A multi-nuclear phthalocyanine catalyst with three-dimensional structure, its preparation method and application

Abstract

The present application relates to a kind of three-dimensional structure polynuclear phthalocyanine catalysts with, metal phthalocyanine core is connected by flexible covalent bond in the polynuclear phthalocyanine catalyst and forms stable three-dimensional structure, greatly reduce the aggregation of metal phthalocyanine, so that the polynuclear core can realize synergistic catalysis.Stable three-dimensional structure makes the catalyst have larger molecular weight, and catalytic center metal is not easy to lose, and is easier to separate and purify in heterogeneous catalytic process.

Description

Technical Field

[0001] This invention relates to the field of heterogeneous catalysts for polynuclear metal phthalocyanines, and particularly to a polynuclear phthalocyanine catalyst with a three-dimensional structure, its preparation method, and its application. Background Technology

[0002] Nitrogen-containing heterocyclic aromatic compounds are common intermediate molecules related to drugs and bioactivity. Representative examples include quinoline, carbazole and its derivatives, which have important applications in dyes, bioactive molecular intermediates, synthetic medicines and other fields.

[0003] For the preparation of nitrogen-containing heterocyclic aromatic compounds and their derivatives such as quinolines and carbazole, this method is a greener, more efficient, and more economical approach compared to the traditional organic synthesis method of oxidative dehydrogenation. In the field of catalysis, noble metal catalysts such as Ir, Pd, Rh, and Pt can be used for the dehydrogenation of nitrogen-containing heterocyclic aromatic compounds and their derivatives, but their scarcity and high cost greatly limit their application in industrial production. Transition metals, especially those from pre-period four, have the potential to replace noble metal catalysts due to their abundant reserves and the unfilled valence d orbitals. For example, Fe, Co, Zn, and Cu can be used for the dehydrogenation of nitrogen-containing heterocyclic aromatic compounds and their derivatives, but these catalysts are currently still in the laboratory stage due to the complexity of ligand synthesis, the complexity of reaction conditions (e.g., the need to add additional stoichiometric organic oxidants and high pressure during catalysis), and the difficulty in reusing the catalysts.

[0004] In nature, cytochrome P450, with its porphyrin-iron core structure, is undoubtedly the most efficient oxygen activator under mild conditions. Structure determines properties, and given that phthalocyanines have a structure remarkably similar to porphyrins, metal phthalocyanine complexes have the potential to activate oxygen and thus catalyze the oxidative dehydrogenation of nitrogen-containing heterocyclic aromatic compounds and their derivatives. However, due to the interaction between electrons in the π bonds, metal phthalocyanines are prone to aggregation, leading to a loss of their catalytic activity. To avoid this aggregation, patent document CN101804361A describes a physical impregnation method to load metal phthalocyanines onto molecular sieves. While simple, this method suffers from the potential loss of catalytic centers, affecting catalytic activity. Summary of the Invention

[0005] The purpose of this invention is to provide a three-dimensional polynuclear phthalocyanine catalyst, its preparation method and application. This catalyst has a stable three-dimensional structure, avoids the aggregation of metal phthalocyanines, and can efficiently catalyze the dehydrogenation of nitrogen heterocyclic compounds such as quinoline and carbazole.

[0006] To achieve the above objectives, the present invention employs the following technical solution:

[0007] A three-dimensional polynuclear phthalocyanine catalyst, wherein the metal phthalocyanine cores are linked by flexible covalent bonds to form a stable three-dimensional structure, is shown in formula (I).

[0008]

[0009] In the formula: M represents one or more of Mg, V, Mn, Fe, Co, Ni, Cu or Zn; This represents an extension of the three-dimensional structure of the catalyst; the molecular formula of Ar is one or more of the following;

[0010]

[0011] Any one of R1-R8 is one of hydrogen, alkyl, alkoxy, alkenyl, cycloalkyl, aryl, or halogen.

[0012] A method for preparing a three-dimensional polynuclear phthalocyanine catalyst includes the following steps:

[0013] 1) The bisphenol monomer, dicyano monomer and the first catalyst are mixed evenly and reacted. After the reaction is completed, the organic phase is dissolved, filtered and washed with a hydrophobic solvent to obtain the cyano monomer product.

[0014] 2) Add a metal salt to the cyano monomer product obtained in step 1), mix well, add a second catalyst, stir well, and carry out the reaction.

[0015] 3) The product obtained in step 2) is thoroughly washed and dried to obtain a three-dimensional polynuclear phthalocyanine catalyst.

[0016] The molar ratio of the bisphenol monomer, dicyano monomer and the first catalyst is 1:(2-2.2):(2-4);

[0017] The diphenol monomer is HO-Ar-OH, which is one or more of hydroquinone, resorcinol, 2-methoxyhydroquinone, 2-chlorohydroquinone, 4,4'-biphenyl, or 3,3'-dimethyl-4,4'-biphenyl; the dicyano monomer is one or more of 4-nitrophthalonitrile, 4-sulfonic acid phthalonitrile, 4-chlorophthalonitrile, or 4-bromophthalonitrile; the first catalyst is one or more of potassium carbonate, sodium carbonate, sodium bicarbonate, potassium hydroxide, sodium hydroxide, sodium methoxide, or triethylamine; the hydrophobic solvent is one or more of ethyl acetate, butyl acetate, dichloromethane, or 1,2-dichloroethane.

[0018] In step 1), the bisphenol monomer, dicyano monomer, and the first catalyst are mixed in an inert gas atmosphere and in a first polar solvent. After the mixing reaction is completed, the first polar solvent is recovered and then dissolved in a hydrophobic solvent. The first polar solvent is one or more of ethanol, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, or dimethyl sulfoxide.

[0019] The reaction temperature in step 1) is 70℃~130℃; the reaction time is 8h~12h.

[0020] The molar ratio of the cyano monomer product, the metal salt, and the second catalyst is 1:(0.5-0.8):(2-2.5); the metal salt is one or more of Mg, V, Mn, Fe, Co, Ni, Cu, or Zn; the second catalyst is one or more of sodium methoxide, sodium ethoxide, triethylamine, aniline, ammonium molybdate, urea, and 1,8-diazabicycloundec-7-ene.

[0021] Step 2) is carried out in an inert gas atmosphere and in a second polar solvent for mixing and reaction. After the reaction is completed, the second polar solvent is recovered. The second polar solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, n-pentanol, quinoline, and ethylene glycol.

[0022] The reaction temperature in step 2) is 150℃-230℃, and the reaction time is 6h-12h.

[0023] In step 3), washing is performed using an aqueous solution of an organic solvent and an acid; the organic solvent is one or more of methanol, ethanol, acetonitrile, ethyl acetate, and acetone; the aqueous solution of the acid is one or more of dilute hydrochloric acid, dilute sulfuric acid, and dilute nitric acid; the mass fraction of the dilute hydrochloric acid, dilute sulfuric acid, and dilute nitric acid is 5% to 10%; the drying is carried out under vacuum conditions, with a vacuum degree of 0.02 MPa to 0.04 MPa and a drying temperature of 70°C to 90°C.

[0024] The inert gas is nitrogen or argon.

[0025] An application of a three-dimensional polynuclear phthalocyanine catalyst, wherein the three-dimensional polynuclear phthalocyanine catalyst is used in the dehydrogenation reaction of nitrogen heterocyclic compounds, the application steps are as follows:

[0026] A three-dimensional polynuclear phthalocyanine catalyst was added to a four-necked flask equipped with a reflux condenser. A nitrogen heterocyclic compound and solvent were added to the four-necked flask. Oxygen was introduced into the reaction system, and the reaction was carried out by heating and stirring. After the reaction was completed, the reaction solution was filtered, and the filtrate was concentrated to remove the solvent, thus obtaining the dehydrogenation product of the nitrogen heterocyclic compound.

[0027] The mass ratio of the three-dimensional polynuclear phthalocyanine catalyst to the nitrogen heterocyclic compound is 1:(8-10); the solvent is one of acetonitrile, toluene, p-xylene, mesitylene or chlorobenzene, and the amount of solvent used is 5-10 times the mass of the nitrogen heterocyclic compound.

[0028] The dehydrogenation reaction temperature is 80℃~140℃; the dehydrogenation reaction time is 20h~24h.

[0029] Compared with the prior art, the beneficial effects of the present invention are:

[0030] 1) The precursor used in the preparation of the three-dimensional multinuclear phthalocyanine catalyst of this invention has low steric hindrance and high cyano group utilization, which can construct more metal phthalocyanine catalytic cores. The substituent groups introduced on the precursor can adjust the electronic structure of the metal valence d orbitals in the square field of the metal phthalocyanine catalytic core, thereby enhancing the catalytic activity of the catalyst.

[0031] 2) In the three-dimensional multinuclear phthalocyanine catalyst prepared by this invention, the metal phthalocyanine catalytic cores are linked by flexible covalent bonds to form a stable three-dimensional structure, which greatly reduces the aggregation of metal phthalocyanines and enables synergistic catalysis by the multi-metal cores. The stable three-dimensional structure gives the catalyst a large molecular weight, making it less prone to loss of the catalytic center metal and easier to separate and purify in heterogeneous catalysis processes.

[0032] 3) The precursor of the three-dimensional polynuclear phthalocyanine catalyst prepared by this invention is simple to synthesize, and the catalyst construction method is simple and controllable with less pollution, making it suitable for industrial production. Attached Figure Description

[0033] 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:

[0034] Figure 1 The image shows the infrared spectrum of the cyano monomer, the precursor of the three-dimensional polynuclear phthalocyanine catalyst in Example 1.

[0035] Figure 2 The image shows the infrared spectrum of the three-dimensional polynuclear phthalocyanine catalyst in Example 1.

[0036] Figure 3 The image shows the XPS spectrum of the three-dimensional polynuclear phthalocyanine catalyst in Example 1.

[0037] Figure 4 The image shows the ultraviolet spectrum of the three-dimensional polynuclear phthalocyanine catalyst in Example 1.

[0038] Figure 5 This is a liquid phase diagram of the dehydrogenation product quinoline in Example 6. Detailed Implementation

[0039] The specific embodiments of the present invention will be further described below with reference to the accompanying drawings:

[0040] The raw materials and reagents used in the following examples are all of analytical grade, and the equipment used is conventional equipment that was purchased directly from the market. No further processing of the drugs is required.

[0041] The cyano monomer precursor used in this invention can be synthesized according to the synthesis method described in the literature Cheng Liu, Jinyan Wang, Encheng Lin, Lishuai Zong, Xigao Jian; Synthesis and properties of phthalonitrile-terminated oligomeric poly(ether imide)s containing phthalazinone moiety; Polymer Degradation and Stability; 2012, 97, 460-468;

[0042] Example 1

[0043] 1) In a nitrogen atmosphere, add 20g hydroquinone, 66g 4-nitrophthalonitrile and 63g potassium carbonate to a four-necked flask, add 250ml of acetonitrile, the first polar solvent, stir to dissolve, react at 80℃ for 8h, then distill to recover acetonitrile, dissolve the product with ethyl acetate, filter, wash the filtrate thoroughly with 5% dilute hydrochloric acid, collect and distill the organic phase to recover ethyl acetate, and remove residual solvent to obtain cyano monomer.

[0044] 2) In a nitrogen atmosphere, 10g of cyano monomer, 3g of sodium methoxide, and 2.2g of cobalt chloride were added to a four-necked flask equipped with a reflux condenser. 50ml of the second polar solvent N,N-dimethylformamide was added, stirred to dissolve, and heated under reflux for 8 hours. N,N-dimethylformamide was then recovered by vacuum distillation.

[0045] 3) The product obtained in step 2) was thoroughly washed with 5% dilute hydrochloric acid, methanol and acetonitrile respectively, and then dried under vacuum at 70°C to obtain a three-dimensional polynuclear phthalocyanine catalyst.

[0046] Example 2

[0047] 1) In a nitrogen atmosphere, add 20g hydroquinone, 60g 4-chlorophthalonitrile and 63g potassium carbonate to a four-necked flask, add 250ml of acetonitrile, the first polar solvent, stir to dissolve, react at 80℃ for 8h, then distill to recover acetonitrile, dissolve the product with ethyl acetate, filter, wash the filtrate thoroughly with 5% dilute hydrochloric acid, collect and distill the organic phase to recover ethyl acetate, and remove the residual solvent to obtain cyano monomer.

[0048] 2) In a nitrogen atmosphere, 10g of cyano monomer, 4.2g of 1,8-diazabicycloundec-7-ene, and 2.2g of cobalt chloride were added to a four-necked flask equipped with a reflux condenser. 50ml of the second polar solvent N,N-dimethylformamide was added, stirred to dissolve, and heated under reflux for 8 hours. N,N-dimethylformamide was then recovered by vacuum distillation.

[0049] 3) The product obtained in step 2) was thoroughly washed with 5% dilute hydrochloric acid, methanol and acetonitrile respectively, and then vacuum dried at 70°C to obtain a three-dimensional polynuclear phthalocyanine catalyst.

[0050] Example 3

[0051] 1) In a nitrogen atmosphere, add 20g hydroquinone, 75g 4-bromophthalonitrile and 63g potassium carbonate to a four-necked flask, add 250ml of acetonitrile, the first polar solvent, stir to dissolve, react at 80℃ for 8h, then distill to recover acetonitrile, dissolve the product with the hydrophobic solvent ethyl acetate, filter, wash the filtrate thoroughly with 5% dilute hydrochloric acid, collect and distill the organic phase to recover ethyl acetate, and remove the residual solvent to obtain cyano monomer.

[0052] 2) In a nitrogen atmosphere, 10g of cyano monomer, 4.2g of 1,8-diazabicycloundec-7-ene, and 3.4g of cobalt acetate tetrahydrate were added to a four-necked flask equipped with a reflux condenser. 50ml of the second polar solvent N,N-dimethylformamide was added, stirred to dissolve, and heated under reflux for 8 hours. N,N-dimethylformamide was then recovered by vacuum distillation.

[0053] 3) The product obtained in step 2) was thoroughly washed with 5% dilute hydrochloric acid, methanol and acetonitrile respectively, and then vacuum dried at 70°C to obtain a three-dimensional polynuclear phthalocyanine catalyst.

[0054] Example 4

[0055] 1) In a nitrogen atmosphere, add 20g hydroquinone, 66g 4-nitrophthalonitrile and 63g potassium carbonate to a four-necked flask, add 250ml of acetonitrile, the first polar solvent, stir to dissolve, react at 80℃ for 8h, then distill to recover acetonitrile, dissolve the product with ethyl acetate, filter, wash the filtrate thoroughly with 5% dilute hydrochloric acid, collect and distill the organic phase to recover ethyl acetate, and remove the residual solvent to obtain cyano monomer.

[0056] 2) In a nitrogen atmosphere, 10g of cyano monomer, 3g of sodium methoxide and 2g of ferrous chloride were added to a four-necked flask equipped with a reflux condenser. 50ml of the second polar solvent N,N-dimethylformamide was added, stirred to dissolve, and heated under reflux for 8 hours. N,N-dimethylformamide was then recovered by vacuum distillation.

[0057] 3) The product obtained in step 2) was thoroughly washed with 5% dilute hydrochloric acid, methanol and acetonitrile respectively, and then vacuum dried at 70°C to obtain a three-dimensional polynuclear phthalocyanine catalyst.

[0058] Example 5

[0059] 1) In a nitrogen atmosphere, add 20g hydroquinone, 60g 4-chlorophthalonitrile and 63g potassium carbonate to a four-necked flask, add 250ml of acetonitrile, the first polar solvent, stir to dissolve, react at 80℃ for 8h, then distill to recover acetonitrile, dissolve the product with ethyl acetate, filter, wash the filtrate thoroughly with 5% dilute hydrochloric acid, collect and distill the organic phase to recover ethyl acetate, and remove the residual solvent to obtain cyano monomer.

[0060] 2) In a nitrogen atmosphere, 10g of cyano monomer, 4.2g of 1,8-diazabicycloundec-7-ene, and 2g of ferrous chloride were added to a four-necked flask equipped with a reflux condenser. 50ml of the second polar solvent N,N-dimethylformamide was added, stirred to dissolve, and heated under reflux for 8 hours. N,N-dimethylformamide was then recovered by vacuum distillation.

[0061] 3) The product obtained in step 2) was thoroughly washed with 5% dilute hydrochloric acid, methanol and acetonitrile respectively, and then vacuum dried at 70°C to obtain a three-dimensional polynuclear phthalocyanine catalyst.

[0062] Example 6 uses the three-dimensional polynuclear phthalocyanine catalyst from Example 1 for the catalytic dehydrogenation of 1,2,3,4-tetrahydroquinoline.

[0063] 10g of 1,2,3,4-tetrahydroquinoline, 1g of three-dimensional polynuclear phthaloline catalyst, and 50g of acetonitrile were added to a four-necked flask equipped with a reflux condenser. The mixture was heated to reflux at 85°C with stirring and oxygen was bubbled in. The reaction was monitored in the liquid phase. After 24 hours, the reaction was completed. The reaction system was cooled, the catalyst was recovered by filtration, and the solvent was recovered by distillation. The yield of the dehydrogenated product quinoline was 96%.

[0064] The above-mentioned three-dimensional polynuclear phthalocyanine catalyst was purified by washing with methanol and acetonitrile and then repeatedly reused for the dehydrogenation reaction of 1,2,3,4-tetrahydroquinoline. The reaction conditions remained unchanged each time, and the reaction time was 24 h. After five reuses, the yield of the dehydrogenated product quinoline was 92%. The activity of the three-dimensional polynuclear phthalocyanine catalyst did not decrease significantly after multiple reuses, indicating that the catalyst has good stability.

[0065] Example 7 uses the three-dimensional polynuclear phthalocyanine catalyst from Example 1 for the catalytic dehydrogenation of 1,2,3,4-tetrahydroquinoline.

[0066] 10g of 1,2,3,4-tetrahydroquinoline, 1g of catalyst, and 50g of toluene were added to a four-necked flask equipped with a reflux condenser. The mixture was heated to reflux at 115°C with stirring and oxygen was bubbled in. The reaction was monitored by liquid phase. After 24 hours, the reaction was completed. The reaction system was cooled, the catalyst was recovered by filtration, and the solvent was recovered by distillation. The yield of the dehydrogenated product quinoline was 97%.

[0067] The above-mentioned three-dimensional polynuclear phthalocyanine catalyst was purified by washing with methanol and acetonitrile and then repeatedly reused for the dehydrogenation reaction of 1,2,3,4-tetrahydroquinoline. The reaction conditions remained unchanged each time, and the reaction time was 24 h. After five reuses, the yield of the dehydrogenation product carbazole was 92%. The activity of the three-dimensional polynuclear phthalocyanine catalyst did not decrease significantly after multiple reuses, indicating that the catalyst has good stability.

[0068] Example 8 uses the three-dimensional polynuclear phthalocyanine catalyst from Example 1 for the catalytic dehydrogenation of 1,2,3,4-tetrahydrocarbazole.

[0069] 10g of 1,2,3,4-tetrahydrocarbazole, 1g of catalyst, and 50g of acetonitrile were added to a four-necked flask equipped with a reflux condenser. The mixture was heated to reflux at 85°C with stirring and oxygen was bubbled in. The reaction was monitored by liquid phase. After 22 hours, the reaction was completed. The reaction system was cooled, the catalyst was recovered by filtration, and the solvent was recovered by distillation. The yield of the dehydrogenated product carbazole was 97%.

[0070] The above-mentioned three-dimensional polynuclear phthalocyanine catalyst was purified by washing with methanol and acetonitrile and then repeatedly reused for the dehydrogenation reaction of 1,2,3,4-tetrahydrocarbazole. The reaction conditions remained unchanged each time, and the reaction time was 22 h. After 5 reuses, the yield of the dehydrogenated carbazole was 92%. The catalyst activity did not decrease significantly after multiple reuses, indicating that the catalyst has good stability.

[0071] Example 9 uses the three-dimensional polynuclear phthalocyanine catalyst from Example 1 for the catalytic dehydrogenation of 1,2,3,4-tetrahydrocarbazole.

[0072] 10g of 1,2,3,4-tetrahydrocarbazole, 1g of catalyst, and 50g of p-xylene were added to a four-necked flask equipped with a reflux condenser. The mixture was heated to reflux at 140°C with stirring and oxygen was bubbled in. The reaction was monitored by liquid phase. After 20 hours, the reaction was completed. The reaction system was cooled, the catalyst was recovered by filtration, and the solvent was recovered by distillation. The yield of the dehydrogenated product carbazole was 97%.

[0073] The above-mentioned three-dimensional polynuclear phthalocyanine catalyst was purified by washing with methanol and acetonitrile and then repeatedly reused for the dehydrogenation reaction of 1,2,3,4-tetrahydrocarbazole. The reaction conditions remained unchanged each time, and the reaction time was 20 h. After five reuses, the yield of the dehydrogenated carbazole was 93%. The activity of the three-dimensional polynuclear phthalocyanine catalyst did not decrease significantly after multiple reuses, indicating that the catalyst has good stability.

[0074] The preferred embodiments of the present invention have been described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the specific details of the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solutions of the present invention, and these simple modifications all fall within the protection scope of the present invention. Furthermore, it should be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. To avoid unnecessary repetition, the present invention will not describe the various possible combinations separately. In addition, various different embodiments of the present invention can also be arbitrarily combined, as long as they do not violate the spirit of the present invention, and should also be considered as the content disclosed by the present invention.

Claims

1. Use of a catalyst having a three-dimensionally structured polynuclear phthalocyanine, characterized in that The three-dimensional polynuclear phthalocyanine catalyst is applied to the dehydrogenation reaction of nitrogen heterocyclic compounds, and the application steps are as follows: A three-dimensional polynuclear phthalocyanine catalyst was added to a four-necked flask equipped with a reflux condenser. A nitrogen heterocyclic compound and solvent were added to the four-necked flask, and oxygen was introduced into the reaction system. The reaction was heated and stirred. After the reaction was completed, the reaction solution was filtered, and the filtrate was concentrated to remove the solvent, thus obtaining the dehydrogenation product of the nitrogen heterocyclic compound. In the aforementioned three-dimensional multinuclear phthalocyanine catalyst, the metal phthalocyanine cores are linked by flexible covalent bonds to form a stable three-dimensional structure. The general structural formula of this multinuclear phthalocyanine catalyst is shown in formula (I): (I) wherein: M represents one or more of Mg, V, Mn, Fe, Co, Ni, Cu or Zn; represents an extension of the three-dimensional structure of the catalyst; Ar has the formula of one or more of the following: ; The preparation method of the three-dimensional polynuclear phthalocyanine catalyst includes the following steps: 1) The bisphenol monomer, dicyano monomer and the first catalyst were mixed evenly and reacted. After the reaction was completed, the mixture was dissolved in a hydrophobic solvent, filtered and washed, and the organic phase was recovered to obtain the cyano monomer product; 2) Add a metal salt to the cyano monomer product obtained in step 1), mix thoroughly, add a second catalyst, stir until homogeneous, and proceed with the reaction; 3) The product obtained in step 2) is thoroughly washed and dried to obtain a three-dimensional polynuclear phthalocyanine catalyst.

2. Use of a catalyst having a three-dimensional structure polynuclear phthalocyanine according to claim 1, characterized in that Any one of R1-R8 is one of hydrogen, alkyl, alkoxy, alkenyl, cycloalkyl, aryl, or halogen.

3. Use of a catalyst having a three-dimensional structure polynuclear phthalocyanine according to claim 1, characterized in that , The molar ratio of the bisphenol monomer, dicyano monomer, and the first catalyst is 1:(2~2.2):(2~4); the bisphenol monomer is HO-Ar-OH, which is one or more of hydroquinone, resorcinol, 2-methoxyhydroquinone, 2-chlorohydroquinone, 4,4'-biphenyl, or 3,3'-dimethyl-4,4'-biphenyl; the dicyano monomer is one or more of 4-nitrophthalonitrile, 4-sulfonic phthalonitrile, 4-chlorophthalonitrile, or 4-bromophthalonitrile; the first catalyst is one or more of potassium carbonate, sodium carbonate, sodium bicarbonate, potassium hydroxide, sodium hydroxide, sodium methoxide, or triethylamine; the hydrophobic solvent is one or more of ethyl acetate, butyl acetate, dichloromethane, or 1,2-dichloroethane. In step 1), the bisphenol monomer, dicyano monomer, and the first catalyst are mixed in an inert gas atmosphere and in a first polar solvent. After the mixing reaction is completed, the first polar solvent is recovered and then dissolved in a hydrophobic solvent. The first polar solvent is one or more of ethanol, acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, or dimethyl sulfoxide. The reaction temperature in step 1) is 70℃~130℃; the reaction time is 8h~12h.

4. Use of a catalyst having a three-dimensional structure polynuclear phthalocyanine according to claim 1, characterized in that , The molar ratio of the cyano monomer product, the metal salt, and the second catalyst is 1:(0.5~0.8):(2~2.5); the metal salt is one or more of Mg, V, Mn, Fe, Co, Ni, Cu, or Zn; the second catalyst is one or more of sodium methoxide, sodium ethoxide, triethylamine, aniline, ammonium molybdate, urea, and 1,8-diazabicycloundec-7-ene. Step 2) involves a mixing reaction in an inert gas atmosphere and in a second polar solvent. After the reaction is complete, the second polar solvent is recovered. The second polar solvent is one or more of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, n-pentanol, quinoline, and ethylene glycol. The reaction temperature in step 2) is 150℃-230℃, and the reaction time is 6h~12h.

5. Use of a catalyst having a three-dimensional structure polynuclear phthalocyanine according to claim 1, characterized in that In step 3), washing is performed using an aqueous solution of an organic solvent and an acid; the organic solvent is one or more of methanol, ethanol, acetonitrile, ethyl acetate, and acetone; the aqueous solution of the acid is one or more of dilute hydrochloric acid, dilute sulfuric acid, and dilute nitric acid; the mass fraction of the dilute hydrochloric acid, dilute sulfuric acid, and dilute nitric acid is 5% to 10%; the drying is carried out under vacuum conditions, with a vacuum degree of 0.02 MPa to 0.04 MPa and a drying temperature of 70°C to 90°C.

6. Use of a catalyst having a three-dimensional structure polynuclear phthalocyanine according to claim 4, characterized in that The inert gas is nitrogen or argon.

7. Use of a catalyst having a three-dimensional structure polynuclear phthalocyanine according to claim 1, characterized in that The mass ratio of the three-dimensional polynuclear phthalocyanine catalyst to the nitrogen heterocyclic compound is 1:(8~10); the solvent is one of acetonitrile, toluene, p-xylene, mesitylene or chlorobenzene, and the amount of solvent used is 5 to 10 times the mass of the nitrogen heterocyclic compound.

8. Use of a catalyst having a three-dimensional structure polynuclear phthalocyanine according to claim 1, characterized in that The dehydrogenation reaction temperature is 80℃~140℃; the dehydrogenation reaction time is 20h~24h.

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