Preparation method and application of tetrastyryl porous organic polymer

Abstract

The application belongs to the technical fields of porous material preparation and sewage treatment, and discloses a preparation method of a tetraphenylstyrene-based porous organic polymer and application thereof, and the porous material is prepared through Suzuki coupling and Friedel-Crafts alkylation reaction: (1) after tetraphenylstyrene units and reaction groups are reacted, the units are dispersed in a first solvent together with a linking group unit, stirring is conducted until all are dissolved, a catalyst is quickly added, and a mixed solution is obtained after uniform mixing; (2) Friedel-Crafts alkylation reaction is conducted on the mixed solution; (3) after the reaction is completed, suction filtration is immediately conducted, the obtained filter cake is washed with a second solvent and then subjected to suction filtration, and after repeated washing and suction filtration, the filter cake is vacuum dried to obtain a target product. 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 high stability, has a high specific surface area, can efficiently adsorb organic pollutants such as methylene blue and rhodamine B, and thus realizes sewage purification.

Description

Technical Field

[0001] This invention belongs to the field of porous material preparation and wastewater treatment technology, and in particular, a method for preparing a porous organic polymer based on tetraphenylethylene and its application in wastewater. Background Technology

[0002] Over the past few decades, with the rapid development of industry worldwide, water pollution has gradually become a global concern. Among various pollutants, organic dyes are a major component of wastewater generated from improper treatment in 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] Adsorption technology, as one of the simplest, most economical, and most recyclable methods, has attracted much attention and research from researchers both domestically and internationally. Various porous materials, such as activated carbon, zeolite, and MOF, have been used as adsorption separation materials; however, their small adsorption capacity, slow removal rate, sensitivity to moisture, and instability limit their application. In contrast, porous organic polymers (POPs) possess characteristics such as large specific surface area, uniform porosity distribution, low density, and strong versatility, exhibiting excellent advantages in the efficient removal of dyes and making them a promising adsorbent. Using Friedel-Crafts alkylation, organic porous polymers, due to their large specific surface area, hydrophobicity, and porous structure, have become a highly promising adsorbent material for adsorbing organic pollutants in water. However, although some synthesized organic porous polymers can achieve high specific surface areas, it is difficult to further improve their adsorption capacity when used for organic matter adsorption. It is well known that organic dye molecules typically have good planar conjugated structures and specific polar functional groups. To improve the adsorption rate of polymers for organic dyes, the polymer structure has been rationally designed.

[0004] Therefore, it is very important to develop a functional material with a large specific surface area and ultra-high adsorption capacity to completely remove organic dyes from wastewater. Summary of the Invention

[0005] The purpose of this invention is to provide a novel three-dimensional porous organic polymer material for adsorbing organic pollutants, thereby improving wastewater treatment and meeting its requirements. The series of porous organic polymers developed in this invention have simple synthesis methods, large specific surface areas, and excellent thermal stability. They exhibit highly efficient adsorption capacity for organic dye removal and have promising application prospects and significant application value in the field of water treatment.

[0006] The technical solution adopted in this invention is:

[0007] A method for preparing a tetraphenylethylene porous organic polymer, wherein the tetraphenylethylene porous organic polymer is prepared by first coupling tetraphenylethylene units with reactive groups (Suzuki), and then reacting them with linking groups via a Friedel-Crafts alkylation reaction. The specific reaction route is shown below:

[0008]

[0009] Furthermore, the preparation method based on tetraphenylethylene porous organic polymer specifically includes the following steps:

[0010] Step S1: After coupling the tetraphenylethylene unit and the reactive group Suzuki, an intermediate product is obtained. The intermediate product is then dispersed with the linking group unit in the first solvent. After stirring until completely dissolved, the catalyst is quickly added and mixed evenly to obtain a mixed solution.

[0011] Step S2: The mixed solution obtained in step S1 is subjected to a Friedel-Crafts alkylation reaction at a temperature of 30–80°C for a reaction time of 12–72 h, preferably at a temperature of 65°C for a reaction time of 48 h.

[0012] Step S3: After the reaction is complete, the filter cake is immediately filtered. The resulting filter cake is washed with a second solvent and then filtered again. After repeated washing and filtration, the filter cake is dried under vacuum to obtain the target product, which is based on tetraphenylethylene porous organic polymer and named POP-TPEs.

[0013] Furthermore, in step S1, the molar ratio of tetraphenylethylene unit to linking group unit is 1:(0.5-2), preferably 1:2.

[0014] Furthermore, the tetraphenylethylene unit is one of the following structural formulas:

[0015]

[0016] The reactive group is one or more of pinacol diester, benzothiadiazole borate, p-phenylboronic acid, or p-bromophenylboronic acid.

[0017] The linking group unit is one of the following structural formulas:

[0018]

[0019] Furthermore, the tetraphenylethylene unit is preferably...

[0020]

[0021] The reactive group is preferably pinacol diester;

[0022] The linker unit is preferably

[0023]

[0024] Further, in step S1, the first solvent is one or more of dichloromethane, N,N-dimethylformamide, tetrahydrofuran, 1,2-dichloroethane, 1,4-dioxane, chloroform, or dimethyl sulfoxide, preferably chloroform.

[0025] Furthermore, the catalyst in step S1 is one or more of FeCl3, AlCl3, boron trifluoride or niobium pentachloride, preferably FeCl3.

[0026] Further, in step S3, the second solvent is one or more of dichloromethane, methanol, N,N-dimethylformamide, tetrahydrofuran, or diethyl ether, preferably methanol.

[0027] Furthermore, the vacuum drying of the filter cake in step S3 specifically involves vacuum drying the filter cake at 60–120°C for 1 day.

[0028] An application of the tetraphenylethylene porous organic polymer as described above, specifically its application in wastewater treatment.

[0029] Furthermore, the porous organic polymer based on tetraphenylethylene is used as an adsorbent to adsorb organic pollutants in wastewater; the organic pollutants are one or more of Rhodamine B, methylene blue, and methyl orange, preferably methylene blue.

[0030] Furthermore, the organic pollutants based on tetraphenylethylene porous organic polymer are adsorbed under stirring, ultrasonic and / or oscillation conditions, preferably under ultrasonic conditions.

[0031] The beneficial effects of this invention are as follows: The invention is rationally designed, the preparation method is simple, the conditions are easily controlled, and it is environmentally friendly; the porous organic polymer based on tetraphenylethylene obtained by this invention has advantages such as large specific surface area and excellent thermal stability, and exhibits highly efficient adsorption capacity in the removal of organic dyes, with an adsorption capacity of up to 600 mg·g for Rhodamine B and methylene blue. -1 The above have good application prospects and great application value in the field of water treatment. Attached Figure Description

[0032] To more clearly illustrate the specific embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the specific embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of the present invention. For those skilled in the art, other drawings can be obtained from these drawings without creative effort.

[0033] Figure 1 These are infrared spectra of POP-TPEs in different proportions;

[0034] Figure 2 These are scanning electron microscope images of POP-TPEs with different proportions. In the figures, a is Example 1, b is Example 4, c is Example 6, and d is Example 8.

[0035] Figure 3 These are thermogravimetric maps of POP-TPEs in different proportions;

[0036] Figure 4 The graph shows the MB adsorption performance of POP-TPEs with different proportions. In the graph, a represents Example 1, b represents Example 4, c represents Example 6, and d represents Example 8.

[0037] Figure 5 The graph shows the BET distribution of POP-TPEs at different proportions. In the graph, a represents Example 1, b represents Example 4, c represents Example 6, and d represents Example 8.

[0038] Figure 6 These are the adsorption kinetic fitting curves of POP-TPEs with different proportions. In the figure, a represents Example 1, b represents Example 4, c represents Example 6, and d represents Example 8. Detailed Implementation

[0039] It should be noted that the following detailed descriptions are illustrative and intended to provide further explanation of this application. Unless otherwise specified, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application pertains.

[0040] It should be noted that the terminology used herein is for the purpose of describing particular implementations only and is not intended to limit the exemplary implementations according to this application. As used herein, the singular form includes the plural form unless the context clearly indicates otherwise. Furthermore, it should be understood that when the terms "comprising" and / or "including" are used in this description, they indicate the presence of features, steps, operations, devices, components, and / or combinations thereof.

[0041] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0042] Example 1

[0043] Tetrabromotetraphenylene (10 g, 15.4 mmol) and pinacol diester (10 g, 30 mmol) were added to a 1000 mL Shrek flask. Under a nitrogen atmosphere, THF (400 mL) and 2 M K2CO3 aqueous solution (80 mL) were added, followed by tetratetraphenylphosphine palladium (1.34 g, 1.2 mmol). The mixture was refluxed at 65 °C for 36 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to give 8.1 g of yellow-green product (TPE-1), with a yield of 98%.

[0044] TPE-1 (1000 mg, 1.85 mmol) and p-dichlorobenzyl (1050 mg, 6 mmol) were added to a 250 mL Shrek tube. Dry chloroform (100 mL) was added under a nitrogen atmosphere, followed by the addition of FeCl3 (4680 mg, 28.8 mmol) in portions. The mixture was refluxed at 65 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to obtain 1.7 g of reddish-brown product.

[0045] Example 2

[0046] Tetrabromotetraphenylene (10 g, 15.4 mmol) and phenylboronic acid (3.6 g, 30 mmol) were added to a 1000 mL Shrek flask. Under a nitrogen atmosphere, THF (400 mL) and 2 M K2CO3 aqueous solution (80 mL) were added, followed by tetratetraphenylphosphine palladium (1.34 g, 1.2 mmol). The mixture was refluxed at 65 °C for 36 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to give 7.5 g of yellow-green product (TPE-1), with a yield of 90%.

[0047] TPE-1 (1000 mg, 1.85 mmol) and p-dichlorobenzyl (1050 mg, 6 mmol) were added to a 250 mL Shrek tube. Dry chloroform (100 mL) was added under a nitrogen atmosphere, followed by the addition of FeCl3 (4680 mg, 28.8 mmol) in portions. The mixture was refluxed at 65 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to obtain 1.5 g of reddish-brown product.

[0048] Example 3

[0049] Tetrabromotetraphenylmethane (9.5 g, 15 mmol) and pinacol diester (10 g, 30 mmol) were added to a 1000 mL Shrek flask. Under a nitrogen atmosphere, THF (400 mL) and 2 M K2CO3 aqueous solution (80 mL) were added, followed by tetratetraphenylphosphine palladium (1.34 g, 1.2 mmol). The mixture was refluxed at 65 °C for 36 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to give 7.3 g of yellow-green product (TPE-1), with a yield of 90%.

[0050] TPE-1 (1000 mg, 1.85 mmol) and biphenyl dichlorobenzyl (1506 mg, 5.96 mmol) were weighed and added to a 250 mL Shrek tube. Dry chloroform (100 mL) was added under a nitrogen atmosphere, followed by the addition of FeCl3 (4680 mg, 28.8 mmol) in portions. The mixture was refluxed at 65 °C for 72 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to obtain 1.9 g of reddish-brown product.

[0051] Example 4

[0052] Tetrabromotetraphenylene (10 g, 15.4 mmol) and pinacol diester (10 g, 30 mmol) were added to a 1000 mL Shrek flask. Under a nitrogen atmosphere, 1,4-dioxane (400 mL) and 2MK2CO3 aqueous solution (80 mL) were added, followed by tetratetraphenylphosphine palladium (1.34 g, 1.2 mmol). The mixture was refluxed at 65 °C for 36 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to give 8.1 g of yellow-green product (TPE-1), with a yield of 98%.

[0053] TPE-1 (1000 mg, 1.85 mmol) and biphenyl dichlorobenzyl (753 mg, 2.98 mmol) were weighed and added to a 250 mL Shrek tube. Dry chloroform (100 mL) was added under a nitrogen atmosphere, followed by the addition of FeCl3 (4680 mg, 28.8 mmol) in portions. The mixture was refluxed at 65 °C for 72 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to obtain 1.4 g of reddish-brown product.

[0054] Example 5

[0055] Tetrabromotetraphenylene (10 g, 15.4 mmol) and pinacol diester (10 g, 30 mmol) were added to a 1000 mL Shrek flask. Under a nitrogen atmosphere, THF (400 mL) and 2 M K2CO3 aqueous solution (80 mL) were added, followed by tetratetraphenylphosphine palladium (1.34 g, 1.2 mmol). The mixture was refluxed at 65 °C for 36 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to give 8.1 g of yellow-green product (TPE-1), with a yield of 98%.

[0056] TPE-1 (1000 mg, 1.85 mmol) and biphenyl dichlorobenzyl (753 mg, 2.98 mmol) were weighed and added to a 250 mL Shrek tube. Dry chloroform (100 mL) was added under a nitrogen atmosphere, followed by the addition of FeCl3 (4680 mg, 28.8 mmol) in batches. The mixture was refluxed at 65 °C for 72 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to obtain 1.5 g of reddish-brown product.

[0057] Example 6

[0058] Tetrabromotetraphenylene (10 g, 15.4 mmol) and pinacol diester (10 g, 30 mmol) were added to a 1000 mL Shrek flask. Under a nitrogen atmosphere, 1,4-dioxane (400 mL) and 2MK2CO3 aqueous solution (80 mL) were added, followed by tetratetraphenylphosphine palladium (1.34 g, 1.2 mmol). The mixture was refluxed at 101 °C for 36 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to give 8.1 g of yellow-green product (TPE-1), with a yield of 98%.

[0059] TPE-1 (1000 mg, 1.85 mmol) and biphenyl dichlorobenzyl (2.99 g, 11.92 mmol) were weighed and added to a 250 mL Shrek tube. Dry 1,2-dichloroethane (100 mL) was added under a nitrogen atmosphere, followed by the addition of FeCl3 (4680 mg, 28.8 mmol) in portions. The mixture was refluxed at 84 °C for 72 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to obtain 3.6 g of reddish-brown product.

[0060] Example 7

[0061] Tetrabromotetraphenylene (10 g, 15.4 mmol) and pinacol diester (10 g, 30 mmol) were added to a 1000 mL Shrek flask. Under a nitrogen atmosphere, THF (400 mL) and 2 M K2CO3 aqueous solution (80 mL) were added, followed by tetratetraphenylphosphine palladium (1.34 g, 1.2 mmol). The mixture was refluxed at 65 °C for 36 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to give 8.1 g of yellow-green product (TPE-1), with a yield of 98%.

[0062] TPE-1 (1000 mg, 1.85 mmol) and 1,1':4',1”-triphenyl,4,4”-bis(chloromethyl)-(9Cl) (3.99 g, 11.92 mmol) were weighed and added to a 250 mL Shrek tube. Dry chloroform (100 mL) was added under a nitrogen atmosphere, followed by the addition of FeCl3 (4680 mg, 28.8 mmol) in portions. The mixture was refluxed at 65 °C for 72 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to obtain 3.6 g of reddish-brown product.

[0063] Example 8

[0064] Tetrabromotetraphenylene (10 g, 15.4 mmol) and phenylboronic acid (3.6 g, 30 mmol) were added to a 1000 mL Shrek flask. Under a nitrogen atmosphere, THF (400 mL) and 2 M K2CO3 aqueous solution (80 mL) were added, followed by tetratetraphenylphosphine palladium (1.34 g, 1.2 mmol). The mixture was refluxed at 65 °C for 36 h. After the reaction was completed, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to give 8.1 g of yellow-green product (TPE-1), with a yield of 98%.

[0065] TPE-1 (1000 mg, 1.85 mmol) and 1,1':4',1”-triphenyl,4,4”-bis(chloromethyl)-(9Cl) (3.99 g, 11.92 mmol) were weighed and added to a 250 mL Shrek tube. Dry chloroform (100 mL) was added under a nitrogen atmosphere, followed by the addition of FeCl3 (4680 mg, 28.8 mmol) in portions. The mixture was refluxed at 65 °C for 72 h. After the reaction was complete, the mixture was cooled to room temperature, filtered, and the filter cake was washed with ethanol and dried in a vacuum oven at 60 °C to obtain 3.6 g of reddish-brown product.

[0066] The porous organic polymers obtained in Examples 1, 4, 6, and 8 are designated as TPE-1, TPE-2, TPE-3, and TPE-4, respectively. Infrared spectra of POP-TPEs with different proportions were obtained, as shown below. Figure 1 As shown. Figure 1 It can be known that 3026cm -1 and 1631cm -1 The peaks at 1609 cm⁻¹ are due to the stretching vibrations of aromatic -CH bonds and aromatic -C=C- bonds, which is the main structure of the polymer; the peaks at 1609 cm⁻¹ are due to the stretching vibrations of aromatic -CH bonds and aromatic -C=C- bonds, respectively. -1 The peak at 2927 cm⁻¹ is due to the stretching vibration of -C=C⁻ in the polymer; the introduction of the biphenyl dichlorobenzyl crosslinking agent leads to the peak at 2927 cm⁻¹. -1 and 2972cm -1 A new peak appears at this point, which belongs to the stretching vibration of the methylene group, and becomes more pronounced with the increase of crosslinking agent dosage. Figure 1 Infrared images of POP-TPEs at different ratios

[0067] The porous organic polymers obtained in Examples 1, 4, 6, and 8 were subjected to scanning electron microscopy (SEM) to obtain SEM images of POP-TPEs with different proportions, denoted as a, b, c, and d, respectively. Figure 2 As shown. Figure 2 It can be seen that all of the above polymers exhibit a rough and irregular porous structure.

[0068] The porous organic polymers obtained in Examples 1, 4, 6, and 8 are designated as TPE-1, TPE-2, TPE-3, and TPE-4, respectively. Thermogravimetric analyses of POP-TPEs with different proportions were obtained by scanning, as shown below. Figure 3 As shown. Figure 3 It can be seen that all of the above polymers exhibit good thermal stability.

[0069] The porous organic polymers obtained in Examples 1, 4, 6, and 8 were subjected to adsorption performance testing. Adsorption performance diagrams of POP-TPEs with different proportions were obtained by scanning, denoted as a, b, c, and d, respectively. Figure 4 As shown. Figure 4 It can be seen that all of the above polymers exhibit excellent adsorption performance for MB.

[0070] The porous organic polymers obtained in Examples 1, 4, 6, and 8 were subjected to BET detection. BET maps of POP-TPEs with different proportions were obtained and denoted as a, b, c, and d, respectively. Figure 5 As shown. Figure 5 It can be seen that the BET of the above polymers increased significantly after the introduction of crosslinking agents.

[0071] The porous organic polymers obtained in Examples 1, 4, 6, and 8 were subjected to adsorption kinetic fitting tests. Adsorption kinetic fitting curves of POP-TPEs with different proportions were obtained by scanning, and are denoted as a, b, c, and d, respectively. Figure 6 As shown. Figure 6 It can be seen that the above polymer adsorption isotherm data were fitted using the Langmuir model and the Freundich model. The coefficient parameters of the Langmuir model are closer to 1, indicating that the polymer is more suitable for the Langmuir model, and the adsorption behavior of the dye is mainly monolayer adsorption.

[0072] Application Example 1

[0073] Methylene blue (MB) dye adsorption experiment

[0074] The porous organic polymers prepared in Examples 1, 3 and 6 were subjected to methylene blue (MB) adsorption studies.

[0075] Test samples: porous organic polymers obtained in Examples 1, 3, and 6;

[0076] Preparation of methylene blue (MB) dye solution: Prepare a methylene blue (MB) dye solution with a concentration of 100 ppm;

[0077] Experimental method: Add 5 mg of the test sample to the sample bottle, add 10 mL of the prepared methylene blue (MB) dye solution, and place it in an oil bath at 25 ℃ for adsorption experiment by stirring; record the UV-Vis spectrum once at 20 s, 40 s, 60 s, 90 s, 120 s, 180 s, 240 s, 300 s, 600 s, and 1200 s respectively, measure the concentration of methylene blue (MB) dye solution using a UV-Vis spectrophotometer, and calculate the adsorption capacity of the porous organic polymer for methylene blue (MB) dye solution.

[0078] The porous organic polymers prepared in Examples 1, 3 and 6 can completely adsorb 100 ppm MB within 20 minutes, 5 minutes and 1 minute, respectively.

[0079] Application Example 2

[0080] Rhodamine B (RhB) dye adsorption experiment

[0081] The porous organic polymers obtained in Examples 1, 3 and 6 were subjected to Rhodamine B (RhB) adsorption studies.

[0082] Test samples: porous organic polymers obtained in Examples 1, 3, and 6;

[0083] Preparation of Rhodamine B (RhB) dye solution: Prepare a Rhodamine B (RhB) dye solution with a concentration of 100 ppm;

[0084] Experimental method: Add 5 mg of the test sample to the sample bottle, add 10 mL of the prepared Rhodamine B (RhB) dye solution, and place in an oil bath at 25℃ for adsorption experiment by stirring; record the UV-Vis spectrum once at 20 s, 40 s, 60 s, 90 s, 120 s, 180 s, 240 s, 300 s, 600 s, and 1200 s respectively, measure the concentration of Rhodamine B (RhB) dye solution using a UV-Vis spectrophotometer, and calculate the adsorption capacity of the porous organic polymer for Rhodamine B (RhB) dye solution.

[0085] The porous organic polymers prepared in Examples 1, 3 and 6 can completely adsorb 100 ppm RhB within 20 minutes, 2 minutes and 1 minute, respectively.

[0086] Application Example 3

[0087] Methyl orange (MO) dye adsorption experiment

[0088] The porous organic polymers obtained in Examples 1, 3 and 6 were subjected to methyl orange (MO) adsorption studies;

[0089] Test samples: porous organic polymers obtained in Examples 1, 3, and 6;

[0090] Preparation of methyl orange (MO) dye solution: Prepare a methyl orange (MO) dye solution with a concentration of 100 ppm;

[0091] Experimental method: Add 5 mg of the test sample to the sample bottle, add 10 mL of the prepared methyl orange (MO) dye solution, and place it in an oil bath at 25 ℃ for adsorption experiment by stirring; record the UV-Vis spectrum once at 20 s, 40 s, 60 s, 90 s, 120 s, 180 s, 240 s, 300 s, 600 s, and 1200 s respectively, measure the concentration of methyl orange (MO) dye solution using a UV-Vis spectrophotometer, and calculate the adsorption capacity of the porous organic polymer for methyl orange (MO) dye solution.

[0092] The porous organic polymers prepared in Examples 1, 3 and 6 did not completely adsorb 100 ppm MO within 20 minutes.

[0093] Application Example 4

[0094] Methylene blue (MB) dye adsorption experiment

[0095] The porous organic polymers obtained in Examples 1, 3 and 6 were subjected to methylene blue (MB) adsorption studies.

[0096] Test samples: porous organic polymers obtained in Examples 1, 3, and 6;

[0097] Preparation of methylene blue (MB) dye solution: Prepare a methylene blue (MB) dye solution with a concentration of 100-600 ppm;

[0098] Experimental method: Add 5 mg of the test sample to the sample bottle, add 10 ml of the prepared methylene blue (MB) dye solution, place in an oil bath at 25 ℃ and stir to carry out the adsorption experiment; after adsorption for 24 h, measure the concentration of methylene blue (MB) dye solution using a UV-Vis spectrophotometer, and calculate the adsorption capacity of the porous organic polymer for methylene blue (MB) dye solutions of different concentrations.

[0099] The porous organic polymers prepared in Examples 1, 3, and 6 achieved adsorption capacities of 627 mg·g for MB. -1 658mg·g -1 and 723 mg·g -1 .

[0100] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A method for preparing a porous organic polymer based on tetraphenylethylene, characterized in that: The tetraphenylethylene-based porous organic polymer is prepared by first coupling tetraphenylethylene units with reactive groups Suzuki, and then reacting them with linking groups via Friedel-Crafts alkylation. The tetraphenylethylene unit is one of the following structural formulas: ； The reactive group is ; The linking group unit is one of the following structural formulas: 。 2. The preparation method based on tetraphenylethylene porous organic polymer according to claim 1, characterized in that, Specifically, the following steps are included: Step S1: The tetraphenylethylene unit and the reactive group Suzuki are coupled to obtain an intermediate product. The intermediate product is then dispersed with the linking group unit in a first solvent. After stirring until completely dissolved, a catalyst is added and mixed evenly to obtain a mixed solution. Step S2: The mixed solution obtained in step S1 is subjected to Friedel-Crafts alkylation reaction at a temperature of 30–80 °C for a time of 12–72 h. Step S3: After the reaction is complete, the filter cake is immediately filtered. The resulting filter cake is washed with a second solvent and then filtered again. After repeated washing and filtration, the filter cake is vacuum dried to obtain the target product based on tetraphenylethylene porous organic polymer.

3. The preparation method based on tetraphenylethylene porous organic polymer according to claim 2, characterized in that: In step S1, the molar ratio of tetraphenylethylene unit to linking group unit is 1:(0.5~2).

4. The preparation method based on tetraphenylethylene porous organic polymer according to claim 2, characterized in that: The first solvent in step S1 is one or more of dichloromethane, N,N-dimethylformamide, tetrahydrofuran, 1,2-dichloroethane, 1,4-dioxane, trichloromethane, or dimethyl sulfoxide.

5. The preparation method based on tetraphenylethylene porous organic polymer according to claim 2, characterized in that: The catalyst in step S1 is one or more of FeCl3, AlCl3, boron trifluoride, or niobium pentachloride.

6. The preparation method based on tetraphenylethylene porous organic polymer according to claim 2, characterized in that: The second solvent in step S3 is one or more of dichloromethane, methanol, N,N-dimethylformamide, tetrahydrofuran, or diethyl ether.

7. An application of a porous organic polymer based on tetraphenylethylene prepared by the method according to any one of claims 1 to 6, characterized in that: The application of tetraphenylethylene porous organic polymer in wastewater treatment.

8. The application of the tetraphenylethylene porous organic polymer according to claim 7, characterized in that: The method uses a porous organic polymer based on tetraphenylethylene as an adsorbent to adsorb organic pollutants in wastewater; the organic pollutants are one or more of Rhodamine B, methylene blue, and methyl orange.

9. The application of the tetraphenylethylene porous organic polymer according to claim 8, characterized in that: The organic pollutants are adsorbed by the tetraphenylethylene porous organic polymer under stirring, ultrasonic and / or oscillation conditions.

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