A method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride

Abstract

The application provides a method for preparing 3,3',4,4'-biphenyl tetracarboxylic dianhydride, which comprises the following steps: adding biphenyl, dianhydride and a promoter into an ionic liquid, adding a part of a catalyst, continuing to react after adding the remaining catalyst and increasing the temperature after the complete reaction of an intermediate at a low temperature, filtering the reaction solution, adding an oxidant into the filtrate and reacting after increasing the temperature, adding the reaction solution into ice water after the complete reaction, filtering after stirring, and obtaining 3,3',4,4'-biphenyl tetracarboxylic dianhydride after water washing the filter cake and stepwise drying in a vacuum drying box. The present application adopts a Fuch reaction instead of a coupling reaction, raw materials are easy to purchase, a one-pot reaction is used, a process is simple and controllable, the yield is high, and the method is suitable for mass production.

Description

Technical Field

[0001] This invention belongs to the field of organic chemical synthesis technology, and in particular relates to a method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride. Background Technology

[0002] Polyimide is polymerized from diamine and dianhydride monomers, with dianhydride monomers being one of the key raw materials for its preparation. The structure of the dianhydride monomer determines the different mechanical properties of polyimide, such as high-temperature resistance, making it suitable for thermal insulation layers; high thermal stability, enabling the production of high-efficiency and high-yield solar cells, and its use as a substrate in thin-film a-Si and CIGS photovoltaic applications; thermoplastic and thermosetting properties, allowing it to replace materials such as glass and metals; and flexibility and good dimensional stability, making it suitable for insulating circuit boards, high-temperature powder coatings, and transformers.

[0003] Currently, the main reported methods for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride are:

[0004] 1. Phthalic anhydride method

[0005] (1) It was obtained by four steps of reaction: esterification, coupling, hydrolysis and anhydride formation, using 4-chlorophthalic anhydride as raw material. The overall yield of the route was 61.9%.

[0006] (2) It was obtained by coupling, hydrolysis and dehydration of sodium 4-chlorophthalic anhydride and sodium phthalate as raw materials, with a yield of 87%.

[0007] 2. o-Xylene method

[0008] BPDA was obtained from 4-chloro / bromo-o-xylene via coupling, oxidation, and dehydration, with an overall yield of 72% in the three-step reaction.

[0009] 3. Other methods

[0010] (1) Patent RU2682170: The product is obtained by coupling, hydrolysis and dehydration of dipropyl iodide or methyl iodide as raw material, with a yield of 37%.

[0011] (2) Patent CN113461646: discloses a method for obtaining BPDA by coupling hydrolysis and dehydration of N-substituted phthalimide as raw material.

[0012] Existing synthetic methods for 3,3',4,4'-biphenyltetracarboxylic dianhydride are lengthy and cannot be combined, requiring multiple separation operations and purification at each step, resulting in low yields. Summary of the Invention

[0013] In view of this, the present invention aims to provide a method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride, in order to solve the problems of complex reaction and low yield.

[0014] To achieve the above objectives, the technical solution of the present invention is implemented as follows:

[0015] A method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride includes the following steps: adding biphenyl, dianhydride and co-catalyst to an ionic liquid, adding a portion of the catalyst, and after the reaction is complete at a low temperature, adding the remaining catalyst and continuing the reaction at a higher temperature. After the intermediate has reacted completely, filtering the reaction solution, adding an oxidant to the filtrate and heating the reaction solution, and after the reaction is complete, adding the reaction solution to ice water, stirring and filtering, washing the filter cake with water and then drying it stepwise in a vacuum drying oven to obtain 3,3',4,4'-biphenyltetracarboxylic dianhydride.

[0016] Furthermore, the molar ratio of biphenyl to dianhydride is 1:(2-2.05), and the mass ratio of biphenyl, ionic liquid, catalyst and co-catalyst is 1:(4-10):(1.5-6):(0.5%-5%).

[0017] Furthermore, the dianhydride is one of succinic anhydride, glutaric anhydride, maleic anhydride, and adipic anhydride.

[0018] Furthermore, the ionic liquid is one or two of the following: 1-ethyl-3-methylimidazolium aluminum chloride, 1-ethyl-3-methylimidazolium methyl sulfate, chloro-1-butyl-3-methylimidazolium, 1-butyl-3-methylimidazolium hexafluoroantimonate, bromo-1-butyl-3-methylimidazolium, 1-butyl-3-methylimidazolium aluminum chloride, 1-butylpyridine aluminochlorochloride, trimethylamine aluminochloride, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-ethyl-3-methylimidazolium trifluoroacetate, 1-ethyl-3-methylimidazolium ferric chloride, 1-butyl-3-methylimidazolium bromide aluminum chloride, 1-pentyl-3-methylimidazolium tetrafluoroborate, 2-methylimidazolium quaternary phosphonium salt, 1-methyl-3-benzylimidazolium hydrothioate, and triethylamine aluminochloride.

[0019] Furthermore, the catalyst is one or more of the following: anhydrous aluminum trichloride ultrafine powder, silica gel aluminum trichloride, solid superacid, trifluoromethanesulfonic acid series, polyphosphoric acid and its supported form, or titanium tetrachloride, phosphotungstic acid, heteropolyacid, and ion exchange resin.

[0020] Furthermore, the solid superacid is SO4. 2- Al2O3, SO4 2- / TiO2 or SO4 2- / ZrO2.

[0021] Furthermore, the trifluoromethanesulfonic acid series includes zinc trifluoromethanesulfonate, bismuth trifluoromethanesulfonate, or aluminum trifluoromethanesulfonate.

[0022] Furthermore, the co-catalyst is one or more of the following: mercaptoacetic acid, thiol, citric acid, phytic acid, montmorillonite, dimethyl aluminum chloride, diisobutyl aluminum chloride, methyl aluminum chloride, and molybdate hydrate.

[0023] Furthermore, the oxidant is one or more of potassium permanganate, methyl ethyl ketone peroxide, tert-butyl peroxide, air, peracetic acid, nitric acid, and sulfuric acid.

[0024] Furthermore, the reaction temperature of the low-temperature reaction is -10℃ to 10℃, and the reaction temperature of the heating reaction is 50℃ to 140℃.

[0025] The reaction formula involved in this invention is as follows:

[0026]

[0027] Compared with existing technologies, the method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride described in this invention has the following advantages: it uses the Friedel-Crafts reaction instead of the coupling reaction, the raw materials are readily available, the route is long but can be carried out in a one-pot process, the process is simple and controllable, the yield is high, and it is suitable for mass production. Attached Figure Description

[0028] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0029] Figure 1 This is an HPLC chromatogram of 3,3',4,4'-biphenyltetracarboxylic dianhydride obtained in Example 1 of the present invention. Detailed Implementation

[0030] It should be noted that, unless otherwise specified, the embodiments and features described in the embodiments of this invention can be combined with each other. Unless otherwise defined, the technical terms used in the following embodiments have the same meaning as commonly understood by those skilled in the art to which this invention pertains. Unless otherwise specified, the experimental reagents used in the following embodiments are conventional biochemical reagents; and the experimental methods described are conventional methods.

[0031] The present invention will now be described in detail with reference to the accompanying drawings and embodiments.

[0032] Option 1 uses succinic anhydride as a raw material.

[0033] The reaction formula for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride from succinic anhydride is as follows:

[0034]

[0035] Example 1

[0036] 154g of biphenyl, 202g of succinic anhydride, 4860g of 1-ethyl-3-methylimidazolium aluminum chloride, and 3g of mercaptoacetic acid were mechanically stirred and cooled to below 10°C. 150g of anhydrous aluminum trichloride ultrafine powder was added, and the mixture was stirred at this temperature for 3 hours. Then, 150g of anhydrous aluminum trichloride ultrafine powder was added, and the temperature was raised to 100°C for 5 hours. After filtration, 1140g of 20% peracetic acid was added dropwise to the filtrate at 50°C, maintaining the reaction temperature below 30°C during the addition process until the reactants were completely reacted. The reaction solution was then added to ice water to crystallize, filtered, and the filter cake was washed with water and dried in a vacuum drying oven at 80°C for 2 hours. The temperature was then raised to 140°C for 3 hours, and finally raised to 220°C for 4 hours to obtain 273g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, an off-white powder with a liquid phase purity of 99.98% and a yield of 92.86%.

[0037] Example 2

[0038] 154g of biphenyl, 202g of succinic anhydride, 3600g of 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, and 5g of dimethylaluminum chloride were mixed and cooled to below 10°C under mechanical stirring. 182g of aluminum trifluoromethanesulfonate was added, and the mixture was stirred at this temperature for 5 hours. Then, another 182g of aluminum trifluoromethanesulfonate was added, and the mixture was heated to 90°C and reacted for 7 hours. The mixture was then filtered. 1350g of 20% peracetic acid was added dropwise to the filtrate at 60°C until the reactants were completely reacted. The reaction solution was then added to ice water to crystallize, filtered, and the filter cake was washed with water and dried in a vacuum drying oven at 80°C for 2 hours. The temperature was then raised to 140°C and dried for 3 hours, and finally raised to 220°C and dried for 4 hours to obtain 252g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, an off-white powder with a liquid phase purity of 99.91% and a yield of 85.71%.

[0039] Example 3

[0040] 154g of biphenyl, 205g of succinic anhydride, 1420g of 1-butyl-3-methylimidazolium hexafluoroantimonate, and 4.6g of methylaluminum chloride were mixed and cooled to below 10°C under mechanical stirring. 140g of polyphosphoric acid was added, and the mixture was stirred at this temperature for 5 hours. Then, 140g of polyphosphoric acid was added, and the temperature was raised to 90°C. After reacting for 7 hours, the mixture was filtered. 1400g of 20% peracetic acid was added dropwise to the filtrate at 60°C until the reactants reacted completely. The reaction solution was added to ice water to crystallize, filtered, and the filter cake was washed with water and dried in a vacuum drying oven at 80°C for 2 hours. Then, the temperature was raised to 140°C and dried for 3 hours. Finally, the temperature was raised to 220°C and dried for 4 hours to obtain 265g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, which was an off-white powder with a liquid phase purity of 99.93% and a yield of 90.14%.

[0041] Option 2 uses maleic anhydride as a raw material.

[0042] The reaction formula for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride from maleic anhydride is as follows:

[0043]

[0044] Example 4

[0045] 154g of biphenyl, 206g of maleic anhydride, 4300g of 1-ethyl-3-methylimidazolium aluminum chloride, and 3g of mercaptoacetic acid were mixed and cooled to below 10°C under mechanical stirring. 150g of anhydrous aluminum trichloride ultrafine powder was added, and the mixture was stirred at this temperature for 3 hours. Then, 150g of anhydrous aluminum trichloride ultrafine powder was added, and the temperature was raised to 105°C. After reacting for 5 hours, the mixture was filtered. 1100g of 20% peracetic acid was added dropwise to the filtrate at 30°C, maintaining the reaction temperature below 30°C during the addition process until the reactants were completely reacted. The reaction solution was then added to ice water to crystallize, filtered, and the filter cake was washed with water and dried in a vacuum drying oven at 80°C for 2 hours. The temperature was then raised to 140°C for 3 hours, and finally raised to 220°C for 4 hours to obtain 265g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, an off-white powder with a liquid phase content of 99.92% and a yield of 90.13%.

[0046] Example 5

[0047] 154g of biphenyl, 206g of maleic anhydride, 3800g of 1-ethyl-3-methylimidazolium trifluoroacetate, and 3g of diisobutylaluminum chloride were cooled to below 10°C under mechanical stirring, and then 139g of solid superacid SO4 was added. 2- Al2O3 was stirred at this temperature for 5 hours, and then 139g of solid superacid SO4 was added. 2- After reacting Al2O3 at 100℃ for 3 hours, the mixture was filtered. 450g of potassium permanganate was added to the filtrate at 60℃, and the reaction continued at 100℃ until the reactants were completely reacted. The reaction solution was then filtered, and the filtrate was added to ice water to crystallize. After filtration, the filter cake was washed with water and dried in a vacuum drying oven at 80℃ for 2 hours. The temperature was then increased to 140℃ for 3 hours, and finally to 220℃ for 4 hours to obtain 250g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, an off-white powder with a yield of 85.03% and a liquid phase content of 99.74%.

[0048] Example 6

[0049] 154g of biphenyl, 206g of maleic anhydride, 4600g of 1-ethyl-3-methylimidazolium sulfate methyl ester salt, and 6g of dimethyl aluminum chloride were mixed and cooled to below 10°C under mechanical stirring. 152g of polyphosphoric acid was added, and the mixture was stirred at this temperature for 2 hours. Then, 152g of polyphosphoric acid was added, and the temperature was raised to 100°C. After reacting for 4 hours, the mixture was filtered. 1380g of 20% peracetic acid was added dropwise to the filtrate at 30°C. After the addition was complete, the reaction continued until the reactants were completely reacted. The reaction solution was added to ice water to crystallize, filtered, and the filter cake was washed with water and dried in a vacuum drying oven at 80°C for 2 hours. Then, the temperature was raised to 140°C and dried for 3 hours. Finally, the temperature was raised to 220°C and dried for 4 hours to obtain 238g of 3,3',4,4'-biphenyltetracarboxylic dianhydride, an off-white powder with a yield of 80.95% and a liquid phase content of 99.92%.

[0050] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride, characterized in that: The process includes the following steps: adding biphenyl, dianhydride and co-catalyst to an ionic liquid, adding a portion of the catalyst, reacting at low temperature, adding the remaining catalyst and continuing to heat the reaction, filtering the reaction solution after the intermediate has completely reacted, adding an oxidant to the filtrate and heating the reaction, adding the reaction solution to ice water after the reaction has completely reacted, stirring and filtering, washing the filter cake with water and drying it stepwise in a vacuum drying oven to obtain 3,3',4,4'-biphenyltetracarboxylic dianhydride; Among them, the dianhydride is succinic anhydride or maleic anhydride; The ionic liquid is selected from any one of 1-ethyl-3-methylimidazolium aluminum chloride, 1-ethyl-3-methylimidazolium trifluoromethanesulfonate, 1-butyl-3-methylimidazolium hexafluoroantimonate, 1-ethyl-3-methylimidazolium trifluoroacetate, and 1-ethyl-3-methylimidazolium methyl sulfate. The co-catalyst is selected from any one of mercaptoacetic acid, aluminum trifluoromethanesulfonate, polyphosphoric acid, and solid superacid SO4²- / Al2O3; The catalyst is selected from any one of anhydrous aluminum trichloride ultrafine powder, dimethyl aluminum chloride, methyl aluminum chloride, and diisobutyl aluminum chloride; the oxidant is peracetic acid or potassium permanganate.

2. The method for preparing 3,3,4,4'-biphenyltetracarboxylic dianhydride according to claim 1, characterized in that: The molar ratio of biphenyl and dianhydride is 1:(2-2.05), and the mass ratio of biphenyl, ionic liquid, catalyst and co-catalyst is 1:(4-10):(1.5-6):(0.5%-5%).

3. The method for preparing 3,3',4,4'-biphenyltetracarboxylic dianhydride according to claim 1, characterized in that: The low-temperature reaction has a reaction temperature of -10℃ to 10℃, and the heating reaction has a reaction temperature of 50℃ to 140℃.

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