CN113651784B - Synthesis method of 3,3', 4' -biphenyl tetracarboxylic dianhydride - Google Patents
Synthesis method of 3,3', 4' -biphenyl tetracarboxylic dianhydride Download PDFInfo
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Abstract
The invention discloses a method for synthesizing 3,3', 4' -biphenyl tetracarboxylic dianhydride, which takes biphenyl as a starting material, firstly reacts with 3-halopropionyl chloride to obtain 5,5' -biindanone, then reacts with 3,3', 4' -biphenyl tetracarboxylic acid through oxidation, and finally dehydrates to form anhydride to obtain 3,3', 4' -biphenyl tetracarboxylic dianhydride; the Friedel-crafts reaction is one-pot method Friedel-crafts acylation and Friedel-crafts alkylation; the friedel-crafts reaction is carried out in the presence of a lewis acid and a promoter sodium chloride. The method of the invention does not need a relatively high-priced and relatively complex catalytic system, and does not need a raw material 4,4' -dimethylbiphenyl which is expensive and not easy to obtain, 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' -biphenyl tetracarboxylic dianhydride.
Background
The 3,3', 4' -biphenyl tetracarboxylic dianhydride (S-BPDA) is an important polyimide monomer, and the wholly aromatic polyimide synthesized by taking the 3,3', 4' -biphenyl tetracarboxylic dianhydride as a raw material is one of the super heat-resistant resins with the highest heat resistance 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 utilizing the 3,3', 4' -biphenyl tetracarboxylic dianhydride are all higher than those of the common wholly aromatic polyimide synthesized by utilizing pyromellitic dianhydride (PMDA). The commercial polyimide film made from the polyimide film has the characteristics of higher rigidity strength, mechanical strength, low shrinkage, low thermal expansion coefficient, extremely low permeability of moisture and other gases and the like, and well promotes the development of high-performance electronic materials.
3,3', 4' -biphenyl tetracarboxylic dianhydride is taken as an important monomer of the full-aromatic polyimide with high performance, the preparation process research of the full-aromatic polyimide is paid attention to, and a great deal of intensive researches are carried out by a plurality of famous companies and research institutions at home and abroad.
Currently, most of the synthesis methods of 3,3', 4' -biphenyl tetracarboxylic dianhydride disclosed in the prior art are coupling methods, including dehalogenation coupling methods and oxidative coupling methods [ see chinese patent document CN1041754A, CN1944419A, CN101016284A, CN101659647A, CN110563678A, CN111620769a, etc. ].
Whether dehalogenation coupling or oxidation coupling, a relatively complex catalytic system with relatively high price is needed, so that the production cost is relatively high, the operation is relatively complex, the equipment requirement is relatively high, and the method is not friendly to the environment.
Chinese patent document CN110818551A discloses a method for synthesizing 3,3', 4' -biphenyl tetracarboxylic acid, which takes 4,4' -dimethylbiphenyl as a starting material, carries out Friedel-crafts acylation reaction with cyclic anhydride to obtain an intermediate, and then carries out oxidation reaction to obtain the 3,3', 4' -biphenyl tetracarboxylic acid.
The method has the advantages of no need of a complex catalytic system with higher price, simpler operation and higher yield, but the adopted raw material 4,4' -dimethylbiphenyl is expensive and not easy to obtain, thereby leading to higher production cost.
Disclosure of Invention
The invention aims to solve the problems and provide a synthesis method of 3,3', 4' -biphenyl tetracarboxylic dianhydride, which has high reaction yield and product purity and low production cost.
The technical scheme for realizing the aim of the invention is as follows: a process for synthesizing 3,3', 4' -diphenyl tetracarboxylic dianhydride includes such steps as Friedel-crafts reaction of diphenyl with 3-halopropionyl chloride to obtain 5,5' -biindanone, oxidizing reaction to obtain 3,3', 4' -diphenyl tetracarboxylic acid, and dewatering to obtain 3,3', 4' -diphenyl tetracarboxylic dianhydride.
The synthetic route is as follows [ wherein: the 3-halopropionyl chloride is specifically 3-chloropropionyl chloride:
the mol ratio of the biphenyl to the 3-halopropionyl chloride is 1:2-1:2.5.
The 3-halogenopropionyl 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, preferably 1:4-1:5.
The lewis acid is aluminum trichloride or ferric trichloride, preferably aluminum trichloride.
The Friedel-crafts reaction is one-pot method 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.
The friedel-crafts reaction is carried out in the absence of a solvent, otherwise 5,5' -biindanone cannot be obtained.
The friedel-crafts reaction is carried out in the presence of a cocatalyst; the mol ratio of the biphenyl to the cocatalyst is 1:2-1:2.5; the cocatalyst is sodium chloride.
The applicant found that: although the one-pot friedel-crafts acylation and friedel-crafts alkylation can be realized only in the presence of lewis acid, the reaction yield and the product purity are obviously lower. For this purpose, the applicant has found through a number of experiments that: by adding the promoter sodium chloride, the reaction yield and the product purity can be greatly improved.
The oxidant adopted in the oxidation reaction is potassium permanganate or concentrated nitric acid; wherein:
when potassium permanganate is used as the oxidizing agent, the molar amount of the oxidizing agent is 8 times or more, preferably 8 to 12 times, the molar amount of the 5,5' -biindanone.
The oxidation reaction temperature using potassium permanganate as the oxidizing agent is 85 ℃ to the reflux temperature, preferably 85 to 95 ℃.
The oxidation reaction using potassium permanganate as oxidant is carried out in pyridine + water mixed solvent; the volume ratio of the pyridine to the water is 1:2-1:8, preferably 1:4-1:5.
When concentrated nitric acid is used as the oxidizing agent, the molar amount of the oxidizing agent is 8 times or less, preferably 5 to 8 times, the molar amount of the 5,5' -biindanone.
The oxidation reaction temperature of the concentrated nitric acid serving as an oxidant is 165-180 ℃.
The oxidation reaction pressure of the concentrated nitric acid used as the oxidant is 0.8-1.0 MPa.
The oxidation reaction using concentrated nitric acid as the oxidant is carried out in water; the water is used in an amount of 5 to 10 times the weight of the 5,5' -biindanone.
The oxidation reaction with 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 process in the art.
The invention has the positive effects that: the method of the invention does not need a relatively high-price and relatively complex catalytic system, and does not need a raw material 4,4' -dimethylbiphenyl (the price of the raw material is 4-5 times of that of the biphenyl) which is expensive and not easy to obtain, thereby greatly reducing the production cost and being suitable for industrial mass production.
Detailed Description
Example 1
The preparation method of the 3,3', 4' -biphenyl tetracarboxylic dianhydride of the present example comprises the following steps:
(1) 61.6g (0.4 mol) of biphenyl, 213.3g (1.6 mol) of aluminum trichloride and 46.8g (0.8 mol) of sodium chloride are added into the reaction device, the temperature is reduced to 5+/-1 ℃ by stirring, 111.7g (0.88 mol) of 3-chloropropionyl chloride is added dropwise, the dropwise is completed for about 1 hour, then the temperature is firstly increased to 60+/-1 ℃ for reaction for 1 hour, and then the temperature is increased to 158+/-1 ℃ for reaction for 5 hours.
After the reaction is finished, cooling to 70+/-1 ℃, slowly transferring the reacted material into 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 with a yield of 82.1% and an HPLC purity of 98.6%.
(2) 78.6g of 5,5' -biindanone (0.3 mol) obtained in the step (1), 0.6L of pyridine and 2.4L of water are added into a reaction device, the mixture is heated to 90+/-1 ℃, 474.0g (3.0 mol) of potassium permanganate is added into the mixture in five times, and each time is separated by 1h, and the mixture reacts until the reaction liquid is red and does not fade.
After the reaction is finished, a proper amount of ethanol is added dropwise to quench the rest potassium permanganate, then the mixture is cooled to room temperature, stirred for 2 hours, manganese dioxide solid is removed by filtration, hydrochloric acid is added dropwise to the filtrate, the pH value is regulated to 1-2, a large amount of white solid is separated out, stirred for 2 hours, filtered and dried under reduced pressure at 80-90 ℃ to obtain 85.2g of white solid powder 3,3', 4' -biphenyl tetracarboxylic acid, the yield is 86.1%, and the HPLC purity is 98.9%.
(3) 66.0g of 3,3', 4' -biphenyltetracarboxylic acid (0.2 mol) obtained in the step (2) was added to a mixed solvent of 85mL of acetic acid and 85mL of acetic anhydride, heated and refluxed for 4 hours, cooled, filtered, washed, and vacuum-dried at 75-80 ℃ to obtain 47.6g of white crystalline powder of 3,3', 4' -biphenyltetracarboxylic dianhydride, with a yield of 81.0%, a content (HPLC) of 99.3% and a melting point of 299.8 ℃.
Comparative example 1
This comparative example is a reaction of biphenyl with 3-halopropionyl chloride, which differs from step (1) of example 1 in that: sodium chloride, a promoter, was not used, as follows:
(1) 61.6g (0.4 mol) of biphenyl and 213.3g (1.6 mol) of aluminum trichloride are added into the reaction device, the temperature is reduced to 5+/-1 ℃ by stirring, 111.7g (0.88 mol) of 3-chloropropionyl chloride is added dropwise, the dripping is completed for about 1 hour, then the temperature is firstly increased to 60+/-1 ℃ for reaction for 1.5 hours, and then the temperature is increased to 158+/-1 ℃ for reaction for 8 hours.
After the reaction is finished, cooling to 70+/-1 ℃ (aluminum trichloride particles still exist in a macroscopic reaction system), slowly transferring the reacted material into 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 a yield of 32.1% and an HPLC purity of 95.6%.
Comparative example 2
This comparative example is a reaction of biphenyl with 3-halopropionyl chloride, which differs from step (1) of example 1 in that: in dichloroethane solvent, specifically as follows:
(1) 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 are added into the reaction device, the temperature is reduced to 5+/-1 ℃ by stirring, 111.7g (0.88 mol) of 3-chloropropionyl chloride is added dropwise, the dropwise is completed for about 1 hour, and then the temperature is increased to 80+/-1 ℃ for reaction for 15 hours.
After the reaction is finished, cooling to 10-15 ℃, slowly transferring the reacted material into a mixture of dilute hydrochloric acid and ice, stirring, layering and concentrating the solvent to obtain a crude product; the crude sample was checked by HPLC and no 5,5' -biindanone was found.
Example 2
The preparation method of the 3,3', 4' -biphenyl tetracarboxylic dianhydride of the present example comprises the following steps:
(1) 61.6g (0.4 mol) of biphenyl, 240.0g (1.8 mol) of aluminum trichloride and 51.5g (0.88 mol) of sodium chloride are added into the reaction device, the temperature is reduced to 0+/-1 ℃ by stirring, 111.7g (0.88 mol) of 3-chloropropionyl chloride is added dropwise, the dropwise is completed for about 1 hour, then the temperature is firstly increased to 65+/-1 ℃ for reaction for 1 hour, and then the temperature is increased to 162+/-1 ℃ for reaction for 4 hours.
After the reaction is finished, cooling to 62+/-1 ℃, slowly transferring the reacted material into 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 with a yield of 82.6% and an HPLC purity of 98.3%.
(2) 78.6g of 5,5' -biindanone (0.3 mol) obtained in the step (1), 0.5L of pyridine and 2.5L of water are added into a reaction device, the mixture is heated to 92+/-1 ℃, 442.4g (2.8 mol) of potassium permanganate is added in four times, each time is separated by 1 hour, and the reaction is carried out until the reaction liquid is red and does not fade.
After the reaction is finished, a proper amount of methanol is added dropwise to quench the residual potassium permanganate, then the mixture is cooled to room temperature, stirred for 2 hours, manganese dioxide solid is removed by filtration, hydrochloric acid is added dropwise to the filtrate, the pH value is regulated to 1-2, a large amount of white solid is separated out, stirred for 2 hours, filtered and dried under reduced pressure at 80-90 ℃ to obtain 83.7g of white solid powder 3,3', 4' -biphenyl tetracarboxylic acid, the yield is 84.5%, and the HPLC purity is 98.6%.
(3) 66.0g of 3,3', 4' -biphenyltetracarboxylic acid (0.2 mol) obtained in the step (2) was added to a mixed solvent of 100mL of toluene and 100mL of acetic anhydride, heated and refluxed for 4 hours, cooled, filtered, and vacuum-dried at 75-80 ℃ to obtain 46.7g of white crystalline powder of 3,3', 4' -biphenyltetracarboxylic dianhydride, with a yield of 79.4%, a content (HPLC) of 99.4% and a melting point of 299.7 ℃.
Example 3
The preparation method of the 3,3', 4' -biphenyl tetracarboxylic dianhydride of the present example comprises the following steps:
(1) 61.6g (0.4 mol) of biphenyl, 240.0g (1.8 mol) of aluminum trichloride and 46.8g (0.8 mol) of sodium chloride are added into the reaction device, the temperature is reduced to 0+/-1 ℃ by stirring, 116.9g (0.92 mol) of 3-chloropropionyl chloride is added dropwise, the dropwise is completed for about 1 hour, then the temperature is firstly increased to 65+/-1 ℃ for reaction for 1 hour, and then the temperature is increased to 158+/-1 ℃ for reaction for 4 hours.
After the reaction is finished, cooling to 65+/-1 ℃, slowly transferring the reacted material into 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 a yield of 82.1% and an HPLC purity of 98.5%.
(2) 78.6g of 5,5' -biindanone (0.3 mol) obtained in the step (1) is added into a high-pressure reaction kettle lined with polytetrafluoroethylene, 600g of water, 2.3g of dimethylaminopyridine and 138mL (2.0 mol) of 65wt% concentrated nitric acid are added, the high-pressure reaction kettle is closed, the temperature is firstly increased to 115+/-1 ℃ for 2 hours, and then the temperature is increased to 172+/-1 ℃ for 12 hours for reaction.
After the reaction is finished, cooling to room temperature, discharging, cooling for crystallization, filtering, washing with water, and drying at 80-90 ℃ under reduced pressure to obtain 81.7g of white solid powder 3,3', 4' -biphenyltetracarboxylic acid, wherein the yield is 82.5%, and the HPLC purity is 98.3%.
(3) 66.0g of 3,3', 4' -biphenyltetracarboxylic acid (0.2 mol) obtained in the step (2) was added to 150mL of acetic anhydride, heated and refluxed for 4 hours, cooled, filtered, and vacuum-dried at 78-90℃to obtain 46.3g of 3,3', 4' -biphenyltetracarboxylic dianhydride as a white crystalline powder, the yield was 78.7%, the content (HPLC) was 99.8%, and the melting point was 300.1 ℃.
Example 4
The preparation method of the 3,3', 4' -biphenyl tetracarboxylic dianhydride of the present example comprises the following steps:
(1) 61.6g (0.4 mol) of biphenyl, 240.0g (1.8 mol) of aluminum trichloride and 51.5g (0.88 mol) of sodium chloride are added into the reaction device, the temperature is reduced to 0+/-1 ℃ by stirring, 150.8g (0.88 mol) of 3-bromopropionyl chloride is added dropwise, the dropwise is completed for about 1 hour, then the temperature is raised to 65+/-1 ℃ for reaction for 1 hour, and then the temperature is raised to 140+/-1 ℃ for reaction for 4 hours.
After the reaction is finished, cooling to 62+/-1 ℃, slowly transferring the reacted material into 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 with a yield of 85.2% and an HPLC purity of 98.6%.
(2) 78.6g of 5,5' -biindanone (0.3 mol) obtained in the step (1), 0.58L of pyridine and 2.4L of water are added into a reaction device, the mixture is heated to 92+/-1 ℃, 474.0g (3.0 mol) of potassium permanganate is added for six times, and the intervals between the two additions are 50 minutes, so that the reaction liquid is red and does not fade.
After the reaction is finished, a proper amount of methanol is added dropwise to quench the residual potassium permanganate, then the mixture is cooled to room temperature, stirred for 2 hours, manganese dioxide solid is removed by filtration, hydrochloric acid is added dropwise to the filtrate, the pH value is regulated to 1-2, a large amount of white solid is separated out, stirred for 2 hours, filtered and dried under reduced pressure at 80-90 ℃ to obtain 84.1g of white solid powder 3,3', 4' -biphenyl tetracarboxylic acid, the yield is 84.9%, and the HPLC purity is 98.9%.
(3) 66.0g of 3,3', 4' -biphenyltetracarboxylic acid (0.2 mol) obtained in the step (2) was added to a mixed solvent of 80mL of toluene and 120mL of acetic anhydride, heated and refluxed for 4 hours, cooled, filtered, and vacuum-dried at 75-80 ℃ to obtain 47.4g of white crystalline powder of 3,3', 4' -biphenyltetracarboxylic dianhydride, with a yield of 80.6%, a content (HPLC) of 99.4% and a melting point of 299.9 ℃.
Example 5
The preparation method of the 3,3', 4' -biphenyl tetracarboxylic dianhydride of the present example comprises the following steps:
(1) 184.8g (1.2 mol) of biphenyl, 720.0g (5.4 mol) of aluminum trichloride and 152.1g (2.6 mol) of sodium chloride are added into the reaction device, the temperature is reduced to 0+/-1 ℃ by stirring, 330.2g (2.6 mol) of 3-chloropropionyl chloride is added dropwise, the dropwise is completed for about 1 hour, then the temperature is firstly increased to 65+/-1 ℃ for reaction for 1 hour, and then the temperature is increased to 162+/-1 ℃ for reaction for 4 hours.
After the reaction is finished, cooling to 62+/-1 ℃, slowly transferring the reacted material into 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 with a yield of 84.9% and an HPLC purity of 98.9%.
(2) 235.8g of 5,5' -biindanone (0.9 mol) obtained in the step (1), 1.5L of pyridine and 7.5L of water are added into a reaction device, the mixture is heated to 92+/-1 ℃, 1.42kg (9 mol) of potassium permanganate is added into the mixture for six times, and each time is separated by 1h, and the mixture reacts until the reaction liquid is red and does not fade.
After the reaction is finished, a proper amount of methanol is added dropwise to quench the residual potassium permanganate, then the mixture is cooled to room temperature, stirred for 2 hours, manganese dioxide solid is removed by filtration, hydrochloric acid is added dropwise to the filtrate, the pH value is regulated to 1-2, a large amount of white solid is separated out, stirred for 2 hours, filtered and dried under reduced pressure at 80-90 ℃ to obtain 252.9g of white solid powder 3,3', 4' -biphenyl tetracarboxylic acid, the yield is 85.2%, and the HPLC purity is 98.8%.
(3) 198.0g of 3,3', 4' -biphenyltetracarboxylic acid (0.6 mol) obtained in the step (2) is added into a reaction flask, and the dehydration reaction is carried out by heating to 215+/-1 ℃ under the vacuum degree of-0.098 MPa.
After the reaction, the temperature is reduced to 135+/-1 ℃, the reacted material is added into 680mL of mixed solvent of acetic anhydride and toluene (V/V=1:4), stirred and crystallized for 2 hours, then cooled to room temperature, filtered and dried in vacuum at 75-80 ℃ to obtain 152.2g of white crystalline powder 3,3', 4' -biphenyl tetracarboxylic dianhydride, the yield is 86.3%, the content (HPLC) is 99.8%, and the melting point is 300.1 ℃.
Claims (6)
1. A method for synthesizing 3,3', 4' -biphenyl tetracarboxylic dianhydride is characterized in that: biphenyl is taken as a starting material, firstly, the biphenyl and 3-halopropionyl chloride undergo Friedel-crafts reaction to obtain 5,5' -biindanone, then 3,3', 4' -biphenyl tetracarboxylic acid is obtained through oxidation reaction, and finally, 3', 4' -biphenyl tetracarboxylic dianhydride is obtained through dehydration to obtain anhydride;
the Friedel-crafts reaction is one-pot method 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;
the friedel-crafts reaction is carried out under the catalysis of lewis acid; the Lewis acid is aluminum trichloride or ferric trichloride;
the friedel-crafts reaction is carried out in the presence of a cocatalyst; the cocatalyst is sodium chloride.
2. The method for synthesizing 3,3', 4' -biphenyltetracarboxylic dianhydride according to claim 1, wherein: the mol ratio of the biphenyl to the 3-halopropionyl chloride is 1:2-1:2.5; the 3-halogenopropionyl chloride is 3-bromopropionyl chloride or 3-chloropropionyl chloride.
3. The method for synthesizing 3,3', 4' -biphenyltetracarboxylic dianhydride according to claim 1 or 2, characterized in that: the molar ratio of the biphenyl to the Lewis acid is 1:3-1:6.
4. The method for synthesizing 3,3', 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' -biphenyltetracarboxylic dianhydride according to claim 1 or 2, characterized in that: the mol ratio of the biphenyl to the cocatalyst is 1:2-1:2.5.
6. The method for synthesizing 3,3', 4' -biphenyltetracarboxylic dianhydride according to claim 4, wherein: the mol ratio of the biphenyl to the cocatalyst is 1:2-1:2.5.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1403434A (en) * | 2002-09-20 | 2003-03-19 | 王明春 | Prepn process of 5-chloro-2,3-dihydro-1-indenone |
| WO2006001443A1 (en) * | 2004-06-28 | 2006-01-05 | Mitsubishi Chemical Corporation | Biphenyltetracarboxylic acid dianhydride and process for producing the same, and polyimide formed from the same and process for producing the same |
| JP2009079008A (en) * | 2007-09-26 | 2009-04-16 | Tamio Hayashi | Method for producing biphenyl-3, 4, 3', 4'-tetracarboxylic acid |
| CN101659647B (en) * | 2008-08-26 | 2011-10-12 | 比亚迪股份有限公司 | Method for preparing diphenyl tetracarboxylic dianhydride |
| CN102040573A (en) * | 2009-10-17 | 2011-05-04 | 比亚迪股份有限公司 | Biphenyltetracarboxylic di-anhydride, preparation method thereof and polymide synthesized by using same |
| CN103012086B (en) * | 2011-09-26 | 2015-11-18 | 江西阿尔法高科药业有限公司 | One prepares the method for 2,3-bihydrogen-1-indenone and derivative thereof |
| CN106518820A (en) * | 2016-10-07 | 2017-03-22 | 常州创索新材料科技有限公司 | Synthesis method of 3,3',4,4'-biphenyltetracarboxylic anhydride |
| CN110563678A (en) * | 2019-10-15 | 2019-12-13 | 上海固创化工新材料有限公司 | Preparation method of 3,3',4,4' -biphenyl tetracarboxylic dianhydride |
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