CN113651784A - Synthetic method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride - Google Patents
Synthetic method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride Download PDFInfo
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Abstract
The invention discloses a method for synthesizing 3,3',4,4' -biphenyl tetracarboxylic dianhydride, which takes biphenyl as a starting raw material, firstly performs Friedel-crafts reaction with 3-halogeno propionyl chloride to obtain 5,5' -biindan ketone, then performs oxidation reaction to obtain 3,3',4,4' -biphenyl tetracarboxylic acid, and finally performs dehydration to obtain anhydride to obtain 3,3',4,4' -biphenyl tetracarboxylic dianhydride; the Friedel-crafts reaction is one-pot Friedel-crafts acylation and Friedel-crafts alkylation; the Friedel-crafts reaction is carried out in the presence of a Lewis acid and a cocatalyst of sodium chloride. The method of the invention does not need a high-price and complex catalytic system, and does not need expensive and difficultly available raw material 4,4' -dimethylbiphenyl, thereby greatly reducing the production cost and being suitable for industrial mass production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a synthesis method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride.
Background
3,3',4,4' -biphenyl tetracarboxylic dianhydride (S-BPDA) is an important polyimide monomer, and the wholly aromatic polyimide synthesized by using the monomer as a raw material is one of super-heat-resistant resins with the highest heat-resistant temperature, has the characteristics of high heat resistance, strong mechanical property, strong hydrolysis resistance, high flexibility and the like, and various performance indexes of the wholly aromatic polyimide synthesized by using the 3,3',4,4' -biphenyl tetracarboxylic dianhydride exceed those of the common wholly aromatic polyimide synthesized by using pyromellitic dianhydride (PMDA). The polyimide film manufactured by DuPont and Nippon corporation has higher rigidity, mechanical strength, low shrinkage, low thermal expansion coefficient, and extremely low moisture and other gas permeability, and has promoted the development of high-performance electronic materials.
3,3',4,4' -biphenyltetracarboxylic dianhydride has been regarded as an important monomer of high-performance wholly aromatic polyimide, and research on the preparation process thereof has been paid much attention, and a great deal of intensive research has been conducted by many well-known companies and research institutes at home and abroad.
Currently, most of the methods for synthesizing 3,3',4,4' -biphenyltetracarboxylic dianhydride disclosed in the prior art are coupling methods, including dehalogenation coupling method and oxidation coupling method [ see chinese patent documents CN1041754A, CN1944419A, CN101016284A, CN101659647A, CN110563678A, CN111620769A, etc. ].
Whether dehalogenation coupling or oxidation coupling is adopted, a relatively high-price and relatively complex catalytic system is required, so that the production cost is relatively high, the operation is relatively complex, the requirement on equipment is relatively high, and the method is not environment-friendly.
Chinese patent document CN110818551A discloses a method for synthesizing 3,3',4,4' -biphenyltetracarboxylic acid, which comprises using 4,4' -dimethylbiphenyl as starting material, first performing friedel-crafts acylation reaction with cyclic acid anhydride to obtain an intermediate, and then performing oxidation reaction to obtain 3,3',4,4' -biphenyltetracarboxylic acid.
Although the method does not need a relatively high-price and relatively complex catalytic system, is relatively simple to operate and relatively high in yield, the adopted raw material 4,4' -dimethylbiphenyl is expensive and is not easy to obtain, so that the production cost is still high.
Disclosure of Invention
The present invention has been made to solve the above problems, and an object of the present invention is to provide a method for synthesizing 3,3',4,4' -biphenyltetracarboxylic dianhydride with high reaction yield and product purity and low production cost.
The technical scheme for realizing the purpose of the invention is as follows: a process for synthesizing 3,3',4,4' -biphenyl tetracarboxylic dianhydride includes such steps as Friedel-crafts reaction between biphenyl and 3-halopropionyl chloride to obtain 5,5' -biindane, oxidizing reaction to obtain 3,3',4,4' -biphenyl tetracarboxylic acid, and dewatering to obtain 3,3',4,4' -biphenyl tetracarboxylic dianhydride.
The synthetic route is as follows [ wherein: the 3-halopropionyl chloride is specifically 3-chloropropionyl chloride):
the molar ratio of the biphenyl to the 3-halopropionyl chloride is 1: 2-1: 2.5.
The 3-halogenated propionyl chloride is 3-bromopropionyl chloride or 3-chloropropionyl chloride.
The Friedel-crafts reaction is carried out under the catalysis of Lewis acid; the molar ratio of the biphenyl to the Lewis acid is 1: 3-1: 6, and preferably 1: 4-1: 5.
The Lewis acid is aluminum trichloride or ferric trichloride, and preferably the aluminum trichloride.
The Friedel-crafts reaction is Friedel-crafts acylation and Friedel-crafts alkylation by a one-pot method.
The Friedel-crafts acylation reaction temperature is 55-70 ℃, and the reaction time is 0.5-2 h.
The Friedel-crafts alkylation reaction temperature is 130-170 ℃, and the reaction time is 3-8 h.
The Friedel-crafts reaction is carried out without solvent, otherwise 5,5' -biindanone is not obtained.
The Friedel-crafts reaction is carried out in the presence of a cocatalyst; the molar ratio of the biphenyl to the cocatalyst is 1: 2-1: 2.5; the cocatalyst is sodium chloride.
The applicant found that: the one-pot Friedel-crafts acylation and Friedel-crafts alkylation can be realized only in the presence of Lewis acid, but the reaction yield and the product purity are obviously lower. To this end, the applicant has found through a large number of experiments: by adding the cocatalyst sodium chloride, the reaction yield and the product purity can be greatly improved.
The oxidizing agent adopted in the oxidation reaction is potassium permanganate or concentrated nitric acid; wherein:
when potassium permanganate is used as an oxidant, the molar amount of the oxidant is more than 8 times of that of the 5,5' -biindanone, and is preferably 8-12 times.
The oxidation reaction temperature of potassium permanganate used as an oxidant is 85 ℃ to reflux temperature, and preferably 85-95 ℃.
The oxidation reaction with potassium permanganate as oxidant is carried out in mixed solvent of pyridine and water; the volume ratio of the pyridine to the water is 1: 2-1: 8, and preferably 1: 4-1: 5.
When concentrated nitric acid is used as the oxidant, the molar amount of the oxidant is less than 8 times, preferably 5-8 times of that of the 5,5' -biindanone.
The oxidation reaction temperature of adopting concentrated nitric acid as an oxidant is 165-180 ℃.
The oxidation reaction pressure of using concentrated nitric acid as an oxidant is 0.8-1.0 MPa.
The oxidation reaction using concentrated nitric acid as an oxidant is carried out in water; the amount of the water is 5-10 times of the weight of the 5,5' -biindanone.
The oxidation reaction by concentrated nitric acid is carried out under the catalysis of dimethylaminopyridine; the dosage of the dimethylaminopyridine is 1-10% of the weight of the 5,5' -biindanone.
The dehydration to the anhydride is a conventional method in the art.
The invention has the following positive effects: the method of the invention does not need a high-price and complex catalytic system, and does not need expensive and difficultly available raw material 4,4' -dimethylbiphenyl (the price is 4-5 times of that of biphenyl), thereby greatly reducing the production cost and being suitable for industrial mass production.
Detailed Description
(example 1)
The preparation method of 3,3',4,4' -biphenyltetracarboxylic dianhydride of this example has the following steps:
adding 61.6g (0.4 mol) of biphenyl, 213.3g (1.6 mol) of aluminum trichloride and 46.8g (0.8 mol) of sodium chloride into a reaction device, stirring and cooling to 5 +/-1 ℃, dropwise adding 111.7g (0.88 mol) of 3-chloropropionyl chloride for about 1h, then heating to 60 +/-1 ℃ for reaction for 1h, and then heating to 158 +/-1 ℃ for reaction for 5 h.
After the reaction is finished, cooling to 70 +/-1 ℃, slowly transferring the reacted materials to a mixture of dilute hydrochloric acid and ice, and stirring for crystallization to obtain a crude product; after drying the crude product, it was recrystallized from 180mL of a mixed solvent of ethyl acetate and petroleum ether (V/V = 1: 1), filtered and dried to give 86.0g of 5,5' -biindanone in 82.1% yield and 98.6% HPLC purity.
Adding 78.6g of 5,5' -biindane ketone (0.3 mol) prepared in the step I, 0.6L of pyridine and 2.4L of water into a reaction device, heating to 90 +/-1 ℃, adding 474.0g of potassium permanganate (3.0 mol) for five times, wherein the addition is separated by 1 hour every time, and reacting until the reaction solution is red and does not fade.
After the reaction is finished, a proper amount of ethanol is dripped to quench the residual potassium permanganate, then the mixture is cooled to room temperature and stirred for 2 hours, manganese dioxide solid is removed by filtration, hydrochloric acid is dripped into the filtrate, the pH value is adjusted to 1-2, a large amount of white solid is separated out, the mixture is stirred for 2 hours, filtered and dried under reduced pressure at 80-90 ℃ to obtain white solid powder 3,3',4,4' -biphenyltetracarboxylic acid 85.2g, the yield is 86.1%, and the HPLC purity is 98.9%.
③ adding 66.0g of the 3,3',4,4' -biphenyltetracarboxylic acid (0.2 mol) prepared in the step (c) into a mixed solvent of 85mL of acetic acid and 85mL of acetic anhydride, heating and refluxing for 4h, cooling, filtering, washing, and drying in vacuum at 75-80 ℃ to obtain 47.6g of white crystalline powder 3,3',4,4' -biphenyltetracarboxylic dianhydride, wherein the yield is 81.0%, the content (HPLC) is 99.3%, and the melting point is 299.8 ℃.
Comparative example 1
This comparative example is the reaction of biphenyl with 3-halopropionyl chloride, differing from the procedure (r) of example 1 in that: the sodium chloride as a cocatalyst is not adopted, and the method comprises the following specific steps:
adding 61.6g (0.4 mol) of biphenyl and 213.3g (1.6 mol) of aluminum trichloride into a reaction device, stirring and cooling to 5 +/-1 ℃, dropwise adding 111.7g (0.88 mol) of 3-chloropropionyl chloride for about 1h, then heating to 60 +/-1 ℃ for reaction for 1.5h, and then heating to 158 +/-1 ℃ for reaction for 8 h.
After the reaction is finished, cooling to 70 +/-1 ℃ (aluminum trichloride particles still exist in a reaction system visible to naked eyes), slowly transferring the reacted materials to a mixture of dilute hydrochloric acid and ice, and stirring for crystallization to obtain a crude product; after drying the crude product, it was recrystallized from 180mL of a mixed solvent of ethyl acetate and petroleum ether (V/V = 1: 1), filtered and dried to give 33.5g of 5,5' -biindanone in 32.1% yield and 95.6% HPLC purity.
Comparative example 2
This comparative example is the reaction of biphenyl with 3-halopropionyl chloride, differing from the procedure (r) of example 1 in that: in dichloroethane solvent, as follows:
adding 61.6g (0.4 mol) of biphenyl, 213.3g (1.6 mol) of aluminum trichloride, 46.8g (0.8 mol) of sodium chloride and 380mL of dichloroethane into a reaction device, stirring and cooling to 5 +/-1 ℃, dropwise adding 111.7g (0.88 mol) of 3-chloropropionyl chloride for about 1 hour, and then heating to 80 +/-1 ℃ for reacting for 15 hours.
After the reaction is finished, cooling to 10-15 ℃, slowly transferring the reacted materials to a mixture of dilute hydrochloric acid and ice, stirring, layering, and concentrating a solvent to obtain a crude product; the crude product is sampled and detected by HPLC, and 5,5' -biindanone is not seen.
(example 2)
The preparation method of 3,3',4,4' -biphenyltetracarboxylic dianhydride of this example has the following steps:
adding 61.6g (0.4 mol) of biphenyl, 240.0g (1.8 mol) of aluminum trichloride and 51.5g (0.88 mol) of sodium chloride into a reaction device, stirring and cooling to 0 +/-1 ℃, dropwise adding 111.7g (0.88 mol) of 3-chloropropionyl chloride for about 1h, then heating to 65 +/-1 ℃ for reaction for 1h, and then heating to 162 +/-1 ℃ for reaction for 4 h.
After the reaction is finished, cooling to 62 +/-1 ℃, slowly transferring the reacted materials to a mixture of dilute hydrochloric acid and ice, and stirring for crystallization to obtain a crude product; after drying the crude product, it was recrystallized from 180mL of a mixed solvent of ethyl acetate and petroleum ether (V/V = 4: 5), filtered and dried to give 86.6g of 5,5' -biindanone in 82.6% yield and 98.3% HPLC purity.
Adding 78.6g of 5,5' -biindane ketone (0.3 mol) prepared in the step I, 0.5L of pyridine and 2.5L of water into a reaction device, heating to 92 +/-1 ℃, adding 442.4g of potassium permanganate (2.8 mol) in four times, wherein the addition is separated by 1 hour every time, and reacting until the reaction liquid is red and does not fade.
After the reaction is finished, a proper amount of methanol is dripped to quench the residual potassium permanganate, then the reaction product is cooled to room temperature and stirred for 2 hours, manganese dioxide solid is removed by filtration, hydrochloric acid is dripped into the filtrate, the pH value is adjusted to 1-2, a large amount of white solid is separated out, the reaction product is stirred for 2 hours, filtered and dried under reduced pressure at the temperature of 80-90 ℃, and white solid powder 3,3',4,4' -biphenyltetracarboxylic acid is obtained in an amount of 83.7g, the yield is 84.5%, and the HPLC purity is 98.6%.
③ adding 66.0g of the 3,3',4,4' -biphenyltetracarboxylic acid (0.2 mol) prepared in the step (c) into a mixed solvent of 100mL of toluene and 100mL of acetic anhydride, heating and refluxing for 4h, cooling, filtering, and drying in vacuum at 75-80 ℃ to obtain 46.7g of white crystalline powder of 3,3',4,4' -biphenyltetracarboxylic dianhydride, wherein the yield is 79.4%, the content (HPLC) is 99.4%, and the melting point is 299.7 ℃.
(example 3)
The preparation method of 3,3',4,4' -biphenyltetracarboxylic dianhydride of this example has the following steps:
adding 61.6g (0.4 mol) of biphenyl, 240.0g (1.8 mol) of aluminum trichloride and 46.8g (0.8 mol) of sodium chloride into a reaction device, stirring and cooling to 0 +/-1 ℃, dropwise adding 116.9g (0.92 mol) of 3-chloropropionyl chloride for about 1h, then heating to 65 +/-1 ℃ for reaction for 1h, and then heating to 158 +/-1 ℃ for reaction for 4 h.
After the reaction is finished, cooling to 65 +/-1 ℃, slowly transferring the reacted materials to a mixture of dilute hydrochloric acid and ice, and stirring for crystallization to obtain a crude product; after drying the crude product, it was recrystallized from 180mL of a mixed solvent of ethyl acetate and petroleum ether (V/V = 5: 4), filtered and dried to give 86.0g of 5,5' -biindanone in 82.1% yield and 98.5% HPLC purity.
② adding 78.6g of 5,5' -biindanone (0.3 mol) prepared in the step I into a high-pressure reaction kettle lined with polytetrafluoroethylene, adding 600g of water, 2.3g of dimethylaminopyridine and 138mL (2.0 mol) of 65wt% concentrated nitric acid, sealing the high-pressure reaction kettle, firstly heating to 115 +/-1 ℃, reacting for 2h, then heating to 172 +/-1 ℃, and reacting for 12 h.
After the reaction is finished, cooling to room temperature, discharging, cooling, crystallizing, filtering, washing with water, and drying at 80-90 ℃ under reduced pressure to obtain white solid powder of 3,3',4,4' -biphenyltetracarboxylic acid 81.7g, wherein the yield is 82.5%, and the HPLC purity is 98.3%.
③ adding 66.0g of the 3,3',4,4' -biphenyltetracarboxylic acid (0.2 mol) prepared in the step II into 150mL of acetic anhydride, heating and refluxing for 4h, cooling, filtering, and drying in vacuum at 78-90 ℃ to obtain 46.3g of white crystalline powder 3,3',4,4' -biphenyltetracarboxylic dianhydride, wherein the yield is 78.7%, the content (HPLC) is 99.8%, and the melting point is 300.1 ℃.
(example 4)
The preparation method of 3,3',4,4' -biphenyltetracarboxylic dianhydride of this example has the following steps:
adding 61.6g (0.4 mol) of biphenyl, 240.0g (1.8 mol) of aluminum trichloride and 51.5g (0.88 mol) of sodium chloride into a reaction device, stirring and cooling to 0 +/-1 ℃, dropwise adding 150.8g (0.88 mol) of 3-bromopropionyl chloride for about 1h, then heating to 65 +/-1 ℃ for reaction for 1h, and then heating to 140 +/-1 ℃ for reaction for 4 h.
After the reaction is finished, cooling to 62 +/-1 ℃, slowly transferring the reacted materials to a mixture of dilute hydrochloric acid and ice, and stirring for crystallization to obtain a crude product; after drying the crude product, it was recrystallized from 180mL of a mixed solvent of ethyl acetate and petroleum ether (V/V = 4: 5), filtered and dried to give 89.3g of 5,5' -biindanone in 85.2% yield and 98.6% HPLC purity.
② adding 78.6g of 5,5' -biindane ketone (0.3 mol) prepared in the step I, 0.58L of pyridine and 2.4L of water into a reaction device, heating to 92 +/-1 ℃, adding 474.0g of potassium permanganate (3.0 mol) in six times, wherein the adding time is 50min apart, and reacting until the reaction solution is red and does not fade.
After the reaction is finished, a proper amount of methanol is dripped to quench the residual potassium permanganate, then the reaction product is cooled to room temperature and stirred for 2 hours, manganese dioxide solid is removed by filtration, hydrochloric acid is dripped into the filtrate, the pH value is adjusted to 1-2, a large amount of white solid is separated out, the reaction product is stirred for 2 hours, filtered and dried under reduced pressure at the temperature of 80-90 ℃, and white solid powder 3,3',4,4' -biphenyltetracarboxylic acid is obtained in an amount of 84.1g, the yield is 84.9%, and the HPLC purity is 98.9%.
③ adding 66.0g of the 3,3',4,4' -biphenyltetracarboxylic acid (0.2 mol) prepared in the step (c) into a mixed solvent of 80mL of toluene and 120mL of acetic anhydride, heating and refluxing for 4h, cooling, filtering, and drying in vacuum at 75-80 ℃ to obtain 47.4g of white crystalline powder 3,3',4,4' -biphenyltetracarboxylic dianhydride, wherein the yield is 80.6%, the content (HPLC) is 99.4%, and the melting point is 299.9 ℃.
(example 5)
The preparation method of 3,3',4,4' -biphenyltetracarboxylic dianhydride of this example has the following steps:
adding 184.8g (1.2 mol) of biphenyl, 720.0g (5.4 mol) of aluminum trichloride and 152.1g (2.6 mol) of sodium chloride into a reaction device, stirring, cooling to 0 +/-1 ℃, dropwise adding 330.2g (2.6 mol) of 3-chloropropionyl chloride for about 1h, then heating to 65 +/-1 ℃ for reaction for 1h, and then heating to 162 +/-1 ℃ for reaction for 4 h.
After the reaction is finished, cooling to 62 +/-1 ℃, slowly transferring the reacted materials to a mixture of dilute hydrochloric acid and ice, and stirring for crystallization to obtain a crude product; after drying the crude product, it was recrystallized from 540mL of a mixed solvent of ethyl acetate and petroleum ether (V/V = 1: 1), filtered and dried to give 266.9g of 5,5' -biindanone in 84.9% yield and 98.9% HPLC purity.
Adding 235.8g of 5,5' -biindane ketone (0.9 mol) prepared in the step I, 1.5L of pyridine and 7.5L of water into a reaction device, heating to 92 +/-1 ℃, adding 1.42kg of potassium permanganate (9 mol) in six times, wherein the addition is separated by 1 hour every time, and reacting until the reaction liquid is red and does not fade.
After the reaction is finished, a proper amount of methanol is dripped to quench the residual potassium permanganate, then the reaction product is cooled to room temperature and stirred for 2 hours, manganese dioxide solid is removed by filtration, hydrochloric acid is dripped into the filtrate, the pH value is adjusted to 1-2, a large amount of white solid is separated out, the reaction product is stirred for 2 hours, filtered and dried under reduced pressure at the temperature of 80-90 ℃, and white solid powder 3,3',4,4' -biphenyltetracarboxylic acid 252.9g is obtained, the yield is 85.2%, and the HPLC purity is 98.8%.
Thirdly, 198.0g of the 3,3',4,4' -biphenyltetracarboxylic acid (0.6 mol) prepared in the second step is added into a reaction bottle, the vacuum degree is controlled to be-0.098 MPa, and the temperature is raised to 215 +/-1 ℃ for dehydration reaction.
After the reaction is finished, the temperature is reduced to 135 +/-1 ℃, the reacted materials are added into 680mL of mixed solvent of acetic anhydride and toluene (V/V = 1: 4), stirred and crystallized for 2h, then cooled to room temperature, filtered, and dried in vacuum at 75-80 ℃ to obtain white crystalline powder of 3,3',4,4' -biphenyl tetracarboxylic dianhydride 152.2g, the yield is 86.3%, the content (HPLC) is 99.8%, and the melting point is 300.1 ℃.
Claims (10)
1. A method for synthesizing 3,3',4,4' -biphenyl tetracarboxylic dianhydride is characterized in that: it uses biphenyl as initial raw material, firstly makes Friedel-crafts reaction with 3-halogeno propionyl chloride to obtain 5,5' -biindan ketone, then makes oxidation reaction to obtain 3,3',4,4' -biphenyl tetracarboxylic acid, finally makes dehydration to obtain anhydride so as to obtain 3,3',4,4' -biphenyl tetracarboxylic dianhydride.
2. The method for synthesizing 3,3',4,4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein: the molar ratio of the biphenyl to the 3-halopropionyl chloride is 1: 2-1: 2.5; the 3-halogenated propionyl chloride is 3-bromopropionyl chloride or 3-chloropropionyl chloride.
3. The method for synthesizing 3,3',4,4' -biphenyltetracarboxylic dianhydride according to claim 1 or 2, wherein: the Friedel-crafts reaction is carried out under the catalysis of Lewis acid; the molar ratio of the biphenyl to the Lewis acid is 1: 3-1: 6; the Lewis acid is aluminum trichloride or ferric trichloride.
4. The method for synthesizing 3,3',4,4' -biphenyltetracarboxylic dianhydride according to claim 3, wherein: the molar ratio of the biphenyl to the Lewis acid is 1: 4-1: 5; the Lewis acid is aluminum trichloride.
5. The method for synthesizing 3,3',4,4' -biphenyltetracarboxylic dianhydride according to claim 1 or 2, wherein: the Friedel-crafts reaction is one-pot Friedel-crafts acylation and Friedel-crafts alkylation; the Friedel-crafts acylation reaction temperature is 55-70 ℃, and the reaction time is 0.5-2 h; the Friedel-crafts alkylation reaction temperature is 130-170 ℃, and the reaction time is 3-8 h.
6. The method for synthesizing 3,3',4,4' -biphenyltetracarboxylic dianhydride according to claim 4, wherein: the Friedel-crafts reaction is one-pot Friedel-crafts acylation and Friedel-crafts alkylation; the Friedel-crafts acylation reaction temperature is 55-70 ℃, and the reaction time is 0.5-2 h; the Friedel-crafts alkylation reaction temperature is 130-170 ℃, and the reaction time is 3-8 h.
7. The method for synthesizing 3,3',4,4' -biphenyltetracarboxylic dianhydride according to claim 1 or 2, wherein: the Friedel-crafts reaction is carried out in the presence of a cocatalyst; the molar ratio of the biphenyl to the cocatalyst is 1: 2-1: 2.5; the cocatalyst is sodium chloride.
8. The method for synthesizing 3,3',4,4' -biphenyltetracarboxylic dianhydride according to claim 4, wherein: the Friedel-crafts reaction is carried out in the presence of a cocatalyst; the molar ratio of the biphenyl to the cocatalyst is 1: 2-1: 2.5; the cocatalyst is sodium chloride.
9. The method for synthesizing 3,3',4,4' -biphenyltetracarboxylic dianhydride according to claim 5, wherein: the Friedel-crafts reaction is carried out in the presence of a cocatalyst; the molar ratio of the biphenyl to the cocatalyst is 1: 2-1: 2.5; the cocatalyst is sodium chloride.
10. The method for synthesizing 3,3',4,4' -biphenyltetracarboxylic dianhydride according to claim 6, wherein: the Friedel-crafts reaction is carried out in the presence of a cocatalyst; the molar ratio of the biphenyl to the cocatalyst is 1: 2-1: 2.5; the cocatalyst is sodium chloride.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114605363A (en) * | 2022-03-11 | 2022-06-10 | 大连新阳光材料科技有限公司 | Preparation method of 3,3',4,4' -benzophenone tetracarboxylic dianhydride |
| CN116332889A (en) * | 2023-05-19 | 2023-06-27 | 山东华夏神舟新材料有限公司 | Preparation method of 3,3',4' -benzophenone tetracarboxylic dianhydride |
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| CN116332889B (en) * | 2023-05-19 | 2023-09-19 | 山东华夏神舟新材料有限公司 | Preparation method of 3,3',4' -benzophenone tetracarboxylic dianhydride |
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