiring complicated operations and complicated equipment. Therefore, it is preferable. Moreover, you may supply these reaction raw materials and catalyst components with a solvent as needed.

  In the present invention, the method of taking out (withdrawing) the reaction solution from each reaction zone is not particularly limited as long as the oxidation dimerization reaction can be performed by continuous operation. Specifically, intermittent extraction may be performed such that extraction starts when the reaction liquid in the reaction zone reaches a predetermined liquid level and stops extraction when the reaction liquid falls to a predetermined liquid level, and is approximately equal to the amount of liquid supplied. An amount of the reaction solution may be continuously extracted with a pump. In particular, a method of installing a horizontal tube or a communication hole at a predetermined height in the reaction zone and extracting it by overflow is preferable because a predetermined amount of liquid can be easily maintained without requiring complicated equipment.

The reaction apparatus used in the present invention is not particularly limited as long as it has a heating function, a stirring function, a gas supply and discharge function, and can continuously react.
In the present invention, a reactor having a liquid phase part having one or a plurality of reaction zones is used. In the reaction apparatus of the present invention, the number of reaction zones is not particularly limited, but is preferably 1 to 30, particularly 1 to 10, and more preferably 1 to 5. Examples of such a reaction apparatus include a raw material supply line 1 and a reaction zone 2 as shown in FIGS. 1 and 2 (2-1, 2-2, 2-3, 2- 4), a liquid phase part comprising at least one reaction zone, comprising a stirring device 3, a gas phase part extraction line 4, a liquid phase part extraction line 5, an air supply line 6, an additional additive solution supply line 7, and the like. And a reaction apparatus (single tank or multi-tank reaction apparatus in which each reaction zone has an independent structure). 3 and 4, raw material supply line 1, reaction zone 2 (2-1, 2-2, 2-3, 2-4, etc.), gas phase part extraction line 4, liquid phase part extraction The liquid phase part comprises a plurality of reaction zones, and the gas phase part communicates with the line 5, the air supply line 6, the additional additive solution supply line 7, the reaction zone partition plate 8, the communication holes 9, and the like. There may also be mentioned a reactor comprising a reactor. Furthermore, a reaction apparatus in which a plurality of reaction apparatuses as shown in FIGS. 3 and 4 are connected as shown in FIG. As described above, as a reaction apparatus used in the present invention, a plurality of reaction zones have independent structures, or the inside is divided into a plurality of reaction zones (liquid phase portions) by a reaction zone partition plate. Those having a structure in which the gas phase portion of each reaction zone communicates are preferably used. A condenser (not shown) is installed in the gas phase part extraction line 4.

  In the reaction apparatus shown in FIGS. 3 and 4, the height of the reaction zone partition plate may be sequentially reduced as shown in FIG. 3, or may be the same as shown in FIG. In such a reaction apparatus, the partition plate has one or more communication holes at arbitrary positions, but in the former case, the partition plate may not have the communication holes. In addition, the reaction liquid is sequentially led to the continuous reaction zone through the communication hole, but in the former case without the communication hole, each reaction zone is sequentially overflowed and led to the final reaction zone. The liquid phase part in each reaction zone may be forcibly stirred and mixed by a stirrer, pump circulation, gas blowing, or the like, or may be stirred or mixed by the flow or convection of the liquid phase part. In addition, the reaction apparatus is heated by passing a heat medium through an external jacket or the like, for example.

  Next, the manufacturing method of this invention is demonstrated using an Example etc. The present invention is not limited to the following examples.

  In the following examples, dimethyl phthalate (hereinafter sometimes abbreviated as DMP) is used as a reaction raw material, and biphenyltetracarboxylic acid tetramethyl ester (hereinafter abbreviated as BPTT), which is a product of an oxidative coupling reaction. Is also manufactured). Here, 3,4,3 ′, 4′-biphenyltetracarboxylic acid tetramethyl ester (hereinafter sometimes abbreviated as s-BPTT) which is an isomer in the oxidative coupling reaction product, The ratio of the amount of 3 ′, 4′-biphenyltetracarboxylic acid tetramethyl ester (hereinafter sometimes abbreviated as a-BPTT) (hereinafter also abbreviated as S / A) and the main product a The catalyst rotation speed with respect to -BPTT (hereinafter sometimes abbreviated as TON) was calculated according to the following calculation formula.

[Example 1]
The reactor is equipped with a raw material supply line, a gas phase part extraction line, and an air supply line as shown in FIG. 1, and when the liquid volume in the reaction zone reaches 100 ml, the reaction liquid is extracted by its own weight due to overflow. An oxidation dimerization reaction was carried out in the following manner using a glass reactor having an internal volume of 100 ml and a liquid phase part extraction line installed at a predetermined position inside.
0.613 mol of DMP, 0.09 mmol of palladium acetate and 0.50 mmol of acetylacetone copper were charged into the reactor (reaction zone), and the air flow was started at a feed rate of 100 ml / min while stirring, and then 2.4. The temperature was raised to 185 ° C at a rate of ° C / min. When the inside of the reactor reaches 185 ° C., it consists of 0.09 mmol of palladium acetate, 0.50 mmol of copper acetylacetone, and 1.1 mmol of acetylacetone (hereinafter sometimes abbreviated as “acach”) per 0.613 mol of DMP. The raw material mixture was continuously supplied at 0.28 ml / min. With the continuous supply of the raw material mixture, the reaction mixture was withdrawn from the liquid phase part withdrawal line due to overflow, and the amount of the reaction mixture in the reaction zone was always kept at 100 ml. Thereafter, while maintaining the temperature inside the reactor at 185 ° C. and the liquid volume in the reaction zone at 100 milliliters, the raw material mixture was continuously supplied to carry out the reaction. The average residence time of the reaction mixture in the reaction zone was 6.0 hours.
After 15 hours, the reaction mixture was sampled, diluted with 10 mM Na phosphate buffer solution and acetonitrile, and the concentration of each component of the reaction mixture was quantified by high performance liquid chromatography. Based on the result, TON of the product a-BPTT was calculated.
The results are shown in Table 1. The TON was 99.

[Example 2]
The oxidation dimerization reaction was carried out in the same manner as in Example 1 except that a 50 ml scale reactor was used instead of the 100 ml scale reactor and the reaction was carried out so that the internal volume was kept constant at 50 ml. went. The reaction was continued for 7 hours. The average residence time of the reaction mixture in the reactor was 3.0 hours.
The results are shown in Table 1. The TON was 59.

Example 3
As an alternative to the raw material mixture consisting of 0.09 mmol of palladium acetate, 0.50 mmol of copper acetylacetone and 1.1 mmol of acetylacetone with respect to 0.613 mol of DMP, 0.09 mmol of palladium acetate with respect to 0.613 mol of DMP, acetylacetone The oxidation dimerization reaction was carried out in the same manner as in Example 1 except that the raw material mixture composed of 0.50 mmol of copper was continuously supplied.
The results are shown in Table 1. The TON was 58.

[Comparative Example 1]
Raw material comprising 0.09 mmol of palladium acetate, 0.50 mmol of copper acetylacetone, and 1.1 mmol of acetylacetone with respect to 0.613 mol of DMP with 0.50 mmol to 0.20 mmol of acetylacetone copper charged in the reactor As in the case of Example 1, except that the raw material mixed solution composed of 0.09 mmol of palladium acetate, 0.20 mmol of acetylacetone copper, and 1.6 mmol of acetylacetone was continuously supplied to 0.613 mol of DMP instead of the mixed solution. Oxidation dimerization reaction was performed. The reaction was continued for 10 hours.
The results are shown in Table 1. The TON was 2.

Example 4
As shown in FIG. 2, a raw material supply line, a gas phase part extraction line, an air supply line, and an additional additive solution supply line are provided, and when the amount of liquid in the reaction zone reaches a certain level, the reaction liquid is caused by its own weight due to overflow. An oxidation dimerization reaction was performed in the following manner using a reaction apparatus in which two glass reactors having a liquid phase extraction line installed at predetermined positions inside the reactor so as to be extracted. The internal volume of the first reactor is 100 milliliters, the internal volume of the second reactor is 50 milliliters, and the reaction mixture taken out (extracted) from the first reactor is the second reactor. Introduced into the reactor.
DMP 0.613 mol, palladium acetate 0.09 mmol, acetylacetone copper 0.50 mmol in the first reactor, DMP 0.306 mmol, palladium acetate 0.045 mmol, acetylacetone copper 0.25 mmol in the second reactor Then, while stirring, air circulation was started at a supply rate of 100 ml / min, and then the temperature was increased to 185 ° C. at a rate of 2.4 ° C./min. When the inside of the reactor reaches 185 ° C., a raw material mixed solution composed of 0.09 mmol of palladium acetate, 0.50 mmol of acetylacetone copper and 0.8 mmol of acetylacetone is added to the first reactor with respect to 0.613 mol of DMP. Continuous feeding was started at 0.42 ml / min. At the same time, a continuous supply of an acetylacetone mixed solution composed of 2.4 mmol of acetylacetone to 0.0613 mol of DMP was started at 0.01 ml / min to the second reactor. Along with continuous supply of the reaction mixture, the reaction mixture is withdrawn from the liquid phase part extraction line due to overflow, the amount of the reaction mixture in the first reaction zone is always 100 ml, the amount of the reaction mixture in the second reaction zone Was always kept at 50 milliliters. Thereafter, while the temperature inside each reactor was kept at 185 ° C., the raw material mixture and the acetylacetone mixture were continuously supplied to carry out an oxidation dimerization reaction. The average residence time of the reaction mixture in the first reactor (reaction zone) is 4 to 4.6 hours, and the average residence time in the second reactor (reaction zone) is 2 to 2.4 hours in total. It was 6-7 hours.
The reaction mixture was sampled every several hours, diluted with 10 mM Na phosphate buffer solution and acetonitrile, and the concentration of each component of the reaction mixture was quantified by high performance liquid chromatography. Based on the result, TON of the product a-BPTT was calculated. The reaction was continued up to 36 hours.
The results are shown in Table 2. The TON was 119.

Example 5
As shown in FIG. 2, a raw material supply line, a gas phase part extraction line, an air supply line, and an additional additive solution supply line are provided, and when the amount of liquid in the reaction zone reaches a certain level, the reaction liquid is caused by its own weight due to overflow. An oxidation dimerization reaction was performed in the following manner using a reaction apparatus in which two glass reactors having a liquid phase extraction line installed at predetermined positions inside the reactor so as to be extracted. The internal volume of the first reactor is 100 milliliters, the internal volume of the second reactor is 50 milliliters, and the reaction mixture taken out (extracted) from the first reactor is the second reactor. Introduced into the reactor.
DMP 0.613 mol, palladium acetate 0.09 mmol, acetylacetone copper 0.50 mmol in the first reactor, DMP 0.306 mmol, palladium acetate 0.045 mmol, acetylacetone copper 0.25 mmol in the second reactor Then, the air flow was started at a supply rate of 100 ml / min while stirring, and then the temperature was raised to 185 ° C. at a rate of 2.0 ° C./min. After reacting at 185 ° C. for 30 minutes, a raw material mixture composed of 0.09 mmol of palladium acetate, 0.50 mmol of acetylacetone copper and 1.6 mmol of acetylacetone was added to 0.613 mol of DMP in the first reactor. Continuous feeding was started at 42 ml / min. At the same time, a continuous supply of an acetylacetone mixed solution consisting of 3.0 mmol of acetylacetone to 0.016 mol / min of DMP was started at 0.01 ml / min. Furthermore, only the second reactor was heated from 185 ° C. to 215 ° C. at a rate of 0.7 ° C./min. Along with the supply of the reaction mixture, the reaction mixture is withdrawn from the liquid phase part extraction line due to overflow, the amount of the reaction mixture in the first reaction zone is always 100 ml, and the amount of the reaction mixture in the second reaction zone is Always kept at 50 ml. Thereafter, while maintaining the temperature inside the first reactor at 185 ° C. and the temperature inside the second reactor at 215 ° C., the supply of the raw material mixture and the acetylacetone mixture was continued to carry out the oxidation dimerization reaction. The average residence time of the reaction mixture in the first reactor (reaction zone) is 4.0 hours, the average residence time in the second reactor (reaction zone) is 2.0 hours, a total of 6.0 hours It became.
After 15 hours, the solution was diluted with 10 mM Na phosphate buffer and acetonitrile, and the concentration of each component of the reaction mixture was quantified by high performance liquid chromatography. Based on the result, TON of the product a-BPTT was calculated.
The results are shown in Table 3. The TON was 145.

Example 6
The reactor is equipped with a raw material supply line, a gas phase part extraction line, and an air supply line as shown in FIG. 1, and when the liquid volume in the reaction zone reaches 100 ml, the reaction liquid is extracted by its own weight due to overflow. An oxidation dimerization reaction was carried out in the following manner using a glass reactor having an internal volume of 100 ml in which a liquid phase part extraction line was installed at a predetermined position inside.
After the reaction of Example 5 was completed, about 110 grams of the reaction mixture in the first reaction zone was charged, and while stirring, air flow was started at a supply rate of 100 ml / min, and then 4.6 ° C./min. The temperature was raised to 220 ° C. at a rate. When the inside of the reactor reached 220 ° C., a raw material mixed solution composed of 0.09 mmol of palladium acetate, 0.50 mmol of acetylacetone copper and 1.8 mmol of acetylacetone was added at 0.42 ml / min with respect to 0.613 mol of DMP. Continuous supply. Along with the supply of the raw material mixture, the reaction mixture was extracted from the liquid phase part extraction line due to overflow, and the amount of the reaction mixture in the reaction zone was always kept at 100 ml. Thereafter, while maintaining the temperature inside the reactor at 220 ° C. and the amount of liquid in the reaction zone at 100 ml, the raw material mixture was continuously supplied to carry out the oxidation dimerization reaction. The average residence time of the reaction mixture in the reaction zone was 4.0 hours.
After 12 hours, the reaction mixture was sampled, diluted with 10 mM Na phosphate buffer solution and acetonitrile, and the concentration of each component of the reaction mixture was quantified by high performance liquid chromatography. Based on the result, TON of the product a-BPTT was calculated.
The results are shown in Table 4. The TON was 144. Table 4 shows the results of the first reaction zone of Example 5 corresponding to the reaction temperature of this example being 185 ° C.

  According to the present invention, a phthalic acid diester is oxidatively coupled with a catalyst containing palladium in the presence of molecular oxygen to form a biphenyltetracarboxylic acid tetraester, particularly 2,3,3 ′, 4′-biphenyltetracarboxylic acid. A production method for continuously producing asymmetric biphenyltetracarboxylic acid tetraesters such as tetraesters, which can be carried out with simple equipment, simple operation, and high productivity, and catalyst efficiency (catalyst rotation speed) ) Can be kept high and a production method that can be carried out more economically can be obtained.

1: Raw material supply line 2 (2-1, 2-2, 2-3, 2-4, etc.): Reaction zone 3: Stirrer 4: Gas phase part extraction line 5: Liquid phase part extraction line 6: For air supply Line 7: Additional solution supply line 8: Reaction zone partition plate 9: Communication hole

Claims (4)

  In a reactor having a liquid phase part having one or a plurality of reaction zones, a catalyst component comprising a phthalic acid diester and at least a palladium compound and a copper salt of 2 to 20 moles relative to the palladium compound in the first reaction zone Phthalic acid continuously or intermittently, molecular oxygen is supplied to the first reaction zone, and a part of the reaction mixture is continuously or intermittently removed from the first reaction zone. A process for producing an asymmetric biphenyltetracarboxylic acid tetraester, characterized by carrying out an oxidative dimerization reaction of a diester.   In a reaction apparatus having a plurality of reaction zones in the liquid phase portion, in the reaction zone after the second reaction zone, a part of the reaction mixture is continuously or intermittently removed from the previous reaction zone and then transferred to the next reaction zone. Introducing in sequence, supplying molecular oxygen to the reaction zone, and performing oxidative dimerization of phthalic acid diester while continuously or intermittently removing a part of the reaction mixture from the last reaction zone The method for producing an asymmetric biphenyltetracarboxylic acid tetraester according to claim 1.   The method for producing an asymmetric biphenyltetracarboxylic acid tetraester according to claim 1 or 2, wherein a β-dicarbonyl compound is further continuously or intermittently supplied as a catalyst component.   In the reaction apparatus having a plurality of reaction zones in the liquid phase part, a catalyst component comprising at least a β-dicarbonyl compound is continuously or intermittently supplied to the reaction zones after the second reaction zone. The method for producing an asymmetric biphenyltetracarboxylic acid tetraester according to any one of claims 1 to 3.

Images