Preparation method of porphyrin conjugated microporous polymer and application thereof in sewage

Abstract

The application discloses a preparation method of a porphyrin-based cationic conjugated microporous polymer and application of the porphyrin-based cationic conjugated microporous polymer in degradation of phenolic pollutants, and belongs to the field of adsorption and degradation materials. The porous material is prepared by taking porphyrin and pyridine monomers as reaction units, and a novel conjugated microporous polymer is prepared through a Sonogashira coupling reaction, and then the porous material is modified through a quaternization reaction to obtain a cationic porous material, and the cationic porous material is named as LDPOs. The reaction condition of the application is easy to control, the environment is friendly, the process is simple, and the operability is good. The obtained porous material has good hydrophilicity and thermal stability, can efficiently degrade organic pollutants such as bisphenol A, bisphenol S, bisphenol F and hexafluorobisphenol A, and has a potential application prospect in sewage treatment.

Description

Technical Field

[0001] This invention relates to the field of adsorption and degradation materials, specifically to a method for preparing a porphyrin conjugated microporous polymer and its application in the rapid degradation of phenolic organic pollutants. Background Technology

[0002] Over the past few decades, with the rapid development of industry worldwide, water pollution has gradually become a global concern. Phenolic compounds are among the most widely used industrial raw materials in various manufacturing industries; however, they possess strong teratogenic and carcinogenic properties, and if inadvertently discharged into natural water bodies, they can cause serious harm to the ecological environment and human survival and development. Therefore, developing a method with excellent removal performance and cost-effectiveness is of paramount importance for purifying phenol-containing wastewater.

[0003] Currently, researchers have developed numerous technologies for the removal of phenolic organic pollutants, such as sedimentation, reverse osmosis, solvent extraction, electrolysis, biodegradation, ozonation, gamma-ray decomposition, photo-Fenton chromatography, photocatalysis, photoelectrocatalysis, and chemical catalysis, as well as the combination of anaerobic photocatalysis and membrane technology. Among these technologies, photocatalysis, as a green and sustainable technique, has advantages such as simplicity, recyclability, good reproducibility, high efficiency, and low cost, and has broad prospects for global environmental remediation. Therefore, it has attracted great attention from many researchers at home and abroad, and many related studies have been carried out. Although the photocatalytic degradation of organic pollutants has been proven to be effective, its industrial application still faces some shortcomings, such as a limited number of active sites and poor hydrophilicity, which limit its degradation performance. To better address existing problems and further improve the adsorption and degradation capacity of conjugated microporous polymers, we have rationally designed its structure by introducing hydrophilic groups through quaternization reactions, further enhancing the interaction between porous materials and phenolic pollutants, thereby significantly improving its adsorption and catalytic performance. Summary of the Invention

[0004] The purpose of this invention is to develop a novel conjugated microporous organic polymer material for degrading organic pollutants, thereby improving wastewater treatment and meeting the needs of wastewater treatment.

[0005] To achieve the objectives of this invention, the following technical solution is provided:

[0006] A method for preparing a porphyrin-based microporous organic polymer includes the following steps:

[0007] Step 1: Disperse the porphyrin-based parent unit and the pyridine-based linking unit into the first solvent and the second solvent, add the catalyst, and react at 60-160°C for 120-180 hours via the Sonogashira coupling reaction.

[0008] Step 2: After the reaction in Step 1 is completed, the filter cake is immediately filtered. The filter cake is washed with a third solvent and then filtered again. The washing and filtration are repeated. The filter cake is then vacuum dried to obtain a novel conjugated microporous polymer based on porphyrin.

[0009] Step 3: Add the conjugated microporous polymer obtained in Step 2 into the reaction vessel and mix it thoroughly with the haloalkanes. The target product, namely the cationic porous material, is obtained through a quaternization reaction.

[0010] Preferably, the parent unit is selected from at least one of the following structural formulas 1, 2 and 3:

[0011]

[0012] Preferably, the parent unit specifically comprises:

[0013]

[0014] The connecting unit is selected from one of the following structural formulas 4, 5 and 6:

[0015]

[0016] Preferably, the connection unit is:

[0017]

[0018] The halohydrocarbon is selected from one of the following structural formulas 7, 8 and 9:

[0019]

[0020] Preferably, the halohydrocarbon is:

[0021]

[0022] Preferably, the first solvent in step one is one or more of dichloromethane, N,N-dimethylformamide, tetrahydrofuran, diisopropylamine, 1,2-dichloroethane, 1,4-dioxane, chloroform, or dimethyl sulfoxide, with N,N-dimethylformamide being the most preferred.

[0023] Preferably, the second solvent in step one is one or more of diisopropylamine, triethylamine, diethylamine or ethylenediamine, with diisopropylamine being the most preferred.

[0024] Preferably, the catalyst in step one is one or more of CuI, KI, AgI or NaI, with CuI being the most preferred.

[0025] Preferably, the temperature after adding the catalyst in step one is controlled at 60-160°C, with a preferred temperature of 150°C.

[0026] Preferably, the heating reaction time in step one is controlled to be 12-96 hours, with a preferred time of 72 hours.

[0027] Preferably, the third solvent in step two is one or more of dichloromethane, N,N-dimethylformamide, tetrahydrofuran, 1,2-dichloroethane, methanol, 1,4-dioxane, chloroform, or dimethyl sulfoxide, with methanol being the most preferred.

[0028] Preferably, the porphyrin-based conjugated microporous polymer of the present invention can also be applied to wastewater treatment. Specifically, the porphyrin-based conjugated microporous polymer is used as a catalyst to degrade organic pollutants in wastewater; the organic pollutants are one or more of BPA, BPS, BPF and BPAF, preferably BPS.

[0029] Preferably, the porphyrin-based conjugated microporous polymer degrades organic pollutants under conditions of stirring, ultrasonication, vibration, and xenon lamp irradiation.

[0030] Preferably, the porphyrin-based conjugated microporous polymer can degrade BPA, BPS, and BPF within 10 minutes.

[0031] This invention provides a method for degrading organic pollutants in wastewater using porphyrin microporous organic polymers, with the following reaction formula:

[0032]

[0033] Beneficial effects: The microporous organic polymer synthesis method developed in this invention is simple, environmentally friendly, has excellent thermal stability and good hydrophilicity, and exhibits high efficiency in the removal of organic pollutants. It has good application prospects and great application value in the field of water treatment. Attached Figure Description

[0034] Figure 1 This is a scanning electron microscope image of the cationic porous material obtained by this invention.

[0035] Figure 2 This is a thermogravimetric diagram of the cationic porous material obtained by the present invention.

[0036] Figure 3 This is a diagram showing the adsorption and degradation of BPS by the cationic porous material obtained in this invention.

[0037] Figure 4 This is a diagram showing the adsorption and degradation of BPA in different water sources by the cationic porous material obtained in this invention.

[0038] Figure 5 This is a cyclic experimental diagram of BPA on the cationic porous material obtained in this invention.

[0039] Figure 6 This is a photocurrent test diagram of the cationic porous material obtained by the present invention. Detailed Implementation

[0040] The present invention will be described in detail below with reference to some specific embodiments. These embodiments are only used to illustrate the present invention and are not intended to limit the scope of the present invention. The preparation schemes in the embodiments are only preferred schemes, but the present invention is not limited to the embodiments.

[0041] Example 1

[0042] 5-10-15-20-tetra(4-bromophenyl)porphyrin (2.78 g, 3 mmol) and 2,5-diethynylpyridine (762 mg, 6 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (200 mL) and diisopropylamine (100 mL) were added, followed by CuI (114.2 mg, 0.6 mmol) and Pd(PPh3)4 (277 mg, 0.24 mmol), respectively. The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to give 2.3 g of a purplish-black product (LDPO-1), with a yield of 89%.

[0043] LDPO-1 (965 mg, 0.86 mmol) was added to a 250 mL Shrek tube, and N,N-dimethylformamide (80 mL) was added under a nitrogen atmosphere, followed by bromoethanol (6.85 g, 55.4 mmol). The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 1.04 g of the black product (LDPO-2), which is the porphyrin-based conjugated microporous polymer.

[0044] Example 2

[0045] 2,9-16-23-tetrabromophthalocyanine (2.49 g, 3 mmol) and 2,5-diethynylpyridine (762 mg, 6 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (200 mL) and triethylamine solution (100 mL) were added, followed by CuI (114.2 mg, 0.6 mmol) and Pd(PPh3)4 (277 mg, 0.24 mmol), respectively. The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to give 1.8 g of a purplish-black product (LDPO-1), with a yield of 76%.

[0046] LDPO-1 (965 mg, 0.86 mmol) was added to a 250 mL Shrek tube, and N,N-dimethylformamide (80 mL) was added under a nitrogen atmosphere, followed by bromoethanol (6.85 g, 55.4 mmol). The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 1.02 g of black product (LDPO-2), which is the porphyrin-based conjugated microporous polymer.

[0047] Example 3

[0048] 5-10-15-20-tetra(4-bromophenyl)porphyrin (2.78 g, 3 mmol) and 2,5-diethynylpyridine (762 mg, 6 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, THF (200 mL) and diisopropylamine solution (100 mL) were added, followed by CuI (114.2 mg, 0.6 mmol) and Pd(PPh3)4 (277 mg, 0.24 mmol), respectively. The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to give 2 g of a purplish-black product (LDPO-1), with a yield of 77%.

[0049] LDPO-1 (965 mg, 0.86 mmol) was added to a 250 mL Shrek tube, and N,N-dimethylformamide (80 mL) was added under a nitrogen atmosphere, followed by bromoethanol (6.85 g, 55.4 mmol). The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 1.04 g of black product (LDPO-2), which is the porphyrin-based conjugated microporous polymer.

[0050] Example 4

[0051] 5-10-15-20-tetra(4-bromophenyl)porphyrin (2.78 g, 3 mmol) and 2,5-diethynylpyridine (762 mg, 6 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (200 mL) and triethylamine solution (100 mL) were added, followed by AgI (140.8 mg, 0.6 mmol) and Pd(PPh3)4 (277 mg, 0.24 mmol), respectively. The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to give 2.1 g of a purplish-black product (LDPO-1), with a yield of 81%.

[0052] LDPO-1 (965 mg, 0.86 mmol) was added to a 250 mL Shrek tube, and N,N-dimethylformamide (80 mL) was added under a nitrogen atmosphere, followed by bromoethanol (6.85 g, 55.4 mmol). The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 1.0 g of the black product (LDPO-2), which is the porphyrin-based conjugated microporous polymer.

[0053] Example 5

[0054] 5-10-15-20-tetra(4-bromophenyl)porphyrin (2.78 g, 3 mmol) and 2,5-diethynylpyrimidine (768 mg, 6 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (200 mL) and diisopropylamine solution (100 mL) were added, followed by CuI (114.2 mg, 0.6 mmol) and Pd(PPh3)4 (277 mg, 0.24 mmol), respectively. The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to give 1.9 g of a purplish-black product (LDPO-1), with a yield of 73%.

[0055] LDPO-1 (965 mg, 0.86 mmol) was added to a 250 mL Shrek tube, and N,N-dimethylformamide (80 mL) was added under a nitrogen atmosphere, followed by (2-bromoethyl)trimethylammonium bromide (13.6 g, 55.4 mmol). The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 990 mg of (LDPO-2) black product, which is the porphyrin-based conjugated microporous polymer.

[0056] Example 6

[0057] 5-10-15-20-tetra(4-bromophenyl)porphyrin (2.78 g, 3 mmol) and 2,5-diethynylpyridine (762 mg, 6 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (200 mL) and diisopropylamine solution (100 mL) were added, followed by CuI (114.2 mg, 0.6 mmol) and Pd(PPh3)4 (277 mg, 0.24 mmol), respectively. The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to give 2.3 g of a purplish-black product (LDPO-1), with a yield of 89%.

[0058] LDPO-1 (965 mg, 0.86 mmol) was added to a 250 mL Shrek tube, and N,N-dimethylformamide (80 mL) was added under a nitrogen atmosphere, followed by 3-bromopropanol (7.64 g, 55.4 mmol). The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 1.07 g (LDPO-2) of black product, which is the porphyrin-based conjugated microporous polymer.

[0059] Example 7

[0060] 1,7-Dibromo-3,4,9,10-perylenetetracarboxylic dianhydride (1.64 g, 3 mmol) and 2,5-diethynylpyridine (762 mg, 6 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (200 mL) and diisopropylamine solution (100 mL) were added, followed by CuI (114.2 mg, 0.6 mmol) and Pd(PPh3)4 (277 mg, 0.24 mmol), respectively. The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to give 1.3 g of a purplish-black product (LDPO-1), with a yield of 68%.

[0061] LDPO-1 (965 mg, 0.86 mmol) was added to a 250 mL Shrek tube, and N,N-dimethylformamide (80 mL) was added under a nitrogen atmosphere, followed by bromoethanol (6.85 g, 55.4 mmol). The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 1.04 g of black product (LDPO-2), which is the porphyrin-based conjugated microporous polymer.

[0062] Example 8

[0063] 5-10-15-20-tetra(4-bromophenyl)porphyrin (2.78 g, 3 mmol) and 2,5-diethynylpyridine (762 mg, 6 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (200 mL) and diisopropylamine solution (100 mL) were added, followed by CuI (114.2 mg, 0.6 mmol) and Pd(PPh3)4 (277 mg, 0.24 mmol), respectively. The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to give 2.1 g of a purplish-black product (LDPO-1), with a yield of 81%.

[0064] LDPO-1 (965 mg, 0.86 mmol) was added to a 250 mL Shrek tube, and 1,4-dioxane (80 mL) was added under a nitrogen atmosphere, followed by bromoethanol (6.85 g, 55.4 mmol). The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 980 mg of the black product, which is the porphyrin-based conjugated microporous polymer.

[0065] Example 9

[0066] 2,9-16-23-tetrabromophthalocyanine (2.49 g, 3 mmol) and 2,5-diethynylpyrimidine (768 mg, 6 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (200 mL) and triethylamine solution (100 mL) were added, followed by AgI (140.8 mg, 0.6 mmol) and Pd(PPh3)4 (277 mg, 0.24 mmol), respectively. The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to give 1.65 g of a purplish-black product (LDPO-1), with a yield of 71%.

[0067] LDPO-1 (965 mg, 0.86 mmol) was added to a 250 mL Shrek tube, and N,N-dimethylformamide (80 mL) was added under a nitrogen atmosphere, followed by bromoethanol (6.85 g, 55.4 mmol). The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 1.04 g of black product (LDPO-2), which is the porphyrin-based conjugated microporous polymer.

[0068] Example 10

[0069] 2,9-16-23-tetrabromophthalocyanine (2.49 g, 3 mmol) and 1,4-diethynylbenzene (756 mg, 6 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (200 mL) and triethylamine solution (100 mL) were added, followed by AgI (140.8 mg, 0.6 mmol) and Pd(PPh3)4 (277 mg, 0.24 mmol), respectively. The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to give 1.7 g of a purplish-black product (LDPO-1), with a yield of 74%.

[0070] LDPO-1 (965 mg, 0.86 mmol) was added to a 250 mL Shrek tube, and N,N-dimethylformamide (80 mL) was added under a nitrogen atmosphere, followed by bromoethanol (6.85 g, 55.4 mmol). The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 1.04 g of black product (LDPO-2), which is the porphyrin-based conjugated microporous polymer.

[0071] Example 11

[0072] 5-10-15-20-tetra(4-bromophenyl)porphyrin (2.78 g, 3 mmol) and 1,4-diethynylbenzene (756 mg, 6 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (200 mL) and triethylamine solution (100 mL) were added, followed by AgI (140.8 mg, 0.6 mmol) and Pd(PPh3)4 (277 mg, 0.24 mmol), respectively. The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to give 1.7 g of a purplish-black product (LDPO-1), with a yield of 65%.

[0073] LDPO-1 (965 mg, 0.86 mmol) was added to a 250 mL Shrek tube, and N,N-dimethylformamide (80 mL) was added under a nitrogen atmosphere, followed by bromoethanol (6.85 g, 55.4 mmol). The mixture was refluxed at 100 °C for 72 hours. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with methanol and dried in a vacuum oven at 60 °C to obtain 1.0 g of the black product (LDPO-2), which is the porphyrin-based conjugated microporous polymer.

[0074] Application Example 1

[0075] BPA photodegradation experiment:

[0076] The polymer obtained in Example 1 was subjected to BPA degradation studies;

[0077] Test sample: The polymer obtained in Example 1;

[0078] Preparation of BPA solution: Prepare a BPA solution with a concentration of 10 ppm using pure water.

[0079] Experimental method: Add 8 mg of the test sample to the sample vial, add 16 mL of the prepared BPA solution, and carry out the degradation experiment under stirring. Take 1 mL of the mixture every 5 min, and after 20 min, take 1 mL of the mixture every 2 min under xenon lamp irradiation. After passing through a 0.22 μm filter membrane, perform HPLC analysis.

[0080] Application Example 2

[0081] BPS photodegradation experiment:

[0082] The polymer obtained in Example 1 was subjected to BPS degradation studies;

[0083] Test sample: The polymer obtained in Example 1;

[0084] Preparation of BPS solution: Prepare a BPS solution with a concentration of 10 ppm using pure water.

[0085] Experimental method: Add 8 mg of the test sample to the sample vial, add 16 mL of the prepared BPS solution, and carry out the degradation experiment under stirring. Take 1 mL of the mixture every 5 min, and after 20 min, take 1 mL of the mixture every 2 min under xenon lamp irradiation. After passing through a 0.22 μm filter membrane, perform HPLC analysis.

[0086] Application Example 3

[0087] BPF photodegradation experiment:

[0088] The polymer obtained in Example 1 was subjected to BPF degradation studies;

[0089] Test sample: The polymer obtained in Example 1;

[0090] Preparation of BPS solution: Prepare a BPF solution with a concentration of 10 ppm using pure water.

[0091] Experimental method: Add 8 mg of the test sample to the sample vial, add 16 mL of the prepared BPF solution, and carry out the degradation experiment under stirring. Take 1 mL of the mixture every 5 min, and after 20 min, take 1 mL of the mixture every 2 min under xenon lamp irradiation. After passing through a 0.22 μm filter membrane, perform HPLC analysis.

[0092] Application Example 4

[0093] BPAF photodegradation experiment:

[0094] The polymer obtained in Example 1 was subjected to BPAF degradation studies;

[0095] Test sample: The polymer obtained in Example 1;

[0096] Preparation of BPAF solution: Prepare a BPAF solution with a concentration of 10 ppm using pure water.

[0097] Experimental method: Add 8 mg of the test sample to the sample vial, add 16 mL of the prepared BPAF solution, and carry out the degradation experiment under stirring. Take 1 mL of the mixture every 5 min, and after 20 min, take 1 mL of the mixture every 2 min under xenon lamp irradiation. After passing through a 0.22 μm filter membrane, perform HPLC analysis.

[0098] Application Example 5

[0099] BPA photodegradation experiment:

[0100] The polymer obtained in Example 1 was subjected to BPA degradation studies;

[0101] Test sample: The polymer obtained in Example 1;

[0102] Preparation of BPA solution: Prepare a BPA solution with a concentration of 10 ppm using tap water.

[0103] Experimental method: Add 8 mg of the test sample to the sample bottle, add 16 mL of BPA solution prepared with tap water, and carry out the degradation experiment under stirring. Take 1 mL of the mixture every 5 min, and after 20 min, take 1 mL of the mixture every 2 min under xenon lamp irradiation. After passing through a 0.22 μm filter membrane, perform HPLC analysis.

[0104] Application Example 6

[0105] BPA photodegradation experiment:

[0106] The polymer obtained in Example 1 was subjected to BPA degradation studies;

[0107] Test sample: The polymer obtained in Example 1;

[0108] Preparation of BPA solution: A BPA solution with a concentration of 10 ppm was prepared using lake water.

[0109] Experimental method: Add 8 mg of the test sample to the sample bottle, add 16 mL of BPA solution prepared with lake water, and carry out the degradation experiment under stirring. Take 1 mL of the mixture every 5 min, and after 20 min, take 1 mL of the mixture every 2 min under xenon lamp irradiation. After passing through a 0.22 μm filter membrane, perform HPLC analysis.

[0110] Application Example 7

[0111] BPA photodegradation experiment:

[0112] The polymer obtained in Example 1 was subjected to BPA degradation studies;

[0113] Test sample: The polymer obtained in Example 1;

[0114] Preparation of BPA solution: A BPA solution with a concentration of 10 ppm was prepared using Yangtze River water.

[0115] Experimental method: Add 8 mg of the test sample to the sample bottle, add 16 mL of BPA solution prepared with Yangtze River water, and carry out the degradation experiment under stirring. Take 1 mL of the mixture every 5 min, and after 20 min, take 1 mL of the mixture every 2 min under xenon lamp irradiation. After passing through a 0.22 μm filter membrane, perform HPLC analysis.

[0116] Application Example 8

[0117] BPA photodegradation cycle experiment:

[0118] The polymer obtained in Example 1 was subjected to BPA degradation studies;

[0119] Test sample: The polymer obtained in Example 1;

[0120] Preparation of BPA solution: Prepare a BPA solution with a concentration of 10 ppm using pure water.

[0121] Experimental method: Add 40 mg of the test sample to the sample bottle, add 80 mL of BPA solution prepared with Yangtze River water, and carry out the degradation experiment under stirring. Take 1 mL of the mixture every 5 min, and after 20 min, take 1 mL of the mixture every 2 min under xenon lamp irradiation. After passing through a 0.22 μm filter membrane, perform HPLC analysis. After the experiment, recover the sample, filter and wash three times, ultrasonically wash with methanol, dry and carry out the next experiment.

[0122] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a porphyrin-based conjugated microporous polymer, characterized in that, Includes the following steps: Step 1: Disperse the porphyrin-based parent unit and the pyridine-based linking unit into the first solvent and the second solvent, add the catalyst, and react at 60-160°C for 120-180 hours via the Sonogashira coupling reaction. Step 2: After the reaction in Step 1 is completed, the filter cake is immediately filtered. The filter cake is washed with a third solvent and then filtered again. The washing and filtration are repeated. The filter cake is then vacuum dried to obtain a novel conjugated microporous polymer based on porphyrin. Step 3: Add the conjugated microporous polymer obtained in Step 2 into the reaction vessel and mix it thoroughly with one of the compounds in structural formulas 7, 8 and 9. The target product, namely the cationic porous material, is obtained through a quaternization reaction. The parent unit is selected from at least one of the following structural formulas 1 and 2: ； The connecting unit is selected from one of the following structural formulas 5 and 6: ； Structural formulas 7, 8, and 9 are respectively: 。 2. The preparation method of the porphyrin-based conjugated microporous polymer according to claim 1, characterized in that, In step one, the first solvent is dichloromethane. N,N- One or more of dimethylformamide, tetrahydrofuran, diisopropylamine, 1,2-dichloroethane, 1,4-dioxane, chloroform, or dimethyl sulfoxide; The second solvent is one or more of diisopropylamine, triethylamine, diethylamine or ethylenediamine; The third solvent is dichloromethane. N,N- One or more of dimethylformamide, tetrahydrofuran, 1,2-dichloroethane, methanol, 1,4-dioxane, chloroform, or dimethyl sulfoxide.

3. The preparation method of the porphyrin-based conjugated microporous polymer according to claim 1, characterized in that, The catalyst in step one is one or more of CuI, KI, AgI or NaI.

4. An application of the porphyrin-based conjugated microporous polymer according to claim 1, characterized in that, The porphyrin-based conjugated microporous polymer is used as a catalyst to degrade organic pollutants in wastewater; The organic pollutant is one or more of BPA, BPS, BPF and BPAF.

5. The application of the porphyrin-based conjugated microporous polymer according to claim 4, characterized in that, The porphyrin-based conjugated microporous polymer degrades organic pollutants under conditions of stirring, ultrasound, vibration, and xenon lamp irradiation.

6. The application of the porphyrin-based conjugated microporous polymer according to claim 5, characterized in that, The porphyrin-based conjugated microporous polymer degrades BPA, BPS, or BPF within 10 minutes.

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