Preparation method of BODIPY porous organic polymer and application thereof in sewage treatment

Abstract

The application discloses a preparation method of a porous organic polymer based on BODIPY and application of the porous organic polymer in sewage treatment, and belongs to the technical fields of porous material preparation and sewage treatment. The polymer is prepared by the following method: (1) after dispersing a mother unit BDPA and a reaction group monomer into N,N-dimethylformamide and diisopropylamine, a catalyst is quickly added, and after catalytic reaction, further reaction is carried out with a modified group monomer; (2) based on a Sonogashira coupling method, coupling reaction is carried out at 60-160 DEG C for 120-180 hours; (3) after reaction, suction filtration is carried out immediately, the filter cake is washed with stirring for 1-4 hours and then suction filtered, and after repeated washing and suction filtering, the filter cake is vacuum dried to obtain the material. The preparation condition of the application is easy to control, the environment is friendly, the process is simple, the operability is good, the obtained material has good hydrophilicity, high thermal stability, can efficiently adsorb and degrade organic pollutants such as rhodamine B (RhB) and methylene blue (MB), and thus sewage purification is realized.

Description

Technical Field

[0001] This invention relates to the fields of porous material preparation and wastewater treatment technology, specifically to a method for preparing a porous organic polymer based on BODIPY and its application in wastewater treatment. Background Technology

[0002] Over the past few decades, rapid population growth and industrialization have led to environmental pollution and energy shortages, making water pollution a hot research topic both domestically and internationally. Among various pollutants, organic dyes are a major component of improperly treated wastewater from the paper, food, plastics, cosmetics, and textile industries. They possess strong biotoxicity and carcinogenicity, posing serious threats to the ecological environment and human survival and development.

[0003] Many technologies have been developed for removing pollutants from water bodies, such as sedimentation, reverse osmosis, solvent extraction, electrolysis, biodegradation, ozonation, sonication, photo-Fenton chromatography, photoelectrocatalysis, and chemical catalysis, as well as the combination of anaerobic photocatalysis and membrane technology. Among these technologies, photocatalytic degradation technology, as the simplest, most economical, most recyclable, and low-cost green and sustainable technology, has broad prospects for global environmental remediation and has attracted much attention and research from researchers both domestically and internationally. Although the photocatalytic degradation of organic pollutants has been proven to be effective, its industrial application still faces some limitations, such as a limited number of active sites and poor hydrophilicity, which restrict its degradation performance. To better address existing problems and further improve the adsorption and degradation capacity of polymers, we have rationally designed the polymer structure.

[0004] Therefore, how to prepare a functional material that can quickly and completely remove pollutants from water remains a huge challenge for researchers worldwide. Summary of the Invention

[0005] The purpose of this invention is to develop a porous organic polymer material based on 4,4-difluoro-boradiazaindacene (BODIPY) to improve wastewater treatment and meet its requirements. The porous organic polymer developed in this invention has a simple synthesis method, is environmentally friendly, exhibits excellent thermal stability and good hydrophilicity, and demonstrates highly efficient degradation capabilities in the removal of organic pollutants. It shows promising application prospects and significant value in the field of water treatment.

[0006] To achieve the objectives of this invention, the following technical solution is provided:

[0007] A method for preparing a BODIPY-based porous organic polymer, characterized by comprising the following steps:

[0008] S1. First, benzoyl chloride (2.8 g, 20 mmol) and 2,4-dimethylpyrrole (3.7 g, 40 mmol) were dispersed in dichloromethane solvent. Triethylamine (20 mL) and boron trifluoride diethyl ether (20 mL) were added under ice bath conditions, and the mixture was stirred overnight at room temperature. After the reaction was complete, the mixture was extracted with dichloromethane and subjected to column chromatography (DCM:PE = 1:2) to give 2.0 g of BDP product, with a yield of 31%.

[0009] S2. BDP (4.0 g, 12.4 mmol) was dispersed in dichloromethane, and N-iodobutyramide (6.7 g, 30 mmol) was added dropwise under ice bath conditions. The mixture was stirred at room temperature for 5 h, and column chromatography (DCM:PE = 1:2) was performed to obtain 6.0 g of BDPI product, with a yield of 84%.

[0010] S3. BDPI (6.8 g, 11.8 mmol), Pd(pph3)4Cl2 (874.8 mg, 1.2 mmol), PPh3 (547 mg, 2.2 mmol), and CuI (711 mg, 7.9 mmol) were added to diisopropylamine (100 mL) and tetrahydrofuran (200 mL). After stirring, azidotrimethylsilane (10.0 g, 101.8 mmol) was added. The mixture was stirred at 60 °C for 4 h. The product was then subjected to column chromatography (DCM) to obtain 5.2 g of BDPSi product, 85%.

[0011] S4. Disperse BDPSi in tetrahydrofuran (100 mL), add tetrabutylammonium fluoride at -78 °C, react for 4 h, extract and then perform column chromatography (DCM:PE = 1:5) to obtain 3.0 g of BDPA product, 85%.

[0012] S5. After dispersing the parent unit BDPA and the reactive monomer in the first solvent and the second solvent, the catalyst is quickly added. After the reaction is completed, it reacts further with the modified monomer.

[0013] S6. The solution after mixing in step S5 is coupled at 60–160 °C for 120–180 hours using the Sonogashira method;

[0014] S7. After the reaction is complete, the filter cake is immediately filtered. The filter cake is washed with a third solvent and then filtered again. After repeated washing and filtration, the filter cake is vacuum dried to obtain the target product, which is based on BODIPY porous organic polymer.

[0015] Preferably, in the method for preparing the BODIPY-based porous organic polymer, the parent unit BDPA is selected from at least one of the following structural formulas 1, 2, and 3:

[0016]

[0017] Preferably, the parent unit BDPA is selected from the following structural formula:

[0018]

[0019] Preferably, the reactive monomer is selected from one of the following structural formulas 4, 5, and 6:

[0020]

[0021] Preferably, the reactive monomer is selected from the following structural formulas:

[0022]

[0023] Preferably, the modified monomer is selected from one of the following structural formulas 7, 8, and 9:

[0024]

[0025] Preferably, the modified monomer group is selected from the following structural formulas:

[0026]

[0027] Preferably, in the preparation method of the BODIPY porous organic polymer, the first solvent in step 5 is one or more of dichloromethane, tetrahydrofuran, 1,2-dichloroethane, N,N-dimethylformamide, chloroform, 1,4-dioxane, or dimethyl sulfoxide, preferably N,N-dimethylformamide.

[0028] Preferably, in the preparation method of the BODIPY porous organic polymer, the second solvent in step 5 is one or more of triethylamine, diisopropylamine, diethylamine or ethylenediamine, preferably diisopropylamine.

[0029] Preferably, in the preparation method based on BODIPY porous organic polymer, the catalyst in step 5 is one or more of CuI, KI, AgI or NaI, with CuI being preferred.

[0030] Preferably, in step 6, the temperature is controlled at 60–160°C after the catalyst is added, with a preferred temperature of 150°C.

[0031] Preferably, in the preparation method based on BODIPY porous organic polymer in step 6, the heating reaction time is controlled to be 12-96 h, with a preferred time of 72 h.

[0032] Preferably, in the preparation method of the BODIPY porous organic polymer, the third solvent in step 7 is one or more of methanol, dichloromethane, tetrahydrofuran, 1,2-dichloroethane, N,N-dimethylformamide, 1,4-dioxane, chloroform, or dimethyl sulfoxide, with methanol being preferred.

[0033] Preferably, in the preparation method of the BODIPY-based porous organic polymer, the BODIPY-based porous organic polymer is used in wastewater treatment.

[0034] Preferably, in the application of the BODIPY-based porous organic polymer, the BODIPY-based porous organic polymer is used as a catalyst to degrade organic pollutants in wastewater; the organic pollutants are one or more of MB and RhB, preferably MB.

[0035] The application of the BODIPY-based porous organic polymer involves the degradation of organic pollutants under conditions of stirring, ultrasound, vibration, and xenon lamp irradiation.

[0036] This invention provides an application of BODIPY porous organic polymer in the removal of organic pollutants from wastewater, capable of degrading MB within 15 minutes and RhB within 30 minutes. The reaction formula is as follows:

[0037] Attached Figure Description

[0038] Figure 1 It is a scanning electron microscope image of porous organic polymers.

[0039] Figure 2 This is a thermogravimetric diagram of a porous organic polymer.

[0040] Figure 3 This is a comparison diagram of the adsorption and degradation of MB by porous organic polymers.

[0041] Figure 4 This is a graph showing the adsorption and degradation of MB in different water sources by porous organic polymers.

[0042] Figure 5 This is a diagram of a cyclic experiment on MB using porous organic polymers.

[0043] Figure 6 This is a graph showing the adsorption and degradation of RhB at different concentrations by porous organic polymers. Detailed Implementation Plan

[0044] 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.

[0045] Example 1

[0046] BDPA (1.78 g, 4.8 mmol) and 1,3,5-trifluoro-2,4,6-triiodobenzene (1.63 g, 3.2 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (150 mL) and diisopropylamine solution (100 mL) were added, followed by CuI (54.7 mg, 0.288 mmol) and Pd(PPh3)4 (222 mg, 0.19 mmol), respectively. The mixture was refluxed at 100 °C for 72 h. 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 1.29 g of a purplish-black product (LBFD-1).

[0047] LBFD-1 (965 mg) was added to a 500 mL Shrek tube, and N,N-dimethylformamide (250 mL) was added under a nitrogen atmosphere, followed by Calixarene-OH (1.285 g, 1.5 mmol). The mixture was refluxed at 100 °C for 72 h. 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 1.12 g of black product (LBFD-2).

[0048] Example 2

[0049] 5-10-15-20-tetratetra(4-ethynylphenyl)porphyrin (1.4 g, 2 mmol) and 1,3,5-trifluoro-2,4,6-triiodobenzene (3.05 g, 6 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (150 mL) and diisopropylamine solution (100 mL) were added, followed by CuI (54.7 mg, 0.288 mmol) and Pd(PPh3)4 (222 mg, 0.19 mmol), respectively. The mixture was refluxed at 100 °C for 72 h. 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 1.19 g of a purplish-black product (LBFD-1).

[0050] LBFD-1 (965 mg) was added to a 500 mL Shrek tube, and N,N-dimethylformamide (250 mL) was added under a nitrogen atmosphere, followed by Calixarene-OH (1.285 g, 1.5 mmol). The mixture was refluxed at 100 °C for 72 h. 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 1.10 g of black product (LBFD-2).

[0051] Example 3

[0052] BDPA (1.78 g, 4.8 mmol) and 1,3,5-trifluoro-2,4,6-triiodobenzene (1.63 g, 3.2 mmol) were added to a 500 mL Shrek flask. Tetrahydrofuran (150 mL) and diisopropylamine solution (100 mL) were added under a nitrogen atmosphere, followed by CuI (54.7 mg, 0.288 mmol) and Pd(PPh3)4 (222 mg, 0.19 mmol), respectively. The mixture was refluxed at 100 °C for 72 h. 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 1.29 g of a purplish-black product (LBFD-1).

[0053] LBFD-1 (965 mg) was added to a 500 mL Shrek tube, and N,N-dimethylformamide (250 mL) was added under a nitrogen atmosphere, followed by Calixarene-Br (1.662 g, 1.5 mmol). The mixture was refluxed at 100 °C for 72 h. 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 (LBFD-2).

[0054] Example 4

[0055] Tris(4-ethynylphenyl)benzene (951 mg, 3 mmol) and 1,3,5-trifluoro-2,4,6-triiodobenzene (2.29 g, 4.5 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (150 mL) and diisopropylamine solution (100 mL) were added, followed by CuI (54.7 mg, 0.288 mmol) and Pd(PPh3)4 (222 mg, 0.19 mmol), respectively. The mixture was refluxed at 100 °C for 72 h. 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 1.12 g of a purplish-black product (LBFD-1).

[0056] LBFD-1 (965 mg) was added to a 500 mL Shrek tube, and N,N-dimethylformamide (250 mL) was added under a nitrogen atmosphere, followed by Calixarene-OH (1.285 g, 1.5 mmol). The mixture was refluxed at 100 °C for 72 h. 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 1.11 g of black product (LBFD-2).

[0057] Example 5

[0058] BDPA (1.78 g, 4.8 mmol) and 1,3,5-trichloro-2,4,6-triiodobenzene (1.78 g, 3.2 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (150 mL) and diisopropylamine solution (100 mL) were added, followed by CuI (54.7 mg, 0.288 mmol) and Pd(PPh3)4 (222 mg, 0.19 mmol), respectively. The mixture was refluxed at 100 °C for 72 h. 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 1.09 g of a purplish-black product (LBFD-1).

[0059] LBFD-1 (965 mg) was added to a 500 mL Shrek tube, and N,N-dimethylformamide (250 mL) was added under a nitrogen atmosphere, followed by Calixarene-OH (1.285 g, 1.5 mmol). The mixture was refluxed at 100 °C for 72 h. 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 1.12 g of black product (LBFD-2).

[0060] Example 6

[0061] BDPA (1.78 g, 4.8 mmol) and 1,3,5-trifluoro-2,4,6-triiodobenzene (1.63 g, 3.2 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (150 mL) and triethylamine solution (100 mL) were added, followed by CuI (54.7 mg, 0.288 mmol) and Pd(PPh3)4 (222 mg, 0.19 mmol), respectively. The mixture was refluxed at 100 °C for 72 h. 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 1.29 g of a purplish-black product (LBFD-1).

[0062] LBFD-1 (965 mg) was added to a 500 mL Shrek tube, and N,N-dimethylformamide (250 mL) was added under a nitrogen atmosphere, followed by Calixarene-Br (1.662 g, 1.5 mmol). The mixture was refluxed at 100 °C for 72 h. 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 (LBFD-2).

[0063] Example 7

[0064] BDPA (1.78 g, 4.8 mmol) and 1,3,5-trifluoro-2,4,6-triiodobenzene (1.63 g, 3.2 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (150 mL) and diisopropylamine solution (100 mL) were added, followed by AgI (67.58 mg, 0.288 mmol) and Pd(PPh3)4 (222 mg, 0.19 mmol), respectively. The mixture was refluxed at 100 °C for 72 h. 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 1.25 g of a purplish-black product (LBFD-1).

[0065] LBFD-1 (965 mg) was added to a 500 mL Shrek tube, and N,N-dimethylformamide (250 mL) was added under a nitrogen atmosphere, followed by Calixarene-Br (1.662 g, 1.5 mmol). The mixture was refluxed at 100 °C for 72 h. 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 (LBFD-2).

[0066] Example 8

[0067] BDPA (1.78 g, 4.8 mmol) and 1,3,5-tribromo-2,4,6-triiodobenzene (2.24 g, 3.2 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (150 mL) and diisopropylamine solution (100 mL) were added, followed by CuI (54.7 mg, 0.288 mmol) and Pd(PPh3)4 (222 mg, 0.19 mmol), respectively. The mixture was refluxed at 100 °C for 72 h. 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 987 mg of a purplish-black product (LBFD-1).

[0068] LBFD-1 (965 mg) was added to a 500 mL Shrek tube, and N,N-dimethylformamide (250 mL) was added under a nitrogen atmosphere, followed by Calixarene-OH (1.285 g, 1.5 mmol). The mixture was refluxed at 100 °C for 72 h. 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 1.12 g of black product (LBFD-2).

[0069] Example 9

[0070] BDPA (1.78 g, 4.8 mmol) and 1,3,5-trifluoro-2,4,6-triiodobenzene (1.63 g, 3.2 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (150 mL) and diisopropylamine solution (100 mL) were added, followed by CuI (54.7 mg, 0.288 mmol) and Pd(PPh3)4 (222 mg, 0.19 mmol), respectively. The mixture was refluxed at 100 °C for 72 h. 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 1.29 g of a purplish-black product (LBFD-1).

[0071] LBFD-1 (965 mg) was added to a 500 mL Shrek tube, and N,N-dimethylformamide (250 mL) was added under a nitrogen atmosphere, followed by Calixarene-Br (1.662 g, 1.5 mmol). The mixture was refluxed at 100 °C for 72 h. 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 (LBFD-2).

[0072] Example 10

[0073] BDPA (1.78 g, 4.8 mmol) and 1,3,5-trifluoro-2,4,6-triiodobenzene (1.63 g, 3.2 mmol) were added to a 500 mL Shrek flask. Under a nitrogen atmosphere, N,N-dimethylformamide (150 mL) and diisopropylamine solution (100 mL) were added, followed by CuI (54.7 mg, 0.288 mmol) and Pd(PPh3)4 (222 mg, 0.19 mmol), respectively. The mixture was refluxed at 100 °C for 72 h. 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 1.29 g of a purplish-black product (LBFD-1).

[0074] LBFD-1 (965 mg) was added to a 500 mL Shrek tube, and N,N-dimethylformamide (250 mL) was added under a nitrogen atmosphere, followed by β-CD (875 mg, 0.771 mmol). The mixture was refluxed at 100 °C for 72 h. 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 of black product (LBFD-2).

[0075] Application Example 1

[0076] MB photodegradation experiment:

[0077] The polymer obtained in Example 1 was subjected to MB degradation studies;

[0078] Test sample: The porous organic polymer obtained in Example 1;

[0079] Preparation of MB solution: Prepare an MB solution with a concentration of 200 ppm using pure water.

[0080] Experimental method: Add 7 mg of the test sample to the sample bottle, add 14 mL of the prepared MB 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 5 min under xenon lamp irradiation. After passing through a 0.22 μm filter membrane, perform ultraviolet-visible spectroscopy analysis.

[0081] Application Example 2

[0082] RhB photodegradation experiment:

[0083] The polymer obtained in Example 1 was subjected to RhB degradation studies;

[0084] Test sample: The porous organic polymer obtained in Example 1;

[0085] Preparation of RhB solution: Prepare an RhB solution with a concentration of 50 ppm using pure water.

[0086] Experimental method: Add 7 mg of the test sample to the sample bottle, add 14 mL of the prepared RhB 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 5 min under xenon lamp irradiation. After passing through a 0.22 μm filter membrane, perform ultraviolet-visible spectroscopy analysis.

[0087] Application Example 3

[0088] RhB photodegradation experiment:

[0089] The polymer obtained in Example 1 was subjected to RhB degradation studies;

[0090] Test sample: The porous organic polymer obtained in Example 1;

[0091] Preparation of RhB solution: Prepare an RhB solution with a concentration of 100 ppm using pure water.

[0092] Experimental method: Add 7 mg of the test sample to the sample bottle, add 14 mL of the prepared RhB 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 5 min under xenon lamp irradiation. After passing through a 0.22 μm filter membrane, perform ultraviolet-visible spectroscopy analysis.

[0093] Application Example 4

[0094] MB photodegradation experiment:

[0095] The polymer obtained in Example 1 was subjected to MB degradation studies;

[0096] Test sample: The porous organic polymer obtained in Example 1;

[0097] Preparation of MB solution: Prepare an MB solution with a concentration of 200 ppm using tap water.

[0098] Experimental method: Add 7 mg of the test sample to the sample bottle, add 14 mL of MB solution prepared with tap water, and carry out the degradation experiment under stirring conditions; take 1 mL of the mixture every 5 min, and after 20 min, take 1 mL of the mixture every 5 min under xenon lamp irradiation, and perform ultraviolet-visible spectroscopy analysis after passing through a 0.22 μm filter membrane.

[0099] Application Example 5

[0100] MB photodegradation experiment:

[0101] The polymer obtained in Example 1 was subjected to MB degradation studies;

[0102] Test sample: The porous organic polymer obtained in Example 1;

[0103] Preparation of MB solution: Prepare an MB solution with a concentration of 200 ppm using lake water.

[0104] Experimental method: Add 7 mg of the test sample to the sample bottle, add 14 mL of MB 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 ultraviolet-visible spectroscopy analysis.

[0105] Application Example 6

[0106] MB photodegradation experiment:

[0107] The polymer obtained in Example 1 was subjected to MB degradation studies;

[0108] Test sample: The porous organic polymer obtained in Example 1;

[0109] Preparation of MB solution: Prepare an MB solution with a concentration of 200 ppm using Yangtze River water.

[0110] Experimental method: Add 7 mg of the test sample to the sample bottle, add 14 mL of MB 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 5 min under xenon lamp irradiation. After passing through a 0.22 μm filter membrane, perform ultraviolet-visible spectroscopy analysis.

[0111] Application Example 7

[0112] MB photodegradation cycle experiment:

[0113] The polymer obtained in Example 1 was subjected to MB degradation studies;

[0114] Test sample: The porous organic polymer obtained in Example 1;

[0115] Preparation of MB solution: Prepare an MB solution with a concentration of 200 ppm using pure water.

[0116] Experimental method: Add 50 mg of the test sample to the sample bottle, add 100 mL of MB solution prepared with Yangtze River water, and carry out the degradation experiment under stirring. Take 1 mL of the mixture every 5 min. After 20 min, take 1 mL of the mixture every 5 min under xenon lamp irradiation. After passing through a 0.22 μm filter membrane, perform ultraviolet-visible spectroscopy analysis. After the experiment, recover the sample, filter and wash three times, ultrasonically wash with methanol, dry and carry out the next experiment.

[0117] 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 porous organic polymers based on BODIPY, characterized in that, Includes the following steps: S1. After dispersing the parent unit BDPA and the reactive monomer in the first solvent and the second solvent, the catalyst is quickly added. After the catalytic reaction is completed, it reacts further with the modified monomer. S2. The solution after mixing in step S1 is coupled at 60–160 °C for 120–180 hours using the Sonogashira method; S3. After the reaction is complete, the filter cake is immediately filtered. The filter cake is washed with a third solvent and then filtered again. After repeated washing and filtration, the filter cake is vacuum dried to obtain the target product, which is based on BODIPY porous organic polymer. The parent unit BDPA is selected from the following structural formula: ； The reactive monomer is selected from one of the following structural formulas 4, 5, and 6: ； The modified monomer is selected from one of the following structural formulas 7, 8, and 9: 。 2. The preparation method based on BODIPY porous organic polymer according to claim 1, characterized in that, In step S1, the first solvent is dichloromethane, tetrahydrofuran, and 1,2-dichloroethane. N,N- One or more of dimethylformamide, chloroform, 1,4-dioxane or dimethyl sulfoxide; The second solvent is one or more of triethylamine, diisopropylamine, diethylamine or ethylenediamine; The third solvent is methanol, dichloromethane, tetrahydrofuran, and 1,2-dichloroethane. N,N- One or more of dimethylformamide, 1,4-dioxane, chloroform, or dimethyl sulfoxide.

3. The preparation method based on BODIPY porous organic polymer according to claim 1, characterized in that, In step S1, the temperature is controlled to be 60–160°C after the catalyst is added. The catalytic heating reaction time was controlled to be 12–96 h.

4. An application of a BODIPY-based porous organic polymer according to any one of claims 1-3, characterized in that, The BODIPY-based porous organic polymer is used to degrade organic pollutants in wastewater. The organic pollutant is one or more of MB and RhB.

5. The application of the BODIPY porous organic polymer according to claim 4, characterized in that, The BODIPY porous organic polymer is used to degrade organic pollutants under conditions of stirring, ultrasound, vibration, and xenon lamp irradiation.

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