Preparation method and application of a hydrophilic porous organic polymer based on boron difluoride dipyrromethene

Abstract

The application discloses a preparation method and application of a hydrophilic porous organic polymer based on fluoroborondipyrrin, and belongs to the technical field of photocatalytic materials. The application designs and prepares a hydrophilic porous organic polymer based on fluoroborondipyrrin by using a Friedel-Crafts reaction for cross-linking and modification after a sulfonation reaction, and modifies the hydrophilic porous organic polymer based on fluoroborondipyrrin by using a sulfonation modification strategy. The porous organic polymer after sulfonation has excellent hydrophilicity and photocatalytic performance, and can efficiently degrade organic pollutants in water. The application provides a high-performance porous organic polymer photocatalyst for degrading organic pollutants in wastewater, and provides a simple and feasible new method and new idea for design and development, performance improvement and practical application of photocatalysts.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of photocatalytic materials, and particularly relates to a preparation method and application of a hydrophilic porous organic polymer based on fluorine boron dipyrrin. BACKGROUND

[0002] In recent years, compared with well-known porous materials such as inorganic materials such as zeolites, porous carbon and silicon dioxide and metal-organic framework compounds, porous organic polymers as a new generation of porous materials have important applications in the field of photocatalysis. In the aspect of photocatalytic degradation, the traditional adsorption technology has the shortcomings of poor adsorption performance, slow adsorption speed and inability to degrade dyes into non-toxic and harmless small molecules. Photocatalytic degradation technology can achieve the purpose of rapid degradation of organic pollutants in the presence of light and photocatalyst, and has the advantages of low energy consumption, sustainability and high efficiency. In addition to the characteristics of porosity and high crystallinity, the optical band gap, energy level and inherent photoelectric properties (including their light absorption range, photoelectric charge lifetime and transient photocurrent response) of the porous organic polymer-based photocatalyst can be adjusted, which provides unlimited possibilities for the continuous optimization of its structure to meet the requirements of efficient photocatalysis, and has a broad application prospect. However, there is still a big gap between the performance of the current porous organic polymer photocatalytic material and the actual application requirements, for example, the catalytic performance needs to be improved, the light utilization rate is low and the dispersibility is poor, which restricts the further application of the material, and therefore it is urgent to develop such materials which are easy to prepare and have high performance.

[0003] The main strategies for constructing porous organic polymer photocatalytic materials are pre-design and post-modification. Pre-design refers to pre-designing the required monomers in terms of structural conformation, doping, polarity (electron donor or electron acceptor) and bonding type, which is a forward-looking strategy for preparing high-performance porous organic polymer photocatalysts. Post-modification refers to the difficulty of perfectly integrating all advantages into a porous organic polymer due to immature synthesis technology, structural complexity of the polymer, economic factors, structural defects and other factors. Therefore, post-modification of the framework of the porous organic polymer (such as sulfonation reaction, metal coordination, addition reaction, ionization, etc.) provides a feasible solution to the problems encountered. Among them, the selection of photosensitive center is an important part of the design of photocatalytic materials, which can be realized and ensured by pre-designing the photocatalytic performance of the material. Boron difluoride dipyrrin is a kind of photosensitizer with excellent performance, the core of which is the connection of left and right pyrrole rings with a boron-nitrogen six-membered heterocyclic ring. The two rings are located in the same conjugate plane, and the two nitrogen atoms and the boron atom are located on the two sides of the boron difluoride dipyrrin core plane, which has excellent chemical stability and photophysical properties. More importantly, the molecular structure is easy to modify. Therefore, the introduction of boron difluoride dipyrrin photosensitive units into the porous organic polymer can well utilize the characteristics of high molar absorption coefficient and high fluorescence quantum yield of boron difluoride dipyrrin to adjust the specific surface area, planar rigidity, conjugation degree and photoelectric performance of the material, thereby improving the transmission efficiency of the carrier in the porous organic polymer and obtaining better photocatalytic performance. It has a very wide application in the field of photocatalysis (mainly including photocatalytic hydrolysis, photocatalytic reduction of carbon dioxide, photocatalytic organic synthesis, photocatalytic sterilization and pollutant degradation, etc.). However, the material itself may have certain shortcomings in the actual application process, such as narrow light absorption range, poor dispersibility, easy to be corroded by light, poor durability and high repetition rate of photo-generated carriers, which restricts the improvement of photocatalytic performance and the application of reagents. Therefore, from the perspective of practical application, further functional post-modification is needed to improve the hydrophilicity, stability, broaden the absorption spectrum to improve the utilization rate of sunlight, so that the material has better practical applicability. SUMMARY

[0004] The purpose of the present application is to develop a preparation method and application of a hydrophilic porous organic polymer based on boron difluoride dipyrrin.

[0005] In order to achieve the purpose of the present application, the following technical solutions are provided:

[0006] A preparation method of a porous organic polymer based on boron difluoride dipyrrin, comprising the following steps:

[0007] (1) Dissolve the boron difluoride dipyrrin derivative and cyanuric chloride in a solvent;

[0008] (2) After the solid in step (1) is fully dissolved, a catalyst is added, and the fully dispersed solution is reacted under a protective atmosphere;

[0009] (3) After the reaction is completed, filtration is performed, and the filter cake is washed with a solvent;

[0010] (4) The filter cake obtained in step (3) is eluted using a Soxhlet extractor, vacuum dried, and a fluorobodipy-based porous organic polymer is obtained.

[0011] As a preferred: the molecular structure of the fluorobodipy derivative in step (1) is

[0012]

[0013] wherein R is one of triphenylamine, N-phenylcarbazole, 9-phenylfluorene, 10-phenylphenothiazine, 10-phenylphenoxazine, 9-phenylanthracene, or perylene.

[0014] As a preferred: the molar ratio of the fluorobodipy derivative and cyanuric chloride in step (1) is 1.5:1 to 6:1; the solvent is one or a combination of N,N-dimethylformamide, diethyl ether, dichloromethane, chloroform, acetone, tetrahydrofuran, acetonitrile, toluene, and methanol.

[0015] As a preferred: the molar ratio of the fluorobodipy derivative and the Lewis acid catalyst in step (2) is 1:2 to 1:6; the Lewis acid catalyst is one or a combination of ferric chloride and aluminum chloride; the protective atmosphere is nitrogen or argon; the reaction temperature is 20 to 100°C; and the reaction time is 12 to 72 hours.

[0016] As a preferred: in step (3), the washing agent is one or a combination of 15% hydrochloric acid solution, water, diethyl ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, and methanol.

[0017] As a preferred: in step (4), the eluent is one or a combination of dichloromethane, acetone, tetrahydrofuran, acetonitrile, and methanol; the elution time is 12 to 36 hours; and after elution, drying is performed under vacuum, the drying temperature is 60 to 100°C, and the drying time is 12 to 24 hours.

[0018] The present application provides a preparation method of a fluorobodipy-based hydrophilic porous organic polymer, comprising the following steps:

[0019] (1) dispersing the fluorobodipy-based porous organic polymer in a solvent;

[0020] (2) after the polymer in step (1) is fully dispersed, adding a hydrophilic modification reagent, and reacting the mixed solution under a protective atmosphere;

[0021] (3) After the reaction is complete, filter the mixture and wash the filter cake with solvent.

[0022] (4) The filter cake obtained in step (3) is eluted with a Soxhlet extractor and vacuum dried to obtain a hydrophilic porous organic polymer based on fluoroboron dipyrrole.

[0023] Preferably, the solvent in step (1) is one or a combination of several of N,N-dimethylformamide, diethyl ether, dichloromethane, chloroform, acetone, tetrahydrofuran, acetonitrile, toluene, and methanol.

[0024] As a preferred embodiment: in step (2), the molar ratio of the porous organic polymer based on fluoroboron dipyrrole to the modifying agent is 1:6 to 1:30; the modifying agent is chlorosulfonic acid; the protective atmosphere is nitrogen or argon; the reaction temperature is 20 to 100°C; and the reaction time is 12 to 72 hours.

[0025] Preferably, in step (3), the detergent is one or a combination of several of the following: water, diethyl ether, N,N-dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, and methanol.

[0026] As a preferred option: in step (4), the eluent is one or a combination of several of dichloromethane, acetone, tetrahydrofuran, acetonitrile, and methanol; the elution time is 12 to 36 hours; after elution, the product is dried under vacuum at a temperature of 60 to 100°C for 12 to 24 hours.

[0027] The hydrophilic porous organic polymer based on fluoroboron dipyrrole prepared by the method of the present invention can be applied to the photocatalytic degradation of organic pollutants.

[0028] Preferred organic pollutants are bisphenol A and rhodamine B; the light source for photocatalytic degradation of organic pollutants is a xenon lamp; and the concentration of organic pollutants is 10–100 mg / L. -1 The amount of hydrophilic porous organic polymer based on fluoroboron dipyrrole is 0.1–1 mg / mL. -1 .

[0029] The beneficial effects of this invention are as follows: A porous organic polymer based on fluoroboron dipyrrole is obtained by polymerizing fluoroboron dipyrrole derivatives and cyanuric chloride using a Friedel-Crafts reaction. This polymer is then modified through a sulfonation post-modification strategy. The sulfonated porous organic polymer exhibits excellent hydrophilicity and photocatalytic performance, enabling it to efficiently degrade organic pollutants in water. This invention provides a high-performance porous organic polymer photocatalyst for degrading organic pollutants in wastewater, offering a simple and easy-to-implement new method and approach for the design, development, performance improvement, and practical application of photocatalysts. Attached Figure Description

[0030] Figure 1 Water contact angle diagram of BTTP, a porous organic polymer based on fluoroboron dipyrrole, prepared in Example 1;

[0031] Figure 2 Water contact angle diagram of BTTP-SO3H, a hydrophilic porous organic polymer based on fluoroboron dipyrrole, prepared in Example 1;

[0032] Figure 3 Impedance diagrams of the porous organic polymer BTTP based on fluoroboron dipyrrole and the hydrophilic porous organic polymer BTTP-SO3H based on fluoroboron dipyrrole prepared in Example 1.

[0033] Figure 4 Photocurrent diagrams of the porous organic polymer BTTP based on fluoroboron dipyrrole and the hydrophilic porous organic polymer BTTP-SO3H based on fluoroboron dipyrrole prepared in Example 1.

[0034] Figure 5 Scanning electron microscope image of BTTP-SO3H, a hydrophilic porous organic polymer based on fluoroboron dipyrrole, prepared in Example 1;

[0035] Figure 6 0.3 mg L prepared in Example 1 -1 The porous organic polymer BTTP based on fluoroboron dipyrrole and the hydrophilic porous organic polymer BTTP-SO3H based on fluoroboron dipyrrole, respectively, photodegraded 50 mg / L of each polymer. -1 Performance comparison chart of bisphenol A. Detailed Implementation Plan

[0036] 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.

[0037] Example 1

[0038] Following the synthetic route:

[0039]

[0040] (1) 10-(4-(diphenylamino)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexaneborane (4.73 g, 9.63 mmol) and cyanuric chloride (1.17 g, 6.42 mmol) and 200 mL of dichloromethane were added to a 500 mL Schlenk flask and stirred thoroughly for 30 minutes under a nitrogen atmosphere.

[0041] (2) After the solution in step (1) is fully mixed, aluminum trichloride (0.69 g, 4.28 mmol) is added to the above reaction solution. After being fully dispersed, the mixed solution is heated to reflux at 70°C for 36 hours under a nitrogen atmosphere.

[0042] (3) After the reaction is complete, the reaction solution is cooled to room temperature and filtered. The filter cake obtained by filtration is washed in sequence with 15% hydrochloric acid solution, water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0043] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, acetone, tetrahydrofuran and methanol for 36 hours. The eluted filter cake was transferred to a vacuum drying oven and dried under vacuum at 60°C for 24 hours to obtain a porous organic polymer BTTP based on fluoroboron dipyrrole with a yield of 98%.

[0044] (5) The porous organic polymer BTTP (2.34 g, 3.63 mmol) based on fluoroboron dipyrrole obtained in step (4) and 200 mL of dichloromethane were placed in a 500 mL Schlenk flask and stirred and dispersed for 30 minutes under a nitrogen atmosphere.

[0045] (6) After the reaction solution in step (5) is fully dispersed, 20 mL of chlorosulfonic acid is slowly added dropwise under ice bath conditions. After all the chlorosulfonic acid has been added, the reaction solution is stirred for 20 minutes and then reacted at room temperature for 36 hours.

[0046] (7) After the reaction is complete, the reaction solution is slowly dripped into ice water, cooled to room temperature and then filtered. The filter cake obtained is washed in sequence with water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0047] (8) The filter cake obtained in step (7) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, acetone, tetrahydrofuran and methanol for 36 hours. The eluted filter cake was transferred to a vacuum drying oven and dried under vacuum at 60°C for 24 hours to obtain a hydrophilic porous organic polymer BTTP-SO3H based on fluoroboron dipyrrole with a yield of 95%.

[0048] Example 2

[0049] Following the synthetic route:

[0050]

[0051] (1) 10-(4-(9-carbazolyl)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4-Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexaneborane (4.71 g, 9.63 mmol) and cyanuric chloride (1.17 g, 6.42 mmol) and 200 mL of dichloromethane were added to a 500 mL Schlenk flask and stirred thoroughly for 30 minutes under a nitrogen atmosphere.

[0052] (2) After the solution in step (1) is fully mixed, aluminum trichloride (0.69 g, 4.28 mmol) is added to the above reaction solution. After being fully dispersed, the mixed solution is heated to reflux at 70°C for 36 hours under a nitrogen atmosphere.

[0053] (3) After the reaction is complete, the reaction solution is cooled to room temperature and filtered. The filter cake obtained by filtration is washed in sequence with 15% hydrochloric acid solution, water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0054] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, acetone, tetrahydrofuran and methanol for 36 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried under vacuum at 60°C for 24 hours to obtain a porous organic polymer BTCZ based on fluoroboron dipyrrole with a yield of 96%.

[0055] (5) The porous organic polymer BTCZ (2.34 g, 3.63 mmol) based on fluoroboron dipyrrole obtained in step (4) and 200 mL of dichloromethane were placed in a 500 mL Schlenk flask and stirred and dispersed for 30 minutes under a nitrogen atmosphere.

[0056] (6) After the reaction solution in step (5) is fully dispersed, 20 mL of chlorosulfonic acid is slowly added dropwise under ice bath conditions. After all the chlorosulfonic acid has been added, the reaction solution is stirred for 20 minutes and then reacted at room temperature for 36 hours.

[0057] (7) After the reaction is complete, the reaction solution is slowly dripped into ice water, cooled to room temperature and then filtered. The filter cake obtained is washed in sequence with water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0058] (8) The filter cake obtained in step (7) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, acetone, tetrahydrofuran and methanol for 36 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried under vacuum at 60°C for 24 hours to obtain a hydrophilic porous organic polymer BTCZ-SO3H based on fluoroboron dipyrrole with a yield of 96%.

[0059] Example 3

[0060] Following the synthetic route:

[0061]

[0062] (1) 10-(4-(9-fluorenyl)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexaneborane (4.7 g, 9.63 mmol) and cyanuric chloride (1.17 g, 6.42 mmol) and 200 mL of dichloromethane were added to a 500 mL Schlenk flask and stirred thoroughly for 30 minutes under a nitrogen atmosphere.

[0063] (2) After the solution in step (1) is fully mixed, aluminum trichloride (0.69 g, 4.28 mmol) is added to the above reaction solution. After being fully dispersed, the mixed solution is heated to reflux at 70°C for 36 hours under a nitrogen atmosphere.

[0064] (3) After the reaction is complete, the reaction solution is cooled to room temperature and filtered. The filter cake obtained by filtration is washed in sequence with 15% hydrochloric acid solution, water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0065] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, acetone, tetrahydrofuran and methanol for 36 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried under vacuum at 60°C for 24 hours to obtain a porous organic polymer BTFR based on fluoroboron dipyrrole with a yield of 90%.

[0066] (5) The porous organic polymer BTFR (2.33 g, 3.63 mmol) based on fluoroboron dipyrrole obtained in step (4) and 200 mL of dichloromethane were placed in a 500 mL Schlenk flask and stirred and dispersed for 30 minutes under a nitrogen atmosphere.

[0067] (6) After the reaction solution in step (5) is fully dispersed, 20 mL of chlorosulfonic acid is slowly added dropwise under ice bath conditions. After all the chlorosulfonic acid has been added, the reaction solution is stirred for 20 minutes and then reacted at room temperature for 36 hours.

[0068] (7) After the reaction is complete, the reaction solution is slowly dripped into ice water, cooled to room temperature and then filtered. The filter cake obtained is washed in sequence with water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0069] (8) The filter cake obtained in step (7) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, acetone, tetrahydrofuran and methanol for 36 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried under vacuum at 60°C for 24 hours to obtain the hydrophilic porous organic polymer BTFR-SO3H based on fluoroboron dipyrrole, with a yield of 96%.

[0070] Example 4

[0071] Following the synthetic route:

[0072]

[0073] (1) 10-(4-(10-phenthiazinyl)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexaneborane (5.02 g, 9.63 mmol) and cyanuric chloride (1.17 g, 6.42 mmol) and 200 mL of dichloromethane were added to a 500 mL Schlenk flask and stirred thoroughly for 30 minutes under a nitrogen atmosphere.

[0074] (2) After the solution in step (1) is fully mixed, aluminum trichloride (0.69 g, 4.28 mmol) is added to the above reaction solution. After being fully dispersed, the mixed solution is heated to reflux at 70°C for 36 hours under a nitrogen atmosphere.

[0075] (3) After the reaction is complete, the reaction solution is cooled to room temperature and filtered. The filter cake obtained by filtration is washed in sequence with 15% hydrochloric acid solution, water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0076] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, acetone, tetrahydrofuran and methanol for 36 hours. The eluted filter cake was transferred to a vacuum drying oven and dried under vacuum at 60°C for 24 hours to obtain a porous organic polymer BTPZ based on fluoroboron dipyrrole with a yield of 97%.

[0077] (5) Place the porous organic polymer BTPZ (2.45 g, 3.63 mmol) based on fluoroboron dipyrrole obtained in step (4) and 200 mL of dichloromethane into a 500 mL Schlenk flask and stir and disperse for 30 minutes under a nitrogen atmosphere.

[0078] (6) After the reaction solution in step (5) is fully dispersed, 20 mL of chlorosulfonic acid is slowly added dropwise under ice bath conditions. After all the chlorosulfonic acid has been added, the reaction solution is stirred for 20 minutes and then reacted at room temperature for 36 hours.

[0079] (7) After the reaction is complete, the reaction solution is slowly dripped into ice water, cooled to room temperature and then filtered. The filter cake obtained is washed in sequence with water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0080] (8) The filter cake obtained in step (7) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, acetone, tetrahydrofuran and methanol for 36 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried under vacuum at 60°C for 24 hours to obtain a hydrophilic porous organic polymer BTPZ-SO3H based on fluoroboron dipyrrole with a yield of 96%.

[0081] Example 5

[0082] Following the synthetic route:

[0083]

[0084] (1) 10-(4-(10-phenoxazinyl)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexaneborane (4.87 g, 9.63 mmol) and cyanuric chloride (1.17 g, 6.42 mmol) and 200 mL of dichloromethane were added to a 500 mL Schlenk flask and stirred thoroughly for 30 minutes under a nitrogen atmosphere.

[0085] (2) After the solution in step (1) is fully mixed, aluminum trichloride (0.69 g, 4.28 mmol) is added to the above reaction solution. After being fully dispersed, the mixed solution is heated to reflux at 70°C for 36 hours under a nitrogen atmosphere.

[0086] (3) After the reaction is complete, the reaction solution is cooled to room temperature and filtered. The filter cake obtained by filtration is washed in sequence with 15% hydrochloric acid solution, water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0087] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, acetone, tetrahydrofuran and methanol for 36 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried under vacuum at 60°C for 24 hours to obtain a porous organic polymer BTPO based on fluoroboron dipyrrole with a yield of 85%.

[0088] (5) The porous organic polymer BTPO (2.39 g, 3.63 mmol) based on fluoroboron dipyrrole obtained in step (4) and 200 mL of dichloromethane were placed in a 500 mL Schlenk flask and stirred and dispersed for 30 minutes under a nitrogen atmosphere.

[0089] (6) After the reaction solution in step (5) is fully dispersed, 20 mL of chlorosulfonic acid is slowly added dropwise under ice bath conditions. After all the chlorosulfonic acid has been added, the reaction solution is stirred for 20 minutes and then reacted at room temperature for 36 hours.

[0090] (7) After the reaction is complete, the reaction solution is slowly dripped into ice water, cooled to room temperature and then filtered. The filter cake obtained is washed in sequence with water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0091] (8) The filter cake obtained in step (7) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, acetone, tetrahydrofuran and methanol for 36 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried under vacuum at 60°C for 24 hours to obtain a hydrophilic porous organic polymer BTPO-SO3H based on fluoroboron dipyrrole with a yield of 95%.

[0092] Example 6

[0093] Following the synthetic route:

[0094]

[0095] (1) 10-(4-(9-anthrayl)phenyl)-5,5-difluoro-1,3,7,9-tetramethyl-5H-4λ 4 ,5λ 4 -Dipyrrolo[1,2-c:2',1'-f][1,3,2]diazacyclohexaneborane (4.82 g, 9.63 mmol) and cyanuric chloride (1.17 g, 6.42 mmol) and 200 mL of dichloromethane were added to a 500 mL Schlenk flask and stirred thoroughly for 30 minutes under a nitrogen atmosphere.

[0096] (2) After the solution in step (1) is fully mixed, aluminum trichloride (0.69 g, 4.28 mmol) is added to the above reaction solution. After being fully dispersed, the mixed solution is heated to reflux at 70°C for 36 hours under a nitrogen atmosphere.

[0097] (3) After the reaction is complete, the reaction solution is cooled to room temperature and filtered. The filter cake obtained by filtration is washed in sequence with 15% hydrochloric acid solution, water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0098] (4) The filter cake obtained in step (3) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, acetone, tetrahydrofuran and methanol for 36 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried under vacuum at 60°C for 24 hours to obtain BTAN, a porous organic polymer based on fluoroboron dipyrrole, with a yield of 88%.

[0099] (5) The porous organic polymer BTAN (2.38 g, 3.63 mmol) based on fluoroboron dipyrrole obtained in step (4) and 200 mL of dichloromethane were placed in a 500 mL Schlenk flask and stirred and dispersed for 30 minutes under a nitrogen atmosphere.

[0100] (6) After the reaction solution in step (5) is fully dispersed, 20 mL of chlorosulfonic acid is slowly added dropwise under ice bath conditions. After all the chlorosulfonic acid has been added, the reaction solution is stirred for 20 minutes and then reacted at room temperature for 36 hours.

[0101] (7) After the reaction is complete, the reaction solution is slowly dripped into ice water, cooled to room temperature and then filtered. The filter cake obtained is washed in sequence with water, methanol, N,N-dimethylformamide, diethyl ether and dichloromethane.

[0102] (8) The filter cake obtained in step (7) was placed in a Soxhlet extractor and eluted sequentially with dichloromethane, acetone, tetrahydrofuran and methanol for 36 hours. The eluted filter cake was then transferred to a vacuum drying oven and dried under vacuum at 60°C for 24 hours to obtain a hydrophilic porous organic polymer BTAN-SO3H based on fluoroboron dipyrrole with a yield of 97%.

[0103] The results of the above embodiments are summarized in Table 1:

[0104] Table 1 Yields of products in each example

[0105]

[0106]

[0107] Application Example 1

[0108] Study on photodegradation of organic pollutant bisphenol A:

[0109] The hydrophilic porous organic polymers based on fluoroboron dipyrrole obtained in Examples 1, 2, 3, 4, 5, and 6 were used to study the photodegradation of the organic pollutant bisphenol A.

[0110] Test samples: hydrophilic porous organic polymers based on fluoroboron dipyrrole obtained in Examples 1, 2, 3, 4, 5, and 6;

[0111] Preparation of bisphenol A solution (organic pollutant): Prepare a solution with a concentration of 10 mg / L. -1 Bisphenol A solution;

[0112] Experimental method: 3 mg of the hydrophilic porous organic polymer based on fluoroboron dipyrrole obtained in Examples 1, 2, 3, 4, 5, and 6, and 10 mL of a 10 mg L solution were added to a constant temperature reactor. -1The bisphenol A solution was thoroughly stirred in the dark to reach adsorption-desorption equilibrium. Then, a photodegradation experiment was conducted using a 300W xenon lamp to simulate sunlight. 1 mL of the reaction solution was taken at 5, 10, 15, 20, and 30 minutes and filtered using a 0.22 μm filter. The concentration of the organic pollutant bisphenol A in the filtrate was monitored and analyzed by high-performance liquid chromatography. The photodegradation efficiency of the hydrophilic porous organic polymer based on fluoroboron dipyrrole for the organic pollutant bisphenol A was calculated, as shown in Table 2.

[0113] The photodegradation efficiency (η) of pollutants is calculated according to the following formula (expressed as a percentage):

[0114]

[0115] Among them, C0(mM) and C t (mM) represents the concentration of pollutants before and after photodegradation (or physical adsorption under dark conditions), respectively.

[0116] Table 2. Photodegradation efficiency of bisphenol A, an organic pollutant, by hydrophilic porous organic polymers based on fluoroboron dipyrrole.

[0117]

[0118]

[0119] Application Example 2

[0120] Photodegradation of organic pollutant Rhodamine B:

[0121] The hydrophilic porous organic polymers based on fluoroboron dipyrrole obtained in Examples 1, 2, 3, 4, 5, and 6 were used to study the photodegradation of the organic pollutant Rhodamine B.

[0122] Test samples: hydrophilic porous organic polymers based on fluoroboron dipyrrole obtained in Examples 1, 2, 3, 4, 5, and 6;

[0123] Preparation of Rhodamine B solution (organic pollutant): Prepare a solution with a concentration of 25 mg / L. -1 Rhodamine B solution;

[0124] Experimental method: 5 mg of the hydrophilic porous organic polymer based on fluoroboron dipyrrole obtained in Examples 1, 2, 3, 4, 5, and 6, and 10 mL of a prepared 25 mg L... were added to a constant temperature reactor. -1Rhodamine B solution was thoroughly stirred in the dark to reach adsorption-desorption equilibrium. Subsequently, a photodegradation experiment was conducted using a 300W xenon lamp to simulate sunlight. 1 mL of the reaction solution was collected at 1, 2, 3, 4, 5, and 10 minutes and filtered using a 0.22 μm filter. The concentration of the organic pollutant Rhodamine B in the solution was monitored and analyzed using UV-HPLC. The photodegradation efficiency of the hydrophilic porous organic polymer based on fluoroboron dipyrrole for the organic pollutant Rhodamine B was calculated, as shown in Table 3.

[0125] The photodegradation efficiency (η) of pollutants is calculated according to the following formula (expressed as a percentage):

[0126]

[0127] Among them, C0(mM) and C t (mM) represents the concentration of pollutants before and after photodegradation (or physical adsorption under dark conditions), respectively.

[0128] Table 3. Photodegradation efficiency of hydrophilic porous organic polymers based on fluoroboron dipyrrole for the organic pollutant Rhodamine B.

[0129]

[0130] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A method for preparing a porous organic polymer based on fluoroboron dipyrrole, characterized in that, The porous organic polymer was prepared by Friedel-Crafts reaction of a fluoroboron dipyrrole derivative with cyanuric chloride under Lewis acid catalysis. The fluoroboron dipyrrole derivatives have the following structural units: Wherein: substituent R is triphenylamine, N 1-Phenylenecarbazole, 9-phenylfluorene, 10-phenylphenthiazine, 10-phenylphenoxazine, 9-phenylanthracene or perylene.

2. The method for preparing porous organic polymers based on fluoroboron dipyrrole according to claim 1, characterized in that, The specific preparation steps of the porous organic polymer are as follows: (1) Dissolve fluoroboron dipyrrole derivatives and cyanuric chloride in a solvent; (2) After the solid in step (1) has fully dissolved, add the Lewis acid catalyst, and react the fully dispersed solution under a protective atmosphere; (3) After the reaction is complete, filter the mixture and wash the filter cake with solvent. (4) The filter cake obtained in step (3) is eluted with a Soxhlet extractor and vacuum dried to obtain a porous organic polymer based on fluoroboron dipyrrole.

3. The method for preparing porous organic polymers based on fluoroboron dipyrrole according to claim 2, characterized in that, The molar ratio of the fluoroboron dipyrrole derivative and cyanuric chloride in step (1) is 1.5:1 to 6:1; The solvent is N , N - One or a combination of several of the following: dimethylformamide, diethyl ether, dichloromethane, chloroform, acetone, tetrahydrofuran, acetonitrile, toluene, and methanol; In step (2), the molar ratio of the fluoroboron dipyrrole derivative and the Lewis acid catalyst is 1:1 to 1:6; the Lewis acid catalyst is one or a combination of ferric chloride and aluminum chloride; the protective atmosphere is nitrogen or argon; the reaction temperature is 20 to 100 °C; and the reaction time is 12 to 72 hours. The solvent used for washing the filter cake in step (3) is 15% hydrochloric acid solution, water, ether, N , N - One or a combination of several of the following: dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, and methanol; The eluent in step (4) is one or a combination of several of dichloromethane, acetone, tetrahydrofuran, acetonitrile, and methanol; the elution time is 12 to 36 hours; the vacuum drying temperature is 60 to 100 ℃, and the vacuum drying time is 12 to 24 hours.

4. A method for preparing a hydrophilic porous organic polymer based on fluoroboron dipyrrole using the porous organic polymer prepared by any one of claims 1 to 3, characterized in that, The specific preparation steps are as follows: (1) The porous organic polymer based on fluoroboron dipyrrole is fully dispersed in a solvent; (2) After the polymer in step (1) is fully dispersed, a hydrophilic modifying agent is added. The modifying agent is chlorosulfonic acid. The mixed solution is reacted under a protective atmosphere. (3) After the reaction is complete, filter the mixture and wash the filter cake with solvent. (4) The filter cake obtained in step (3) is eluted with a Soxhlet extractor and vacuum dried to obtain a hydrophilic porous organic polymer based on fluoroboron dipyrrole.

5. The method for preparing the hydrophilic porous organic polymer based on fluoroboron dipyrrole according to claim 4, characterized in that, The solvent in step (1) is N , N - One or a combination of several of the following: dimethylformamide, diethyl ether, dichloromethane, chloroform, acetone, tetrahydrofuran, acetonitrile, toluene, and methanol.

6. The method for preparing the hydrophilic porous organic polymer based on fluoroboron dipyrrole according to claim 4, characterized in that, In step (2), the molar ratio of the porous organic polymer based on fluoroboron dipyrrole and the modifying reagent is 1:6 to 1:30; the protective atmosphere is nitrogen or argon; the reaction temperature is 20 to 100 °C; and the reaction time is 12 to 72 hours.

7. The method for preparing the hydrophilic porous organic polymer based on fluoroboron dipyrrole according to claim 4, characterized in that, The solvent used for washing the filter cake in step (3) is water, ether, N , N - One or a combination of several of the following: dimethylformamide, dichloromethane, acetone, tetrahydrofuran, acetonitrile, and methanol; The eluent in step (4) is one or a combination of several of dichloromethane, acetone, tetrahydrofuran, acetonitrile, and methanol; the elution time is 12 to 36 hours; the vacuum drying temperature is 60 to 100 ℃, and the vacuum drying time is 12 to 24 hours.

8. An application of a hydrophilic porous organic polymer based on fluoroboron dipyrrole, characterized in that, The hydrophilic porous organic polymer prepared by the method described in claim 5 is used for photocatalytic degradation of organic pollutants; the organic pollutant is bisphenol A or rhodamine B; the light source for photocatalytic degradation of organic pollutants is a xenon lamp.

9. The application of the hydrophilic porous organic polymer based on fluoroboron dipyrrole according to claim 8, characterized in that, During photocatalytic degradation, the concentration of the organic pollutant is 10–100 mg / L. -1 The amount of the hydrophilic porous organic polymer based on fluoroboron dipyrrole is 0.1–1 mg / mL. -1 .

Images