Methods for improving catalyst longevity in the preparation of bis(imino)pyridine compounds and metal organic frameworks

Abstract

The application relates to the technical field of bis(imino)pyridine compounds, and discloses a method for preparing 2,6-bis(imino)pyridine compounds and a metal organic framework material. The method comprises contacting a bisacylpyridine, a halogenated aniline or an aniline with a catalyst, wherein the catalyst is a metal organic framework material, ligands of the metal organic framework material are provided by a substance with a structure as shown in formula (1), and a coordination metal M is selected from one of Zn, Co and Zr; in formula (1), M' is selected from one of Li, Na, K, Cs, Ca and Mg. The method can improve the yield of 2,6-bis(imino)pyridine compounds.

Description

Technical Field

[0001] This invention relates to the field of bis(imino)pyridine compounds, specifically to a method for improving catalyst lifetime and a metal-organic framework material during the preparation of bis(imino)pyridine compounds. Background Technology

[0002] 2,6-bis(imino)pyridine compounds with transition metal complexes are very important organometallic compounds, serving as catalysts for many organic chemical reactions, such as propylene polymerization, ethylene polymerization, or reactions characterized by transition metals. Complexation with the transition metal ruthenium readily catalyzes reactions such as olefin metathesis, making the synthesis of 2,6-bis(imino)pyridine ligands crucial. The commonly used industrial method for synthesizing 2,6-bis(imino)pyridine compounds involves using p-toluenesulfonic acid, formic acid, or acetic acid as catalysts to react pyridine diones with aniline derivatives (J.Am.Chem.Soc.1998,120,4049; Angew.Chem.,Int.Ed.Engl.1999,38,428; J.Am.Chem.Soc.1999,121,8728; CN01105268.8; WO 01 / 07491 A1). These catalytic reactions must be carried out at 110-150℃, and the post-processing is relatively complex.

[0003] Therefore, it is of great significance to study and develop a method for preparing 2,6-bis(imino)pyridine compounds. Summary of the Invention

[0004] The purpose of this invention is to overcome the aforementioned technical problems existing in the prior art.

[0005] To achieve the above objectives, the first aspect of the present invention provides a method for improving the catalyst lifetime during the preparation of bis(imino)pyridine compounds, the method comprising contacting a bisacylpyridine, a haloaniline, or an aniline with a catalyst, wherein the catalyst is a metal-organic framework material, the ligand of the metal-organic framework material is provided by a substance with the structure shown in formula (1), and the coordinating metal M is selected from Zn, Co, and Zr; in formula (1), M' is selected from Li, Na, K, Cs, Ca, and Mg;

[0006]

[0007] A second aspect of the present invention provides a metal-organic framework material, which is a metal-organic framework material as defined in any one of claims 1-5 or an acidified product as described in any one of claims 6-9.

[0008] The third aspect of the present invention provides a method for preparing a metal-organic framework material, wherein the preparation method is the method for preparing a metal-organic framework material as defined in any one of claims 6-9.

[0009] Compared with the prior art, the technical solution provided by the present invention has at least the following advantages:

[0010] (1) The metal-organic framework material provided by the present invention has a stable structure and good performance. Furthermore, the catalyst and the product are easy to separate and can be reused repeatedly, which is more environmentally friendly and has a lower cost. It has a very broad application prospect in future industrial applications.

[0011] (2) The catalyst provided by the present invention can be used in the synthesis of 2,6-bis(imino)pyridine compounds. The yield of the catalyst of the present invention is much higher than that of industrial catalysts (p-toluenesulfonic acid, formic acid, acetic acid). Moreover, after the catalyst of the present invention is used repeatedly 10 times, the yield of 2,6-bis(imino)pyridine compounds remains basically unchanged.

[0012] (3) The synthesis method of the 2,6-bis(imino)pyridine compounds prepared in this invention serves as an important ligand for the synthesis of polyethylene catalysts and an important ligand for the synthesis of 4-methyl-1-pentene, thereby improving the synthesis efficiency, reducing the synthesis cost, and greatly reducing the production cost of polyolefins. Detailed Implementation

[0013] The endpoints and any values ​​of the ranges disclosed herein are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of the various ranges, the endpoint values ​​of the various ranges and individual point values, and individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed herein.

[0014] The first aspect of the present invention provides a method for improving the catalyst lifetime during the preparation of bis(imino)pyridine compounds, the method comprising contacting a bisacylpyridine, a haloaniline or aniline with a catalyst, wherein the catalyst is a metal-organic framework material, the ligand of the metal-organic framework material is provided by a substance with the structure shown in formula (1), the coordinating metal M is selected from Zn, Co and Zr; in formula (1), M' is selected from Li, Na, K, Cs, Ca and Mg;

[0015]

[0016] According to some embodiments of the present invention, the metal-organic framework material has a structure as shown in formula (2):

[0017]

[0018] According to some embodiments of the present invention, the specific surface area of ​​the metal-organic framework material is 10-1000 m². 2 / g, pore volume is 1-10mL / g, and most probable pore size is 2-9nm.

[0019] Preferably, the specific surface area of ​​the metal-organic framework material is 400-800 m². 2 / g, more preferably 400-501m 2 / g, with a pore volume of 5-9 mL / g, more preferably 5.1-8.9 mL / g, and a most probable pore size of 3-8 nm, more preferably 5-8 nm.

[0020] According to some embodiments of the present invention, the diacylpyridine is at least one of 2,6-dicarboxypyridine, 2,6-diacetylpyridine, and 2,6-dipropionylpyridine.

[0021] According to some embodiments of the present invention, halogenated aniline compounds include 4-fluoroaniline and / or 4-chloroaniline.

[0022] According to some embodiments of the present invention, the contact is carried out in solvent A, wherein solvent A is at least one selected from toluene, n-hexane, cyclohexane, petroleum ether, and dioxane, preferably at least one selected from toluene, n-hexane, and cyclohexane.

[0023] According to some embodiments of the present invention, the weight ratio of bisacylpyridine, haloaniline, metal-organic framework material and solvent A is (1-5):(1-20):(0.01-12):(1-150), preferably (1-5):(1.6-12):(0.5-1):(4-100).

[0024] According to some embodiments of the present invention, the weight ratio of bisacylpyridine, aniline, metal-organic framework material and solvent A is (1-5):(1-20):(0.01-12):(1-150), preferably (1-5):(1.6-12):(0.5-1):(4-100).

[0025] According to some embodiments of the present invention, the contact conditions include: a temperature of 0-60°C, preferably 20-45°C; and a time of 1-20 hours, preferably 2-15 hours.

[0026] According to some embodiments of the present invention, the method further includes solid-liquid separation, concentration and recrystallization of the contacted products.

[0027] According to some embodiments of the present invention, the method for preparing the metal-organic framework material includes the following steps:

[0028] (1) In the presence of a first solvent and a monobasic acid, the compound shown in formula (3) is subjected to a coordination reaction with the metal source to be coordinated, wherein the monobasic acid has more than 4 carbon atoms.

[0029] (2) Optionally, the product of the coordination reaction is acidified;

[0030] In formula (II), M” is selected from one of Li, Na, K, Cs, Ca and Mg; the metal in the metal source to be coordinated is selected from one of Zn, Co and Zr.

[0031]

[0032] According to some embodiments of the present invention, in step (1), the conditions of the coordination reaction may include: a temperature of 80-200°C, preferably 100-150°C; and a time of 5-30h, preferably 10-24h.

[0033] According to some embodiments of the present invention, the molar ratio of the compound shown in formula (3), the metal source to be coordinated, the monobasic acid and the first solvent can be 1:(1.5-5):(0-20):(1-100); preferably 1:(2-3):(0-10):(2-50).

[0034] In this invention, the addition of an acid (such as acetic acid) in the coordination reaction can act as a template agent, forming catalytically active vacancies on the crystal surface, which can then be used for subsequent modification.

[0035] According to some embodiments of the present invention, the metal source to be coordinated may be selected from ZrCl4, Co(NO3)2 6H2O and Zn(acac)2.

[0036] According to some embodiments of the present invention, the first solvent may be selected from at least one of N,N-dimethylformamide, dimethyl sulfoxide and N-methylpyrrolidone, preferably N,N-dimethylformamide.

[0037] According to some embodiments of the present invention, the monocarboxylic acid is selected from carboxylic acids containing a benzene ring, preferably from C6-C10 carboxylic acids containing a benzene ring, and more preferably from benzoic acid and / or phenylacetic acid.

[0038] In this invention, there are no particular limitations on the post-processing of the coordination reaction in step (1), as long as it meets the requirements of this invention. For example, it can be carried out as follows: the materials of the coordination reaction are centrifuged and filtered (1000-10000 rpm), and washed with a washing solvent (e.g., DMF and methanol in sequence) (which can be repeated 2-5 times); then dried at 90-180℃ for 5-10 hours. There are no particular limitations on the type and amount of washing solvent, as long as it meets the requirements of this invention.

[0039] According to some embodiments of the present invention, in step (1), the preparation step of the compound represented by formula (3) includes: in the presence of a second solvent and a metal halide, 4,4'-biphenyl dicarboxylic acid is subjected to a substitution reaction with chlorosulfonate to obtain the compound represented by formula (3).

[0040] According to some embodiments of the present invention, the conditions for the substitution reaction may include: a temperature of 30-100°C, preferably 40-80°C; and a time of 5-30 h, preferably 10-24 h.

[0041] According to some embodiments of the present invention, the molar ratio of 4,4'-biphenyl dicarboxylic acid, chlorosulfonate and metal halide can be 1:(0.5-2):(0.01-1), preferably 1:(0.8-1.2):(0.05-0.5).

[0042] According to some embodiments of the present invention, the metal halide is selected from at least one of RuCl3, FeCl3, AlCl3 and PdCl2, preferably selected from at least one of RuCl3, FeCl3 and AlCl3.

[0043] According to some embodiments of the present invention, the second solvent is selected from at least one of dichloromethane, 1,2-dichloromethane and chloroform; preferably dichloromethane.

[0044] According to some embodiments of the present invention, the amount of the second solvent used is 20-80 mL, preferably 30-60 mL, relative to 1 g of 4,4'-biphenyldicarboxylic acid.

[0045] There are no particular limitations on the post-processing operations of the above substitution reaction, as long as they meet the requirements of this invention. Preferably, before obtaining the compound shown in formula (3), the following post-processing operations can be performed: the material from the substitution reaction is filtered and washed with a washing solvent (e.g., dichloromethane and methanol sequentially) (this can be repeated 2-5 times); then dried at 60-100°C for 5-10 hours. There are no particular limitations on the type and amount of washing solvent, as long as they meet the requirements of this invention.

[0046] According to some embodiments of the present invention, in step (2), the acidification is carried out in the presence of an inorganic acid, the concentration of which is 0.1-18.4 mol / L, preferably 1-10 mol / L.

[0047] In this invention, the inorganic acid can be selected from at least one of hydrochloric acid, sulfuric acid, and nitric acid, preferably sulfuric acid. The nitric acid is preferably dilute nitric acid (concentration can be 0.1-1 mol / L). The sulfuric acid is preferably dilute sulfuric acid (concentration can be 0.1-5 mol / L).

[0048] According to some embodiments of the present invention, the acidification conditions may include: a temperature of 0°C to 100°C, preferably 20°C to 50°C; and a time of 5-30 hours, preferably 10-24 hours.

[0049] According to some embodiments of the present invention, the amount of the inorganic acid used is 0.2-10 mol, preferably 0.4-5 mol, relative to each mole of the compound represented by formula (3).

[0050] Those skilled in the art will understand that after acidification, M” in formula (3) is transformed from metal to H, thereby obtaining a strongly acidic metal-organic framework material.

[0051] In this invention, before obtaining the metal-organic framework material, the following post-processing operation can be performed: the acidified material system is filtered, and the obtained solid is washed with water (this can be repeated 2-5 times). There is no particular limitation on the amount of water used for washing.

[0052] The synthetic route for 2,6-bis(imino)pyridine compounds in this invention is shown below:

[0053]

[0054] Among them, A 1 and A 2 Each independently is H and / or C 1-6 Hydrocarbon groups (e.g., methyl, ethyl, isopropyl, etc.), R 1 R 2 R 3 R 4 R 5 Each is independently H and / or a halogen (e.g., Cl, F, Br, I).

[0055] A second aspect of the present invention provides a metal-organic framework material, which is a metal-organic framework material as defined above or an acidified product as described above.

[0056] A third aspect of the present invention provides a method for preparing a metal-organic framework material, which is the method for preparing a metal-organic framework material as defined above.

[0057] The present invention will be described in detail below through embodiments.

[0058] The raw materials and solvents used in the following examples were all commercially available;

[0059] Specific surface area, total pore volume, and most probable pore size were obtained by nitrogen physical adsorption (purchased from Anton Paconta Instruments, model Autosorb-iQ).

[0060] Example 1

[0061] (1) Add 1.04 g of RuCl3, 24.20 g of 4,4'-biphenyldicarboxylic acid, 16.5% sodium chlorosulfonate and 1000 mL of 1,2-dichloroethane to the reaction flask, and carry out the substitution reaction at 50 °C for 10 h. After filtration, the solid is washed three times with 100 mL of 1,2-dichloroethane and three times with 100 mL of methanol. It is dried at 80 °C for 8 h to obtain a white powder (confirmed by NMR to be the compound shown in formula (3), where M” is Na) 38.9 g. Then, Zn(acac)2, the compound shown in formula (3), DMF and benzoic acid are subjected to a coordination reaction (calcination crystallization) at 120 °C in a molar ratio of 2.5:1:40:6 for 24 h. After centrifugation and filtration at 4000 rpm, the solid is washed three times with 50 mL of DMF and three times with 50 mL of methanol. The solid is dried at 105 °C for 8 h to obtain a white solid (metal-organic framework material).

[0062] (2) Add 24 mL of 5 mol / L sulfuric acid to the white solid obtained in step (1) and acidify it for 5 h under stirring at 25 °C; filter and wash the solid three times with 50 mL of water to obtain the acidified metal-organic framework material (Zn is the metal center).

[0063] Specific surface area is 501 m² 2 / g, total pore volume = 8.7mL / g, most probable pore size = 6nm.

[0064] Example 2

[0065] (1) Add 1.04 g of RuCl3, 24.20 g of 4,4'-biphenyldicarboxylic acid, 16.5 g of sodium chlorosulfonate and 1000 mL of 1,2-dichloroethane to the reaction flask, and carry out the substitution reaction at 50 °C for 10 h. After filtration, the solid is washed three times with 100 mL of 1,2-dichloroethane and three times with 100 mL of methanol. It is dried at 80 °C for 8 h to obtain a white powder (confirmed by NMR to be the compound shown in formula (3), where M” is Na) 38.9 g. Then, ZrCl4, the compound shown in formula (3), DMF and benzoic acid are subjected to a coordination reaction (calcination crystallization) at 120 °C in a molar ratio of 2.5:1:40:6 for 24 h. After centrifugation and filtration at 4000 rpm, the solid is washed three times with 50 mL of DMF and three times with 50 mL of methanol. The solid is dried at 105 °C for 8 h to obtain a white solid (metal-organic framework material).

[0066] (2) Add 24 mL of 5 mol / L sulfuric acid to the white solid obtained in step (1) and acidify it for 12 h under stirring at 25 °C; filter and wash the solid three times with 50 mL of water to obtain the acidified metal-organic framework material (Zr is the metal center).

[0067] Specific surface area is 428 m² 2 / g, total pore volume = 8mL / g, most probable pore size = 5nm.

[0068] Example 3

[0069] (1) Add 1.04 g of RuCl3, 24.20 g of 4,4'-biphenyldicarboxylic acid, 16.5 g of sodium chlorosulfonate and 1000 mL of 1,2-dichloroethane to a reaction flask, and carry out the substitution reaction at 50 °C for 10 h. Filter the solid, wash it three times with 100 mL of 1,2-dichloroethane and three times with 100 mL of methanol, and dry it at 80 °C for 8 h to obtain a white powder (confirmed by NMR to be the compound shown in formula (3), where M” is Na) 38.9 g. Then, add Co(NO3)2 The compound shown in formula (3), DMF and benzoic acid were subjected to a coordination reaction (calcination crystallization) at 120°C in a molar ratio of 2.5:1:40:6 for 24 h. After centrifugation and filtration at 4000 rpm, the solid was washed three times with 50 mL of DMF and three times with 50 mL of methanol. The solid was dried at 105°C for 8 h to obtain a white solid (metal-organic framework material).

[0070] (2) Add 24 mL of 5 mol / L sulfuric acid to the white solid obtained in step (1) and acidify it for 5 h under stirring at 25 °C; filter and wash the solid three times with 50 mL of water to obtain the acidified metal-organic framework material (Co is the metal center).

[0071] Specific surface area is 489 m² 2 / g, total pore volume = 8.9mL / g, most probable pore size = 8nm.

[0072] Test Example 1

[0073] The metal-organic framework material prepared in the above examples was used as a catalyst to evaluate its catalytic performance in the preparation of 2,6-bis(imino)pyridine compounds. 0.49 g of 2,6-diacetylpyridine, 0.89 g of 4-fluoroaniline, and 0.3 g of the metal-organic framework material were added to a 100 mL flask. 40 mL of toluene was added, and the mixture was heated to 40-45 °C. The reaction was stopped after 15 h. The reaction product was then filtered to obtain a single-use metal-organic framework material. The filtered solution was concentrated, and the solid obtained after concentration was recrystallized from methanol (the solid was dissolved in methanol at 80 °C, and the temperature was gradually lowered to 30 °C-0 °C, causing crystals to gradually precipitate, which were then separated by filtration). The solids were weighed, and the yield of the 2,6-bis(imino)pyridine compounds was calculated. The results are shown in Table 1.

[0074] Test Example 2

[0075] The test was conducted according to the method in Test Example 1, except that 4-fluoroaniline was replaced with an equimolar amount of 4-chloroaniline.

[0076] Test Example 3

[0077] This test example illustrates the stability of the metal-organic framework material prepared in the above embodiments as a catalyst.

[0078] 2,6-bis(imino)pyridine compounds were prepared according to the method of Test Example 1, except that the metal-organic framework material obtained from the filtration in Test Example 1 was reused. The average yield of 2,6-bis(imino)pyridine compounds after 5 reuses was calculated, and the results are shown in Table 1. The number of reuses required to reduce the yield of 2,6-bis(imino)pyridine compounds to 95% was also investigated, and the results are shown in Table 1.

[0079] The formula for calculating the yield of 2,6-bis(imino)pyridine compounds is: (amount of 2,6-bis(imino)pyridine compound) ÷ (amount of 2,6-diacetylpyridine) × 100%.

[0080] Table 1

[0081]

[0082] Comparative Test Case 1

[0083] Add 0.49 g of 2,6-diacetylpyridine, 0.89 g of 4-fluoroaniline, and 2.6 mg of p-toluenesulfonic acid to a 100 mL flask. Heat to reflux (110-120 °C) for 24 h. After the reaction is complete, wash twice with saturated sodium carbonate solution and twice with distilled water. Extract the aqueous phase twice with diethyl ether. Dry and concentrate the solid and recrystallize it from methanol (dissolve the solid in methanol at 80 °C, gradually cool to 30 °C-0 °C, crystals gradually precipitate, and then filter to separate). The yield is 80%.

[0084] A comparison of Test Example 1 with Comparative Test Example 1 of this application shows that the method of this invention not only improves the yield of 2,6-bis(imino)pyridine compounds but also reduces the reaction temperature and energy consumption. Furthermore, the catalyst of this invention can be recycled multiple times while maintaining a substantially constant yield, thus reducing production costs. In contrast, the catalyst (p-toluenesulfonic acid) in Comparative Test Example 1 cannot be reused, and the purification process for 2,6-bis(imino)pyridine compounds is complex, increasing production costs.

[0085] The preferred embodiments of the present invention have been described in detail above; however, the present invention is not limited thereto. Within the scope of the inventive concept, various simple modifications can be made to the technical solutions of the present invention, including combinations of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as the content disclosed in the present invention and are all within the protection scope of the present invention.

Claims

1. A method for preparing bis(imino)pyridine compounds, characterized in that, The method includes contacting a bisacylpyridine, a haloaniline, or an aniline with a catalyst, wherein the catalyst is a metal-organic framework material, the ligands of the metal-organic framework material are provided by a substance with the structure shown in formula (1), and the coordinating metal M is selected from Zn, Co, and Zr; in formula (1), M' is selected from Li, Na, K, and Cs; （1）； The specific surface area of ​​the metal-organic framework material is 10-1000 m². 2 / g, pore volume is 1-10mL / g, most probable pore size is 2-9nm; The preparation method of the metal-organic framework material includes the following steps: (1) In the presence of a first solvent and a monobasic acid, the compound shown in formula (3) is subjected to a coordination reaction with the metal source to be coordinated, wherein the monobasic acid is selected from benzoic acid and / or phenylacetic acid; (2) Acidify the product of the coordination reaction; In formula (3), M'' is selected from one of Li, Na, K, and Cs; the metal in the metal source to be coordinated is selected from one of Zn, Co, and Zr. （3）。 2. The method according to claim 1, wherein, The metal-organic framework material has a structure as shown in formula (2): （2）。 3. The method according to claim 1, wherein, The specific surface area of ​​the metal-organic framework material is 400-800 m². 2 / g, pore volume is 5-9mL / g, and most probable pore size is 3-8nm.

4. The method according to claim 1, wherein, The specific surface area of ​​the metal-organic framework material is 400-501 m². 2 / g, pore volume is 5.1-8.9mL / g, and most probable pore size is 5-8nm.

5. The method according to claim 1, wherein, The diacylpyridine is at least one of 2,6-dicarboxypyridine, 2,6-diacetylpyridine, and 2,6-dipropionylpyridine; And / or, the halogenated aniline is 4-fluoroaniline and / or 4-chloroaniline; And / or, the contact conditions include: a temperature of 0-60°C; and a time of 1-20 hours. And / or, the contact is carried out in solvent A, wherein solvent A is at least one of toluene, n-hexane, cyclohexane, petroleum ether, and dioxane.

6. The method according to claim 1, wherein, The contact conditions include: a temperature of 20-45℃ and a time of 2-15 hours.

7. The method according to claim 5, wherein, Solvent A is at least one of toluene, n-hexane, and cyclohexane.

8. The method according to claim 5, wherein, The weight ratio of bisacylpyridine, haloaniline, metal-organic framework material and solvent A is (1-5):(1-20):(0.01-12):(1-150).

9. The method according to claim 5, wherein, The weight ratio of bisacylpyridine, haloaniline, metal-organic framework material and solvent A is (1-5):(1.6-12):(0.5-1):(4-100).

10. The method according to claim 5, wherein, The weight ratio of bisacylpyridine, aniline, metal-organic framework material and solvent A is (1-5):(1-20):(0.01-12):(1-150).

11. The method according to claim 5, wherein, The weight ratio of bisacylpyridine, aniline, metal-organic framework material and solvent A is (1-5):(1.6-12):(0.5-1):(4-100).

12. The method according to claim 1, wherein, The method also includes solid-liquid separation, concentration, and recrystallization of the contacted products.

13. The method according to claim 1, wherein, In step (1), the conditions for the coordination reaction include: a temperature of 80-200℃ and a time of 5-30h; And / or, the molar ratio of the compound shown in formula (3), the metal source to be coordinated, the monobasic acid, and the first solvent is 1:(1.5-5):(6-20):(1-100); And / or, the metal source to be coordinated is selected from one of ZrCl4, Co(NO3)26H2O and Zn(acac)2; And / or, the first solvent is selected from at least one of N,N-dimethylformamide, dimethyl sulfoxide, and N-methylpyrrolidone.

14. The method according to claim 1, wherein, In step (1), the conditions for the coordination reaction include: a temperature of 100-150℃ and a time of 10-24h.

15. The method according to claim 1, wherein, The molar ratio of the compound shown in formula (3), the metal source to be coordinated, the monobasic acid, and the first solvent is 1:(2-3):(6-10):(2-50).

16. The method according to claim 1, wherein, The first solvent is N,N-dimethylformamide.

17. The method according to claim 1, wherein, In step (1), the preparation steps of the compound shown in formula (3) include: in the presence of a second solvent and a metal halide, 4,4'-biphenyl dicarboxylic acid is subjected to a substitution reaction with chlorosulfonate to obtain the compound shown in formula (3).

18. The method according to claim 17, wherein, The conditions for the substitution reaction include: a temperature of 30-100℃ and a time of 5-30h.

19. The method of claim 17, wherein, The conditions for the substitution reaction include: a temperature of 40-80℃ and a time of 10-24h.

20. The method of claim 17, wherein, The molar ratio of 4,4'-biphenyl dicarboxylic acid, chlorosulfonate, and metal halide is 1:(0.5-2):(0.01-1).

21. The method according to claim 17, wherein, The molar ratio of 4,4'-biphenyl dicarboxylic acid, chlorosulfonate, and metal halide is 1:(0.8-1.2):(0.05-0.5).

22. The method according to claim 17, wherein, The metal halide is selected from at least one of RuCl3, FeCl3, AlCl3 and PdCl2.

23. The method according to claim 17, wherein, The metal halide is selected from at least one of RuCl3, FeCl3 and AlCl3.

24. The method of claim 17, wherein, The second solvent is selected from at least one of dichloromethane, 1,2-dichloroethane, and chloroform.

25. The method according to claim 17, wherein, The second solvent is dichloromethane.

26. The method according to claim 17, wherein, The amount of the second solvent used is 20-80 mL relative to 1 g of 4,4'-biphenyldicarboxylic acid.

27. The method according to claim 17, wherein, The amount of the second solvent used is 30-60 mL relative to 1 g of 4,4'-biphenyldicarboxylic acid.

28. The method according to claim 1, wherein, In step (2), the acidification is carried out in the presence of an inorganic acid selected from at least one of hydrochloric acid, sulfuric acid, and nitric acid; And / or, the acidification conditions include: a temperature of 0°C to 100°C; The time is 5-30 hours.

29. The method according to claim 28, wherein, The inorganic acid is sulfuric acid.

30. The method according to claim 1, wherein, The acidification conditions include: a temperature of 20°C to 50°C and a time of 10-24 hours.

31. The method according to claim 28, wherein, The amount of the inorganic acid used is 0.2-10 mol relative to each mole of the compound represented by formula (3).

32. The method according to claim 28, wherein, The amount of the inorganic acid used is 0.4-5 mol relative to each mole of the compound represented by formula (3).

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