A porous organic polymer and a preparation method and application thereof

Abstract

The application discloses a kind of porous organic polymers and its preparation method and application, belong to photocatalytic material technical field.The application is synthesized by Suzuki coupling reaction design and synthesis a kind of porous organic polymer based on BODIPY, and on the basis of it is prepared by hydrophilic modification and obtains a kind of cationic BODIPY-based porous organic polymer.The polymer can be under xenon lamp irradiation, adsorb and photocatalytic degradation pesticide, dye and other organic pollutants in water, show excellent adsorption performance and photocatalytic performance, porous organic polymer and hydrophilic porous organic polymer prepared by the application all have excellent photocatalytic performance, the application has good application prospect and potential application value in water treatment field.

Description

TECHNICAL FIELD

[0001] The present application relates to the preparation and application of a photocatalytic material, in particular to a porous organic polymer and a preparation method and application thereof. BACKGROUND

[0002] Pesticides, dyes and other organic pollutants in wastewater usually contain strong biological toxicity and carcinogenicity, and their chemical structures are very stable and difficult to decompose naturally in water. At present, there are three methods for wastewater treatment, namely physical adsorption method, biological degradation method and advanced oxidation method. Although the traditional physical adsorption method can quickly adsorb organic pollutants, it cannot effectively degrade the pollutants; the biological degradation method can degrade organic pollutants, but it takes a long time to degrade, it is difficult to domesticate, and it is easy to cause secondary pollution; and the advanced oxidation method can generate active species with strong oxidation ability under light or high temperature conditions, and then quickly and efficiently degrade organic pollutants into water and carbon dioxide, realizing the complete purification of the contaminated water body. As a new advanced oxidation method, photocatalytic technology uses solar energy as energy, which has the advantages of large storage capacity, wide irradiation range, cleanliness and renewability, etc., and shows many advantages such as simple operation, low energy consumption and high efficiency, and is one of the most promising wastewater treatment methods at present.

[0003] As a new type of organic material, porous organic polymers (POPs) are widely used in chemical sensing, biomedical, photocatalysis and other fields due to their high activity, high specific surface area, good stability and easy recovery. In the field of photocatalysis, POPs show better performance than traditional photocatalysts, however, POPs driven photocatalysis still faces many challenges, such as narrow light absorption range, rigid planar hydrophobic structure makes it difficult to disperse in water, easy to be decomposed by light corrosion, and single function also limits its more extensive application to some extent.

[0004] To solve these problems, it is necessary to introduce functional groups by pre-designing the structure of the material to improve the structure of the material, enhance the light absorption performance, improve the stability, and further improve the hydrophilicity of the material through post-modification, so as to improve the photocatalytic performance. SUMMARY

[0005] The first object of the present application is to provide a porous organic polymer capable of efficiently photocatalytically degrading organic pollutants in water, the second object of the present application is to provide a preparation method of the porous organic polymer, solving the problem of how to react to prepare the porous organic polymer, the third object of the present application is to provide a hydrophilic porous organic polymer, solving the problem of how to improve the hydrophilicity of the porous organic polymer, the fourth object of the present application is to provide a preparation method of the hydrophilic porous organic polymer, solving the problem of how to react to prepare the hydrophilic porous organic polymer, and the fifth object of the present application is to provide an application of the porous organic polymer or the hydrophilic porous organic polymer in photocatalytic degradation of water-soluble organic pollutants, solving the problem of how to apply the porous organic polymer or the hydrophilic porous organic polymer to photocatalytic degradation of water-soluble organic pollutants.

[0006] The technical scheme is that the porous organic polymer provided by the present application has a structure as shown in formula (I):

[0007]

[0008] wherein the R1 group is selected from H, the R2 is selected from a phenyl group, and the R3 is or H, the R4 is N or C, the n is 0 or 1, and the m is 0 or 1.

[0009] In order to obtain the porous organic polymer, the present application discloses a preparation method of the porous organic polymer, comprising the following steps:

[0010]

[0011] the R5 is selected from the X is halogen, and the R1 group is the same as above.

[0012] The present application is prepared by using BODIPY derivative, 2,1,3-benzothiadiazole-4,7-bis(pinacol borate) as a connecting unit through Suzuki coupling reaction to obtain a BODIPY-based polymer, and then using a hydrophilic modification reagent to modify the BODIPY-based polymer to obtain a cationic modified BODIPY porous organic polymer. The BODIPY derivative is compound III.

[0013] Preferably, the base is potassium carbonate or cesium carbonate, the catalyst is tetrakis(triphenylphosphine)palladium and / or 1,1-bis(diphenylphosphino)ferrocene palladium dichloride, and the R5 is The reaction solvent is one or more of N,N-dimethylformamide, dichloromethane, trichloromethane, acetone, tetrahydrofuran, acetonitrile, toluene, ethanol and methanol.

[0014] Preferably, the molar ratio of the compound III to the compound II is 1-3:1-5, preferably 1.71-3.42:1.14-5.14. The specific reaction steps are as follows:

[0015] (1) In a mixing container, sequentially add BODIPY derivative, 2,1,3-benzothiadiazole-4,7-bis(pinacol borate), N,N-dimethylformamide, base, and ultrasonically mix;

[0016] (2) Replace the reaction system of step (1) with nitrogen or argon three times, add tetrakis(triphenylphosphine)palladium, and continue to pass nitrogen for 5-10 minutes. Increase the temperature to reflux, and react at 60-120℃ for 3-5 days. After the reaction, cool to room temperature, and filter to separate to obtain a solid product; the reaction time is preferably 24-72 hours;

[0017] (3) After washing and drying the solid product obtained in step (2), use one or more of water, diethyl ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, ethanol, and methanol as a solvent for washing, and finally use one or more of dichloromethane, acetone, tetrahydrofuran, acetonitrile, ethanol, and methanol for Soxhlet extraction for 24-72 hours. After drying the solid at 40-60℃ under vacuum, compound I is obtained.

[0018] Preferably, the preparation method of the compound III is as follows:

[0019]

[0020] The X is I, Br, or Cl.

[0021] First, compound VI and V are dispersed into dichloromethane solvent, trifluoroacetic acid is added, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), triethylamine (Et3N), and boron trifluoride diethyl ether (BF3·Et2O) are sequentially added under ice bath conditions, and stirred at room temperature overnight. After the reaction is completed, column chromatography is performed to obtain compound IV. Compound IV is dispersed into dichloromethane, a halogenated reagent is added under ice bath conditions, and stirred at room temperature. After the reaction is completed, column chromatography is performed to obtain compound III.

[0022]

[0023] In the formula, R1 is the same as that of compound I.

[0024] In order to obtain the above-mentioned hydrophilic porous organic polymer, the application discloses a preparation method of a hydrophilic porous organic polymer, which comprises the following steps:

[0025] The hydrophilic modification reagent is The q is greater than or equal to 1.

[0026] Preferably, the molar ratio of the compound I to the hydrophilic modification reagent is 1-2:5-15, the reaction condition is that chloroform is used as the solvent, aluminum trichloride or ferric trichloride is used as the Lewis acid, the molar ratio of the compound I to the Lewis acid is 1:5-15, and the reaction is carried out in an oil bath at 20-120℃ for 2-4 days. In some embodiments, the hydrophilic modification reagent is 2-bromoethyl trimethylammonium bromide, and the specific steps are as follows:

[0027] (1) sequentially adding the compound I, the hydrophilic modification reagent, and chloroform in a mixing container and uniformly ultrasonicating;

[0028] (2) replacing the reaction system with nitrogen or argon three times, adding aluminum trichloride or ferric trichloride as the Lewis acid, and continuing to pass nitrogen for 5-10 minutes. The reaction is carried out at 60-120℃ under reflux for 24-72 hours, and after the reaction, the reaction system is cooled to room temperature, and the solid product is separated by filtration;

[0029] (3) washing and drying the solid product, and then washing the solid product with one or more of water, diethyl ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, ethanol, and methanol as the solvent, and finally performing Soxhlet extraction with one or more of dichloromethane, acetone, tetrahydrofuran, acetonitrile, ethanol, and methanol, for 24-72 hours. After the solid is vacuum dried at 40-60℃, a cation-modified BODIPY porous organic polymer, i.e., the compound VII, is obtained.

[0030] The application further applies the above porous organic polymer or the hydrophilic porous organic polymer to photocatalytic degradation of water-soluble organic pollutants.

[0031] Preferably, the water-soluble organic pollutants include water-soluble dyes and pesticides, and the working concentration of the porous organic polymer or the hydrophilic porous organic polymer is not less than 0.1 mg / mL, and is preferably 0.1-1 mg / mL. In some embodiments, the light source used for photocatalysis is a xenon lamp, and the water-soluble organic pollutants are one or more of Congo red, 2,4-D, methyl orange, and methylene blue in water at a concentration of 50-200 ppm.

[0032] Advantages: Compared with the prior art, the application has the following advantages: the porous organic polymer and the hydrophilic porous organic polymer prepared by the application both have excellent photocatalytic performance, the efficiency of photocatalytic degradation of Congo red in water within 40 minutes can reach 100%, and the efficiency of photocatalytic degradation of 2,4-D in water within 90 minutes can also be high.

[0033] The BODIPY derivative, 2,1,3-benzothiadiazole-4,7-bis(pinacol borate) is used as a raw material to prepare a porous organic polymer, and the yield can reach 87%; further, a hydrophilic modification reagent is used to perform cation modification on the porous organic polymer, and the hydrophilicity of the porous organic polymer is effectively improved, and then the photocatalytic degradation performance of the porous organic polymer in a water environment is significantly improved, and the yield of the hydrophilic porous organic polymer is also as high as 97%. The present application has good application prospect and potential application value in the field of water treatment. BRIEF DESCRIPTION OF DRAWINGS

[0034] Figure 1 Reaction formula of the cation-modified BODIPY porous organic polymer iB-TDZ;

[0035] Figure 2 Water contact angle diagram of the BODIPY-based original polymer B-TDZ-1 prepared in Example 1;

[0036] Figure 3 Water contact angle diagram of the cation-modified BODIPY porous organic polymer iB-TDZ-1 prepared in Example 1;

[0037] Figure 4 Scanning electron microscope diagram of the cation-modified BODIPY porous organic polymer iB-TDZ-1 prepared in Example 1;

[0038] Figure 5 Impedance diagram of the BODIPY-based original polymer B-TDZ-1 and the cation-modified BODIPY porous organic polymer iB-TDZ-1 prepared in Example 1;

[0039] Figure 6 Photocurrent diagram of the BODIPY porous organic polymer B-TDZ-1 and the cation-modified BODIPY porous organic polymer iB-TDZ-1 prepared in Example 1;

[0040] Figure 7 Performance comparison diagram of the BODIPY-based original polymer and the cation-modified BODIPY porous organic polymer iB-TDZ-1 prepared in Example 1 in dark adsorption and photodegradation of 100ppm Congo red at a concentration of 0.5mg / mL;

[0041] Figure 8 Performance comparison diagram of the BODIPY-based original polymer B-TDZ-1 and the cation-modified BODIPY porous organic polymer iB-TDZ-1 prepared in Example 1 in dark adsorption and photodegradation of 100ppm 2,4-D at a concentration of 0.5mg / mL;

[0042] Figure 9Infrared spectra of the BODIPY-based original polymer B-TDZ-1 and the cationic modified BODIPY porous organic polymer iB-TDZ-1 prepared in Example 1;

[0043] Figure 10 Solid carbon spectra of the BODIPY-based original polymer B-TDZ-1 and the cationic modified BODIPY porous organic polymer iB-TDZ-1 prepared in Example 1. DETAILED DESCRIPTION

[0044] The technical solutions of the present application will be further described below in combination with the drawings.

[0045] Example 1: A hydrophilic porous organic polymer, the structural formula is as follows:

[0046]

[0047] The preparation method of the above hydrophilic porous organic polymer is as follows:

[0048] (1) Preparation of 5,5-difluoro-2,8-diiodo-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4L4,5L4-dipyrrolo[1,2-c:2,1-f][1,3,2]diazaborinine, the reaction formula is as follows:

[0049]

[0050] First, 4-iodobenzaldehyde (4.6 g, 20 mmol) and 2,4-dimethylpyrrole (3.7 g, 4.0 mL, 40 mmol) were dispersed in dichloromethane (200 mL) solvent, and trifluoroacetic acid was added, and 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (4.5 g, 20 mmol) dissolved in 20 mL of tetrahydrofuran, triethylamine (60 mL) and boron trifluoride diethyl ether (60 mL) were added in turn under ice bath conditions, and stirred at room temperature overnight. After the reaction was completed, dichloromethane was extracted, and column chromatography (DCM:PE = 1:2) was performed to obtain 5,5-difluoro-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4L4,5L4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine 3.2 g, yield 35%. 5,5-difluoro-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4L4,5L4-dipyrrolo[1,2-c:2',1'-f][1,3,2]diazaborinine (2.2 g, 4.8 mmol) was dispersed in dichloromethane (60 mL) solvent, and N-iodosuccinimide (NIS) was added under ice bath conditions, and stirred at room temperature for 4 hours. After the reaction was completed, dichloromethane was extracted, and column chromatography (DCM:PE = 1:2) was performed to obtain 5,5-difluoro-2,8-diiodo-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4L4,5L4-dipyrrolo[1,2-c:2,1-f][1,3,2]diazaborinine 2.7 g, yield 87%.

[0051] (2) In a 500 mL Schlenk flask, 200 mL of N,N-dimethylformamide, 5,5-difluoro-2,8-diiodo-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4L4,5L4-dipyrrolo[1,2-c:2,1-f][1,3,2]diazaborinine (2.4 g, 3.42 mmol) and 2,1,3-benzothiadiazole-4,7-diboronic acid pinacol ester (2.0 g, 5.14 mmol) were added in turn, and stirred for 20 minutes or ultrasonically mixed to uniformly disperse the mixture; nitrogen was introduced into the 500 mL Schlenk flask, and the nitrogen was replaced three times, and 10 mL of 2 mol / L potassium carbonate aqueous solution and tetrakis(triphenylphosphine)palladium (242 mg, 0.21 mmol) were added in turn under nitrogen, and nitrogen was continued to be introduced for 5-10 minutes, and the reaction was refluxed at 100°C in an oil bath for 3 days to form a dark brown solid, and after cooling to room temperature, the product was separated by filtration;

[0052]

[0053] (3) The product is washed with N,N-dimethylformamide, tetrahydrofuran and methanol multiple times, and then Soxhlet extraction is performed for two days using N,N-dimethylformamide, tetrahydrofuran and dichloromethane as solvents, respectively, and the obtained solid product is dried in a vacuum drying box at 40-60°C for 24 hours to obtain the BODIPY porous organic polymer B-TDZ-1, with a yield of 87%, which is compound I.

[0054] (4) B-TDZ-1 (0.80 g, 1.34 mmol) obtained in step (3) and 2-bromoethyltrimethylammonium bromide (1.80 g, 6.68 mmol) and chloroform are added to a reaction container, and ultrasonic mixing is performed, and then the reaction system is replaced with nitrogen three times, and aluminum chloride or ferric chloride is added as a Lewis acid, and nitrogen is continuously passed for 5-10 minutes. The temperature is increased to reflux, and the reaction is performed at 65°C in an oil bath for 3 days to generate a black solid, and after the reaction, the temperature is cooled to room temperature, and the solid product is separated by filtration; the solid product is washed with N,N-dimethylformamide, tetrahydrofuran and methanol multiple times, and then Soxhlet extraction is performed for two days using N,N-dimethylformamide, tetrahydrofuran and dichloromethane as solvents, respectively, and the obtained solid product is dried in a vacuum drying box at 40-60°C for 24 hours to obtain the cation-modified BODIPY porous organic polymer iB-TDZ-1, with a yield of 97%, which is compound VII. The reaction formula is as follows:

[0055]

[0056] Compounds I and VII are characterized, and the results are shown in Figure 9 and Figure 10 The micro-morphology of compound VII is shown in Figure 4 , which presents a loose and porous morphology.

[0057] The hydrophilicity of compounds I and VII is tested, and the results are shown in Figure 2 and Figure 3 After comparison, it can be seen that the hydrophilicity of compound I is poor, while the cation-modified compound VII has excellent hydrophilicity. The improvement of hydrophilicity is conducive to the photocatalytic degradation of water-soluble pollutants in a water environment.

[0058] The photocatalytic performance of compounds I and VII is tested, and the results are shown in Figure 5 and Figure 6 Compounds I and VII have good photocatalytic reaction characteristics.

[0059] Example 2: The rest is the same as example 1, except that:

[0060] In a 500 mL Schlenk flask, 200 mL of N,N-dimethylformamide, 5,5-difluoro-2,8-diiodo-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4L4,5L4-dipyrrolo[1,2-c:2,1-f][1,3,2]diazaborinine (1.20 g, 1.71 mmol) and 2,1,3-benzothiadiazole-4,7-diboronic acid pinacol ester (0.44 g, 1.14 mmol) were added successively, and the mixture was stirred for 20 min to uniformly disperse; the 500 mL Schlenk flask was purged with nitrogen, and potassium carbonate and tetrakis(triphenylphosphine)palladium (127 mg, 0.11 mmol) were added successively under the nitrogen atmosphere, and the reaction was carried out in a 100°C oil bath for 3 days to form a dark brown solid, which was separated by filtration after cooling to room temperature; the product was washed with N,N-dimethylformamide, tetrahydrofuran and methanol for several times, and then subjected to Soxhlet extraction with N,N-dimethylformamide, tetrahydrofuran and dichloromethane as solvents for two days, and the obtained solid product was dried in a 100°C vacuum drying oven for 24 hours to obtain the BODIPY porous organic polymer B-TDZ-2, with a yield of 86%.

[0061] The obtained B-TDZ-2 (0.80 g, 1.34 mmol) and 2-bromoethyltrimethylammonium bromide (1.80 g, 6.68 mmol) were reacted with chloroform as the solvent and aluminum chloride as the Lewis acid, and the reaction was carried out in a 65°C oil bath for 3 days to form a black solid, which was separated by filtration after cooling to room temperature; the product was washed with N,N-dimethylformamide, tetrahydrofuran and methanol for several times, and then subjected to Soxhlet extraction with N,N-dimethylformamide, tetrahydrofuran and dichloromethane as solvents for two days, and the obtained solid product was dried in a 40-60°C vacuum drying oven for 24 hours to obtain the cation-modified BODIPY porous organic polymer iB-TDZ-2, with a yield of 95%.

[0062] Example 3: The rest is the same as Example 1, except that:

[0063] In a 500 mL Schlenk flask, 200 mL of N,N-dimethylformamide, 5,5-difluoro-2,8-diiodo-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4L4,5L4-dipyrrolo[1,2-c:2,1-f][1,3,2]diazaborinine (2.4 g, 3.42 mmol) and 2,1,3-benzothiadiazole-4,7-diboronic acid pinacol ester (0.66 g, 1.71 mmol) were added successively, and the mixture was stirred for 20 min to uniformly disperse; the 500 mL Schlenk flask was purged with nitrogen, and potassium carbonate and tetrakis(triphenylphosphine)palladium (242 mg, 0.21 mmol) were added successively under the nitrogen environment, and the reaction was carried out in a 100°C oil bath for 3 days to form a dark brown solid, which was separated by filtration after cooling to room temperature; the product was washed with N,N-dimethylformamide, tetrahydrofuran and methanol for several times, and then subjected to Soxhlet extraction with N,N-dimethylformamide, tetrahydrofuran and dichloromethane as solvents for two days, and the obtained solid product was dried in a vacuum drying oven at 40-60°C for 24 hours to obtain the BODIPY porous organic polymer B-TDZ-3, with a yield of 83%.

[0064] The obtained B-TDZ-3 (0.80 g, 1.34 mmol) and 2-bromoethyltrimethylammonium bromide (1.80 g, 6.68 mmol) were reacted with chloroform as the solvent and aluminum chloride as the Lewis acid, and the reaction was carried out in a 65°C oil bath for 3 days to form a black solid, which was separated by filtration after cooling to room temperature; the product was washed with N,N-dimethylformamide, tetrahydrofuran and methanol for several times, and then subjected to Soxhlet extraction with N,N-dimethylformamide, tetrahydrofuran and dichloromethane as solvents for two days, and the obtained solid product was dried in a vacuum drying oven at 80°C for 24 hours to obtain the cation-modified BODIPY porous organic polymer iB-TDZ-3, with a yield of 96%.

[0065] Example 4: The rest is the same as Example 1, except that:

[0066] In a 500 mL Schlenk flask, 200 mL of N,N-dimethylformamide, 5,5-difluoro-2,8-diiodo-10-(4-iodophenyl)-1,3,7,9-tetramethyl-5H-4L4,5L4-dipyrrolo[1,2-c:2,1-f][1,3,2]diazaborinine (1.2 g, 1.71 mmol) and 2,1,3-benzothiadiazole-4,7-diboronic acid pinacol ester (0.66 g, 1.71 mmol) were added successively, and the mixture was stirred for 20 min to uniformly disperse; the 500 mL Schlenk flask was purged with nitrogen, and potassium carbonate and tetrakis(triphenylphosphine)palladium (127 mg, 0.11 mmol) were added successively under the nitrogen atmosphere, and the reaction was carried out in a 100°C oil bath for 3 days to form a dark brown solid, which was separated by filtration after cooling to room temperature; the product was washed with N,N-dimethylformamide, tetrahydrofuran and methanol for several times, and then subjected to Soxhlet extraction with N,N-dimethylformamide, tetrahydrofuran and dichloromethane as solvents for two days, and the obtained solid product was dried in a vacuum drying oven at 40°C for 24 hours to obtain the BODIPY porous organic polymer B-TDZ-4, with a yield of 81%.

[0067] The obtained B-TDZ-4 (0.80 g, 1.34 mmol) and 2-bromoethyltrimethylammonium bromide (1.80 g, 6.68 mmol) were reacted with chloroform as the solvent and aluminum chloride as the Lewis acid, and the reaction was carried out in a 65°C oil bath for 3 days to form a black solid, which was separated by filtration after cooling to room temperature; the product was washed with N,N-dimethylformamide, tetrahydrofuran and methanol for several times, and then subjected to Soxhlet extraction with N,N-dimethylformamide, tetrahydrofuran and dichloromethane as solvents for two days, and the obtained solid product was dried in a vacuum drying oven at 40-60°C for 24 hours to obtain the cation-modified BODIPY porous organic polymer iB-TDZ-4, with a yield of 96%.

[0068] Example 5: Study on photodegradation of organic pollutant Congo red

[0069] The porous organic polymers obtained in Examples 1, 2, 3 and 4 were subjected to a study on photodegradation of organic pollutant Congo red;

[0070] Test sample: The porous organic polymers obtained in Examples 1, 2, 3 and 4;

[0071] Preparation of organic pollutant Congo red solution: A Congo red dye solution with a concentration of 100 ppm was prepared.

[0072] Experimental method: 10 mg of the test sample was added to the sample bottle, along with 20 mL of the prepared Congo red dye solution. The bottle was placed in a constant temperature reactor and stirred for xenon lamp degradation experiments. 2 mL of the reaction solution was taken at 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, and 40 min and filtered using a 0.22 μm filter. The concentration of the Congo red dye solution in the filtrate was measured using a UV-Vis spectrophotometer. The photodegradation efficiency of the cationic modified BODIPY porous organic polymer for the organic pollutant Congo red was calculated.

[0073] The photodegradation efficiency (η) of pollutants is calculated according to the following formula (expressed as a percentage):

[0074]

[0075] Among them, C0(mM) and C t (mM) represents the concentration of pollutants before and after photodegradation (or physical adsorption under dark conditions), respectively.

[0076] The results are as follows Figure 7 As shown in Table 1:

[0077] Table 1. Degradation effect of hydrophilic porous organic polymers on Congo red.

[0078]

[0079] From Table 1 and Figure 7 It is evident that both compound I and compound VII possess photocatalytic degradation properties of Congo red. Compound VII can degrade the vast majority of Congo red within 40 minutes, and the photocatalytic degradation efficiency of compound VII is significantly higher than that of compound I.

[0080] Example 6: Study on photodegradation of 2,4-D pesticide:

[0081] The porous organic polymers obtained in Examples 1, 2, 3 and 4 were subjected to photodegradation of 2,4-drop pesticides.

[0082] Test samples: porous organic polymers obtained in Examples 1, 2, 3 and 4;

[0083] Preparation of 2,4-D pesticide solution: Prepare a 100 ppm 2,4-D pesticide solution;

[0084] Test method: 5 mg of test sample was added to a sample bottle, 10 ml of prepared 2,4-D pesticide solution was added, and it was placed in a constant temperature reactor for stirring and xenon lamp photodegradation experiment; 1 mL of reaction solution was taken at 5 min, 10 min, 20 min, 30 min, 40 min, 50 min, 70 min, and 90 min, respectively, and filtered using a 0.22 μm filter, and the filtrate was measured by high performance liquid chromatography to measure the concentration of 2,4-D pesticide, and the photodegradation efficiency of the cation-modified BODIPY porous organic polymer on the organic pollutant 2,4-D was calculated.

[0085] The photodegradation efficiency (η) of the pollutant was calculated according to the following formula (in %):

[0086]

[0087] Wherein, C0(mM) and C t (mM) represent the pollutant concentration before and after photodegradation (or physical adsorption under dark conditions), respectively.

[0088] The results are shown in Table 1 and Table 2: Figure 8

[0089] Table 2 Degradation effect of hydrophilic porous organic polymer on 2,4-D

[0090]

[0091] As shown in Table 2 and Figure 8 It can be seen that both compound I and compound VII have the characteristics of photocatalytic degradation of 2,4-D, and compound VII can degrade most of 2,4-D within 90 min, and the photocatalytic degradation efficiency of compound VII is significantly higher than that of compound I.

[0092] Example 7: The rest is the same as example 1, except that:

[0093] Compound III is replaced by the following compound:

[0094]

[0095] The palladium catalyst is replaced by 1,1-bis(diphenylphosphino) ferrocene palladium dichloride instead of tetrakis(triphenylphosphine) palladium.

[0096] Potassium carbonate is replaced by cesium carbonate. The nitrogen atmosphere is replaced by an argon atmosphere.

[0097] The molar ratio of compound I to hydrophilic modification reagent 2-bromoethyl trimethylammonium bromide is 1:15;

[0098] The Lewis acid is replaced by ferric chloride instead of aluminum chloride; the molar ratio of compound I to Lewis acid is 1:5;​

[0099] The reaction solvent and the solvents used in the elution, extraction and washing processes can be arbitrarily selected from conventional solvents as needed, and these solvents include one or more of water, diethyl ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, ethanol, methanol, toluene.

[0100] The structure of the compound I prepared in this example is:

[0101]

[0102] The structure of the compound VII prepared in this example is:

[0103]

[0104] Example 8: The rest are the same as Example 1, except that:

[0105] The compound III is replaced by the following compound:

[0106]

[0107] The palladium catalyst is replaced by 1,1-bis(diphenylphosphino) ferrocene palladium dichloride.

[0108] The potassium carbonate is replaced by cesium carbonate. The nitrogen atmosphere is replaced by an argon atmosphere.

[0109] The hydrophilic modification reagent is replaced by The molar ratio of compound I to the hydrophilic modification reagent is 2:5;

[0110] The Lewis acid is replaced by ferric trichloride; the molar ratio of compound I to the Lewis acid is 1:15;

[0111] The reaction solvent and the solvents used in the elution, extraction and washing processes can be arbitrarily selected from conventional solvents as needed, and these solvents include one or more of water, diethyl ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, ethanol, methanol, toluene.

[0112] The structure of the compound I prepared in this example is:

[0113]

[0114] The structure of the compound VII prepared in this example is:

[0115]

[0116] Example 9: The rest are the same as Example 1, except that:

[0117] Compound III is replaced by the following compound:

[0118]

[0119] The palladium catalyst is replaced by 1,1-bis(diphenylphosphino) ferrocene palladium dichloride instead of tetrakis(triphenylphosphine) palladium.

[0120] The molar ratio of compound I to the hydrophilic modification reagent is 1:10;

[0121] The Lewis acid is replaced by ferric chloride instead of aluminum chloride; the molar ratio of compound I to the Lewis acid is 1:10;

[0122] The reaction solvent and the solvents used in the elution, extraction and washing processes can be arbitrarily selected from conventional solvents as needed, and these solvents include one or more of water, diethyl ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, ethanol, methanol, toluene.

[0123] The structure of compound I prepared in this example is:

[0124]

[0125] The structure of compound VII prepared in this example is:

[0126]

[0127] Example 10: The rest are the same as Example 1, except that:

[0128] Compound III is replaced by the following compound:

[0129]

[0130] The molar ratio of compound I to the hydrophilic modification reagent is 1:15;

[0131] The Lewis acid is replaced by ferric chloride instead of aluminum chloride; the molar ratio of compound I to the Lewis acid is 1:7; the structure of compound I prepared in this example is:

[0132]

[0133] The structure of compound VII prepared in this example is:

[0134]

[0135] Example 11: The rest are the same as Example 1, except that:

[0136] Compound III is replaced by the following compound:

[0137]

[0138] The palladium catalyst is replaced by palladium on carbon.

[0139] The molar ratio of compound I to hydrophilic modifying agent is 1:15;

[0140] The Lewis acid is replaced by iron trichloride; the molar ratio of compound I to Lewis acid is 1:15; the structure of compound I prepared in this example is:

[0141]

[0142] The structure of compound VII prepared in this example is:

[0143]

[0144] Example 12: The rest are the same as example 1, except that:

[0145] Compound III is replaced by the following compound:

[0146]

[0147] The molar ratio of compound I to hydrophilic modifying agent is 1:13;

[0148] The Lewis acid is replaced by iron trichloride; the molar ratio of compound I to Lewis acid is 1:10; the structure of compound I prepared in this example is:

[0149]

[0150] The structure of compound VII prepared in this example is:

[0151]

[0152] Example 13: The rest are the same as example 1, except that:

[0153] Compound III is replaced by the following compound:

[0154]

[0155] The molar ratio of compound I to hydrophilic modifying agent is 2:9;

[0156] The molar ratio of compound I to aluminum trichloride is 1:9;

[0157] The structure of compound I prepared in this example is:

[0158]

[0159] The compound VII prepared in this example has the structure:

[0160]

[0161] Example 14: The rest are the same as Example 1, except that:

[0162] The compound III is replaced by the following compound:

[0163]

[0164] The palladium catalyst is replaced by 1,1-bis(diphenylphosphino) ferrocene palladium dichloride. The potassium carbonate is replaced by cesium carbonate.

[0165] The molar ratio of compound I to the hydrophilic modification reagent is 1:15;

[0166] The Lewis acid is replaced by ferric trichloride; the molar ratio of compound I to the Lewis acid is 1:5; the compound I prepared in this example has the structure:

[0167]

[0168] The compound VII prepared in this example has the structure:

[0169]

[0170] Example 15: The rest are the same as Example 1, except that:

[0171] The compound III is replaced by the following compound:

[0172]

[0173] The molar ratio of compound I to the hydrophilic modification reagent is 2:15;

[0174] The Lewis acid is replaced by ferric trichloride; the molar ratio of compound I to the Lewis acid is 1:13; the compound I prepared in this example has the structure:

[0175]

[0176] The compound VII prepared in this example has the structure:

[0177]

[0178] It is tested that the hydrophilicity and photocatalytic activity of the porous organic polymers and the hydrophilic porous organic matters prepared in Examples 7-15 are similar to those of Examples 1-4.

Claims

1. A hydrophilic porous organic polymer, characterized by, The structure is shown as formula (VII): wherein the R1group is selected from H, said R2is selected from phenyl, R3is or H, R4is N or C, said n is 0 or 1, said m is 0 or 1; said q >

1.

2. The method for preparing a hydrophilic porous organic polymer according to claim 1, characterized by, The method comprises the following steps: The hydrophilic modifying agent is q is >

1.

3. The method for producing a hydrophilic porous organic polymer according to claim 2, wherein The preparation method of the compound I is: Said R5is selected from Said X is I, Br, Cl.

4. The method for producing a hydrophilic porous organic polymer according to claim 3, wherein The base is potassium carbonate or cesium carbonate, the catalyst is tetrakis(triphenylphosphine)palladium and / or 1,1-bis(diphenylphosphino)ferrocene palladium dichloride, the R5is The reaction solvent is one or more of N,N-dimethylformamide, dichloromethane, trichloromethane, acetone, tetrahydrofuran, acetonitrile, toluene, ethanol and methanol.

5. The method for preparing the hydrophilic porous organic polymer according to claim 3, characterized in that, The molar ratio of the compound III to the compound II is 1-3:1-5. The preparation method of the compound III is: The X is I, Br or Cl.

6. The method for preparing the hydrophilic porous organic polymer according to claim 2, characterized in that, The molar ratio of the compound I to the hydrophilic modification reagent is 1-2:5-15, the reaction condition is that chloroform is used as a solvent, aluminum chloride or ferric chloride is used as a Lewis acid to perform the reaction, and the reaction is performed in an oil bath at 60-120 DEG C for 2-4 days.

7. The application of the hydrophilic porous organic polymer in photocatalytic degradation of water-soluble organic pollutants according to claim 1.

8. Use according to claim 7, characterized in that, The water-soluble organic pollutants include water-soluble dyes and pesticides, and the working concentration of the hydrophilic porous organic polymer is not less than 0.1 mg / mL.

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