Synthesis method and application of super-crosslinked polymer
The preparation of carbazole-fluorene-containing hypercrosslinked polymers via FeCl3-promoted anaerobic synthesis has solved the problem of porous material synthesis, achieved efficient carbon dioxide adsorption, and promoted the development of CO2 capture materials.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- CHINA NAT PETROLEUM CORP
- Filing Date
- 2023-10-10
- Publication Date
- 2026-06-02
AI Technical Summary
Existing technologies make it difficult to efficiently synthesize porous organic hypercrosslinked polymers, resulting in insufficient adsorption performance of carbon dioxide capture materials.
Using FeCl3 as an oxidation promoter, a carbazole-fluorene-containing hypercrosslinked polymer was synthesized under anaerobic and anhydrous conditions. The polymer was then prepared by methanol quenching and washing to obtain a porous polymer with a high specific surface area.
The synthesized hypercrosslinked polymer exhibits highly efficient carbon dioxide adsorption performance, providing new materials and synthesis strategies, offering new ideas for CO2 capture, and advancing the research field.
Smart Images
Figure CN119798655B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of hypercrosslinked polymer technology, and more particularly to a method for synthesizing and applying a hypercrosslinked polymer. Background Technology
[0002] The petroleum industry involves the release and generation of carbon dioxide during oil and gas extraction, transportation, and energy conversion. The negative impacts of carbon dioxide, including the greenhouse effect and acid rain, have a significant negative impact on society. Currently, carbon dioxide capture, utilization, and storage (CCUS) technology is an important means of addressing the greenhouse effect.
[0003] Physical adsorption is an important research area at CCUS, and related adsorption material research mainly focuses on porous organic polymers. Currently, this primarily covers metal-organic frameworks (MOFs), covalent organic frameworks (COFs), conjugated microporous polymers (CMPs), and hyper-crosslinked porous organic polymers (HCPs). Among these, HCPs have the advantage of simpler synthesis conditions and easier operation compared to MOFs and COFs, and the advantage of a larger specific surface area compared to CMPs, making them more suitable for gas adsorption.
[0004] Therefore, how to synthesize porous organic hypercrosslinked polymers has become a technical challenge to be solved. Summary of the Invention
[0005] The purpose of this invention is to provide a method for synthesizing hypercrosslinked polymers to solve the above-mentioned problems.
[0006] To achieve the above objectives, the present invention provides a method for synthesizing a hypercrosslinked polymer, the method comprising:
[0007] FeCl3 solid was placed into the reactor, and the reactor was kept in an oxygen-free and water vapor-free state.
[0008] A mixed solution of substrate and reactant is added to a reactor to carry out the first reaction, thereby obtaining the first reactant;
[0009] The first reaction product was quenched with methanol, and the quenched product was filtered to obtain the second product.
[0010] The second product was washed and dried to obtain a hypercrosslinked polymer;
[0011] The substrates include 2,7-bis(azacarbazolyl)-9,9-difluorofluorene or 2,7-bis(azacarbazolyl)-9,9-dimethylfluorene; the reactants include dimethoxymethane or 1,4-dimethoxybenzene.
[0012] This invention also provides an application of hypercrosslinked polymers in CO2 adsorption.
[0013] The technical effects and advantages of this invention are as follows:
[0014] The carbazole-fluorene-containing HCP material involved in this invention is a porous polymer containing N and F atoms and is an effective CO2 adsorbent. This patent is the first to propose a synthesis method for this type of material and apply it to the effective adsorption of CO2. It can provide a more advanced synthesis strategy for the synthesis of this type of porous material, offer new ideas and materials for CO2 capture, and to a certain extent lead the progress of this research field.
[0015] Other features and advantages of the invention will be set forth in the following description, and will be apparent in part from the description, or may be learned by practicing the invention. The objects and other advantages of the invention can be realized and obtained by means of the structures pointed out in the description and the drawings. Attached Figure Description
[0016] Figure 1 This is a flowchart of the synthesis method for hypercrosslinked polymers;
[0017] Figure 2 Infrared characterization of bis[2,7-bis(azacarbazolyl)-9,9-difluorofluorenyl]methane hypercrosslinked polymer (FFCM-HCP);
[0018] Figure 3 The image shows the SEM spectra of the bis[2,7-bis(azacarbazolyl)-9,9-difluorofluorenyl]methane hypercrosslinked polymer (FFCM-HCP).
[0019] Figure 4A The specific surface area characterization results of the bis[2,7-bis(azacarbazolyl)-9,9-difluorofluorenyl]methane hypercrosslinked polymer (FFCM-HCP) are shown in the figure.
[0020] Figure 4B The figure shows the pore size distribution characterization results of the bis[2,7-bis(azacarbazolyl)-9,9-difluorofluorenyl]methane hypercrosslinked polymer (FFCM-HCP). Detailed Implementation
[0021] The technical solution of the present invention will now be clearly and completely described with reference to the accompanying drawings. Furthermore, the described embodiments are merely some, not all, of the embodiments of the present invention. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.
[0022] It should be noted that the structures, proportions, sizes, etc., illustrated in the accompanying drawings are merely for illustrative purposes to aid those skilled in the art and to facilitate understanding and reading. They are not intended to limit the scope of the invention and therefore have no substantial technical significance. Any modifications to the structure, changes in proportions, or adjustments to size, without affecting the effectiveness and purpose of the invention, should still fall within the scope of the technical content disclosed herein. Furthermore, the terms "upper," "lower," "left," "right," "middle," and "one" used in this specification are merely for clarity and not intended to limit the scope of the invention. Changes or adjustments to their relative relationships, without substantially altering the technical content, should also be considered within the scope of the invention.
[0023] Conjugated microporous polymers (CMPs) allow for pore structure control from a molecular design perspective. To achieve high-capacity CO2 absorption, it is necessary to increase the specific surface area of the material and, more importantly, increase the number of electron-rich heteroatoms (e.g., N, F) on the polymer backbone to promote more stable interactions between CO2 molecules and these electron-rich atoms and groups. The carbazole-fluorene-containing HCP material involved in this invention is a porous polymer containing N and F atoms and is an effective CO2 adsorbent. This patent is the first to propose a synthetic method for this type of material and apply it to the effective adsorption of CO2. It can provide a more advanced synthetic strategy for the synthesis of this type of porous material, offering new ideas and materials for CO2 capture, and to some extent leading the progress of this research field.
[0024] The following combination Figure 1 A detailed introduction to the synthesis methods of hypercrosslinked polymers is provided:
[0025] A method for synthesizing a hypercrosslinked polymer, the method comprising:
[0026] 1. Place solid FeCl3 into the reactor and keep the reactor in an oxygen-free and water vapor-free state.
[0027] 2. Add the mixed solution of substrate and reactant to the reactor to carry out the first reaction and obtain the first reactant.
[0028] The method involves dissolving the substrate and reactants in a solvent to obtain a mixed solution; wherein the solvent includes one of the following: 1,2-dichloroethane, dichloromethane, or trichloromethane.
[0029] The substrates include 2,7-bis(azacarbazolyl)-9,9-difluorofluorene or 2,7-bis(azacarbazolyl)-9,9-dimethylfluorene; the reactants include dimethoxymethane or 1,4-dimethoxybenzene.
[0030] The mass ratio of FeCl3 to the substrate ranges from 3:1 to 6:1; the mass ratio of the substrate to the reactants ranges from 1:1 to 1:6. A larger amount of FeCl3 is used because it is an oxidation promoter to ensure sufficient substrate reaction. The ratio of substrate to reactants is between 1 / 1 and 1 / 6 because the substrate is expensive, and ensuring its complete reaction is crucial.
[0031] 3. Add methanol to the first reaction product to quench it, and filter the quenched product to obtain the second product.
[0032] The conditions for the first reaction include: a reaction temperature of 80-150℃ and a reaction time of 24-48h.
[0033] Methanol can also be a polar solvent containing oxygen atoms, such as ethanol, tetrahydrofuran, or diethyl ether, and its main purpose is to deactivate FeCl3.
[0034] 4. The second product is washed and dried to obtain a hypercrosslinked polymer.
[0035] The process of washing and drying the second product to obtain a hypercrosslinked polymer includes: ultrasonically washing the second product with methanol to obtain an ultrasonically washed solid; dispersing the ultrasonically washed solid with 60 mL of concentrated hydrochloric acid to obtain a dispersion solution; diluting the concentrated hydrochloric acid with water to obtain a diluted solid; washing the diluted solid with methanol, and performing a Soxhlet extraction on the washed solid with methanol and tetrahydrofuran to obtain an extracted solid; and drying the extracted solid in a vacuum drying oven to obtain the hypercrosslinked polymer.
[0036] Specifically, the second product is ultrasonically washed with methanol 3-5 times. The diluted solid is washed with methanol 3-5 times. The drying conditions include: drying time of 24-48 hours and drying temperature of 120-150°C.
[0037] Among them, 2,7-bis(azacarbazolyl)-9,9-difluorofluorene + dimethoxymethane yields a bis[2,7-bis(azacarbazolyl)-9,9-difluorofluorene]methane hypercrosslinked polymer;
[0038] 2,7-Di(azacarbazolyl)-9,9-difluorofluorene + 1,4-dimethoxybenzene yields a bis[2,7-di(azacarbazolyl)-9,9-difluorofluorene]benzene hypercrosslinked polymer;
[0039] 2,7-Di(azacarbazolyl)-9,9-dimethylfluorene + dimethoxymethane yields a bis[2,7-di(azacarbazolyl)-9,9-dimethylfluorene]methane hypercrosslinked polymer;
[0040] 2,7-Di(azacarbazolyl)-9,9-dimethylfluorene + 1,4-dimethoxybenzene yields a bis[2,7-di(azacarbazolyl)-9,9-dimethylfluorene]benzene hypercrosslinked polymer.
[0041] The present invention also provides an application of hypercrosslinked polymers in CO2 adsorption.
[0042] To better explain this scheme, examples of hypercrosslinked polymers synthesized under different conditions are also provided below.
[0043] Example 1
[0044] FeCl3 solid (2.256 mmol, 365.9 mg) was added to a 100 mL three-necked round-bottom flask. The reaction system was evacuated and purged with nitrogen three times to ensure that there was no oxygen or water vapor in the reaction flask. 2,7-bis(azacarbazolyl)-9,9-difluorofluorene (0.376 mmol, 200 mg) and dimethoxymethane (2.256 mmol, 171.7 mg) were dissolved in 55 mL of 1,2-dichloroethane and added dropwise to the reaction system using a syringe. After the addition was complete, the mixture was heated to 80 °C and refluxed for 48 hours under nitrogen protection. After the reaction was completed, 30 mL of methanol was added to quench the reaction, and stirring was continued for 1 hour. The reaction mixture was filtered to obtain a brownish-black solid. The solid was ultrasonically washed three times with 30 mL of methanol. The solid was dispersed in 60 mL of concentrated hydrochloric acid and magnetically stirred for 1 hour. The concentrated hydrochloric acid was diluted with water, filtered, and the solid was washed with 20 mL of methanol three times. The solid was then extracted with methanol and tetrahydrofuran for 24 h each, and dried in a vacuum drying oven at 120 °C for 24 h to finally obtain the target product FFCM-HCP, a reddish-brown solid of 161.2 mg.
[0045] Example 2
[0046] FeCl3 solid (2.256 mmol, 365.9 mg) was added to a 100 mL three-necked round-bottom flask. The reaction system was evacuated and purged with nitrogen three times to ensure that there was no oxygen or water vapor in the reaction flask. 2,7-bis(azacarbazolyl)-9,9-difluorofluorene (0.376 mmol, 200 mg) and dimethoxymethane (2.256 mmol, 171.7 mg) were dissolved in 55 mL of 1,2-dichloroethane and added dropwise to the reaction system using a syringe. After the addition was complete, the mixture was heated to 140 °C and refluxed for 48 hours under nitrogen protection. After the reaction was completed, 30 mL of methanol was added to quench the reaction, and stirring was continued for 1 hour. The reaction mixture was filtered to obtain a brownish-black solid. The solid was ultrasonically washed three times with 30 mL of methanol. The solid was dispersed in 60 mL of concentrated hydrochloric acid and magnetically stirred for 1 hour. The concentrated hydrochloric acid was diluted with water, filtered, and the solid was washed with 20 mL of methanol three times. The solid was then extracted with methanol and tetrahydrofuran for 24 h each, and dried in a vacuum drying oven at 120 °C for 24 h to finally obtain the target product FFCM-HCP, a reddish-brown solid of 193.0 mg.
[0047] Example 3
[0048] FeCl3 solid (2.256 mmol, 365.9 mg) was added to a 100 mL three-necked round-bottom flask. The reaction system was evacuated and purged with nitrogen three times to ensure that there was no oxygen or water vapor in the reaction flask. 2,7-bis(azacarbazolyl)-9,9-difluorofluorene (0.376 mmol, 200 mg) and dimethoxymethane (2.256 mmol, 171.7 mg) were dissolved in 55 mL of 1,2-dichloroethane and added dropwise to the reaction system using a syringe. After the addition was complete, the mixture was heated to 150 °C and refluxed for 48 hours under nitrogen protection. After the reaction was completed, 30 mL of methanol was added to quench the reaction, and stirring was continued for 1 hour. The reaction mixture was filtered to obtain a brownish-black solid. The solid was ultrasonically washed three times with 30 mL of methanol. The solid was dispersed in 60 mL of concentrated hydrochloric acid and magnetically stirred for 1 hour. The concentrated hydrochloric acid was diluted with water, filtered, and the solid was washed with 20 mL of methanol three times. The solid was then extracted with methanol and tetrahydrofuran for 24 hours each, and dried in a vacuum drying oven at 120°C for 24 hours to finally obtain the target product FFCM-HCP, a reddish-brown solid of 215.2 mg.
[0049] Example 4
[0050] FeCl3 solid (2.256 mmol, 365.9 mg) was added to a 100 mL three-necked round-bottom flask. The reaction system was evacuated and purged with nitrogen three times to ensure that there was no oxygen or water vapor in the reaction flask. 2,7-bis(azacarbazolyl)-9,9-difluorofluorene (0.376 mmol, 200 mg) and dimethoxymethane (2.256 mmol, 171.7 mg) were dissolved in 55 mL of 1,2-dichloroethane and added dropwise to the reaction system using a syringe. After the addition was complete, the mixture was heated to 150 °C and refluxed for 24 hours under nitrogen protection. After the reaction was completed, 30 mL of methanol was added to quench the reaction, and stirring was continued for 1 hour. The reaction mixture was filtered to obtain a brownish-black solid. The solid was ultrasonically washed three times with 30 mL of methanol. The solid was dispersed in 60 mL of concentrated hydrochloric acid and magnetically stirred for 1 hour. The concentrated hydrochloric acid was diluted with water, filtered, and the solid was washed with 20 mL of methanol three times. The solid was then extracted with methanol and tetrahydrofuran for 24 hours each, and dried in a vacuum drying oven at 120°C for 24 hours to finally obtain the target product FFCM-HCP, a reddish-brown solid of 181.0 mg.
[0051] Example 5
[0052] FeCl3 solid (1.128 mmol, 183.0 mg) was added to a 100 mL three-necked round-bottom flask. The reaction system was evacuated and purged with nitrogen three times to ensure that there was no oxygen or water vapor in the reaction flask. 2,7-bis(azacarbazolyl)-9,9-difluorofluorene (0.376 mmol, 200 mg) and dimethoxymethane (2.256 mmol, 171.7 mg) were dissolved in 55 mL of 1,2-dichloroethane and added dropwise to the reaction system using a syringe. After the addition was complete, the mixture was heated to 140 °C and refluxed for 48 hours under nitrogen protection. After the reaction was completed, 30 mL of methanol was added to quench the reaction, and stirring was continued for 1 hour. The reaction mixture was filtered to obtain a brownish-black solid. The solid was ultrasonically washed three times with 30 mL of methanol. The solid was dispersed in 60 mL of concentrated hydrochloric acid and magnetically stirred for 1 hour. The concentrated hydrochloric acid was diluted with water, filtered, and the solid was washed with 20 mL of methanol three times. The solid was then extracted with methanol and tetrahydrofuran for 24 hours each, and dried in a vacuum drying oven at 120°C for 24 hours to finally obtain the target product FFCM-HCP, 172.0 mg of reddish-brown solid.
[0053] Example 6
[0054] FeCl3 solid (1.128 mmol, 183.0 mg) was added to a 100 mL three-necked round-bottom flask. The reaction system was evacuated and purged with nitrogen three times to ensure that there was no oxygen or water vapor in the reaction flask. 2,7-bis(azacarbazolyl)-9,9-difluorofluorene (0.376 mmol, 200 mg) and dimethoxymethane (1.128 mmol, 85.9 mg) were dissolved in 55 mL of 1,2-dichloroethane and added dropwise to the reaction system using a syringe. After the addition was complete, the mixture was heated to 140 °C and refluxed for 48 hours under nitrogen protection. After the reaction was completed, 30 mL of methanol was added to quench the reaction, and stirring was continued for 1 hour. The reaction mixture was filtered to obtain a brownish-black solid. The solid was ultrasonically washed three times with 30 mL of methanol. The solid was dispersed in 60 mL of concentrated hydrochloric acid and magnetically stirred for 1 hour. The concentrated hydrochloric acid was diluted with water, filtered, and the solid was washed with 20 mL of methanol three times. The solid was then extracted with methanol and tetrahydrofuran for 24 hours each, and dried in a vacuum drying oven at 120°C for 24 hours to finally obtain the target product FFCM-HCP, 122.0 mg of reddish-brown solid.
[0055] Example 7
[0056] FeCl3 solid (2.256 mmol, 365.9 mg) was added to a 100 mL three-necked round-bottom flask. The reaction system was evacuated and purged with nitrogen three times to ensure that there was no oxygen or water vapor in the reaction flask. 2,7-bis(azacarbazolyl)-9,9-difluorofluorene (0.376 mmol, 200 mg) and 1,4-dimethoxybenzene (2.25 mmol, 311.0 mg) were dissolved in 55 mL of 1,2-dichloroethane and added dropwise to the reaction system using a syringe. After the addition was complete, the mixture was heated to 140 °C and refluxed for 48 hours under nitrogen protection. After the reaction was completed, 30 mL of methanol was added to quench the reaction, and stirring was continued for 1 hour. The reaction mixture was filtered to obtain a brownish-black solid. The solid was ultrasonically washed three times with 30 mL of methanol. The solid was dispersed in 60 mL of concentrated hydrochloric acid and magnetically stirred for 1 hour. The concentrated hydrochloric acid was diluted with water, filtered, and the solid was washed with 20 mL of methanol three times. The solid was then subjected to Soxhlet extraction with methanol and tetrahydrofuran for 24 h each, and the solid was dried in a vacuum drying oven at 120 °C for 24 h to finally obtain the target product bis[2,7-bis(azacarbazolyl)-9,9-difluorofluorenyl]
[0057] Benzene hypercrosslinked polymer, reddish-brown solid, 161.0 mg.
[0058] Example 8
[0059] FeCl3 solid (2.256 mmol, 365.9 mg) was added to a 100 mL three-necked round-bottom flask. The reaction system was evacuated and purged with nitrogen three times to ensure that there was no oxygen or water vapor in the reaction flask. 2,7-bis(azacarbazolyl)-9,9-difluorofluorene (0.376 mmol, 200 mg) and dimethoxymethane (0.376 mmol, 45.9 mg) were dissolved in 55 mL of 1,2-dichloroethane and added dropwise to the reaction system using a syringe. After the addition was complete, the mixture was heated to 150 °C and refluxed for 48 hours under nitrogen protection. After the reaction was completed, 30 mL of methanol was added to quench the reaction, and stirring was continued for 1 hour. The reaction mixture was filtered to obtain a brownish-black solid. The solid was ultrasonically washed three times with 30 mL of methanol. The solid was dispersed in 60 mL of concentrated hydrochloric acid and magnetically stirred for 1 hour. The concentrated hydrochloric acid was diluted with water, filtered, and the solid was washed with 20 mL of methanol three times. The solid was then extracted with methanol and tetrahydrofuran for 24 h each, and dried in a vacuum drying oven at 120 °C for 24 h to finally obtain the target product FFCM-HCP, a reddish-brown solid of 162.0 mg.
[0060] Example 9
[0061] FeCl3 solid (2.286 mmol, 370.6 mg) was added to a 100 mL three-necked round-bottom flask. The reaction system was evacuated and purged with nitrogen three times to ensure that there was no oxygen or water vapor in the reaction flask. 2,7-Di(azacarbazolyl)-9,9-dimethylfluorene (0.381 mmol, 200 mg) and dimethoxymethane (2.286 mmol, 279.1 mg) were dissolved in 55 mL of 1,2-dichloroethane and added dropwise to the reaction system using a syringe. After the addition was complete, the mixture was heated to 150 °C and refluxed for 48 hours under nitrogen protection. After the reaction was completed, 30 mL of methanol was added to quench the reaction, and stirring was continued for 1 hour. The reaction mixture was filtered to obtain a brownish-black solid. The solid was ultrasonically washed three times with 30 mL of methanol. The solid was dispersed in 60 mL of concentrated hydrochloric acid and magnetically stirred for 1 hour. The concentrated hydrochloric acid was diluted with water, filtered, and the solid was washed with 20 mL of methanol three times. The solid was then extracted with methanol and tetrahydrofuran for 24 h each, and dried in a vacuum drying oven at 120 °C for 24 h to finally obtain bis[2,7-bis(azacarbazolyl)-9,9-dimethylfluorenyl]methane hypercrosslinked polymer, 224.3 mg of reddish-brown solid.
[0062] Example 10
[0063] FeCl3 solid (2.286 mmol, 370.6 mg) was added to a 100 mL three-necked round-bottom flask. The reaction system was evacuated and purged with nitrogen three times to ensure that there was no oxygen or water vapor in the reaction flask. 2,7-Di(azacarbazolyl)-9,9-dimethylfluorene (0.381 mmol, 200 mg) and 1,4-dimethoxybenzene (2.286 mmol, 316.0 mg) were dissolved in 55 mL of 1,2-dichloroethane and added dropwise to the reaction system using a syringe. After the addition was complete, the mixture was heated to 150 °C and refluxed for 48 hours under nitrogen protection. After the reaction was completed, 30 mL of methanol was added to quench the reaction, and stirring was continued for 1 hour. The reaction mixture was filtered to obtain a brownish-black solid. The solid was ultrasonically washed three times with 30 mL of methanol. The solid was dispersed in 60 mL of concentrated hydrochloric acid and magnetically stirred for 1 hour. Concentrated hydrochloric acid was diluted with water in the system, filtered, and the solid was washed with 20 mL × 3 mL of methanol. Then, the solid was extracted with methanol and tetrahydrofuran for 24 h each, and the solid was dried in a vacuum drying oven at 120 °C for 24 h to finally obtain bis[2,7-bis(azacarbazolyl)-9,9-dimethylfluorenyl]benzene hypercrosslinked polymer, 236.5 mg of reddish-brown solid.
[0064] The present invention also characterized the bis[2,7-bis(azacarbazolyl)-9,9-difluorofluorenyl]methane hypercrosslinked polymer (FFCM-HCP) obtained in Example 1 by infrared spectroscopy, as follows: Figure 2 As shown. According to Figure 2 The main absorption peaks are observed to be ν 3455, 2928, 1639, 1285, 1480, 1112, 1022, 939, and 620 cm⁻¹, respectively. -1 The broad absorption peak at 3500-3000 cm⁻¹ corresponds to the CH bond on the aromatic ring, and the peak at 2928 cm⁻¹ corresponds to the CH bond on the aromatic ring. -1 The absorption peak at 1285 cm⁻¹ represents the methylene group. -1 The absorption peak at 1022 cm⁻¹ is due to the CN bond on the carbazole ring, while the peak at 1022 cm⁻¹ is due to the CN bond on the carbazole ring. -1 The absorption peak at that point corresponds to the -CF2 bond after fluorene modification.
[0065] The present invention also performed SEM tests on the bis[2,7-bis(azacarbazolyl)-9,9-difluorofluorenyl]methane hypercrosslinked polymer (FFCM-HCP) obtained in Example 1. The SEM spectra are shown below. Figure 3 As shown. According to Figure 3 It can be seen that the material is a spherical cluster at the microscopic level, with a particle diameter of less than 200 nm and interspersed with pore structures, indicating that the material can be used for gas adsorption.
[0066] The present invention also characterized the pore structure of the bis[2,7-bis(azacarbazolyl)-9,9-difluorofluorenyl]methane hypercrosslinked polymer (FFCM-HCP) obtained in Example 1, such as... Figure 4AThe specific surface area characterization results of FFCM-HCP, such as... Figure 4B The results represent the pore size distribution. Figure 4A The adsorption and desorption of N2 at 77K indicates that the material has a microporous and mesoporous structure, with a BET of 507m. 2 / g. Figure B characterizes the pore size distribution of the material, showing that the average pore size is 4.4 nm and the micropore volume is 0.146 cm³. 3 / g.
[0067] Finally, it should be noted that the above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the protection scope of the present invention.
Claims
1. A method for synthesizing a hypercrosslinked polymer, characterized in that, The method includes: FeCl3 solid was placed into the reactor, and the reactor was kept in an oxygen-free and water vapor-free state. A mixed solution of substrate and reactant is added to a reactor to carry out a first reaction, obtaining a first reactant; the mass ratio of FeCl3 to substrate is in the range of 3:1 to 6:1; the mass ratio of substrate to reactant is in the range of 1:1 to 1:
6. The first reactant was quenched with methanol, and the quenched product was filtered to obtain the second product. The second product was washed and dried to obtain a hypercrosslinked polymer; The substrate includes 2,7-bis(azirazolyl)-9,9-difluorofluorene or 2,7-bis(azirazolyl)-9,9-dimethylfluorene; the reactant includes dimethoxymethane or 1,4-dimethoxybenzene.
2. The method according to claim 1, characterized in that, A mixed solution is obtained by dissolving the substrate and reactant in a solvent; wherein the solvent includes one of the following: 1,2-dichloroethane, dichloromethane, or trichloromethane.
3. The method according to claim 1, characterized in that, The conditions for the first reaction include: a reaction temperature range of 80-150℃ and a reaction time range of 24-48h.
4. The method according to claim 1, characterized in that, The second product is washed and dried to obtain a hypercrosslinked polymer, comprising: The second product was ultrasonically washed with methanol to obtain the ultrasonically washed solid. The ultrasonicated solid was dispersed using concentrated hydrochloric acid to obtain a dispersion solution; Dilute concentrated hydrochloric acid with water to obtain a diluted solid; The diluted solid was washed with methanol, and the washed solid was subjected to Soxhlet extraction with methanol and tetrahydrofuran to obtain the extracted solid. The extracted solid was placed in a vacuum drying oven and dried to obtain a hypercrosslinked polymer.
5. The method according to claim 4, characterized in that, The second product is ultrasonically washed with methanol 3-5 times.
6. The method according to claim 4, characterized in that, The diluted solid is washed with methanol 3-5 times.
7. The method according to claim 4, characterized in that, The drying conditions include: a drying time of 24-48 hours and a drying temperature of 120-150°C.
8. The application of the hypercrosslinked polymer prepared by the synthesis method according to any one of claims 1-7 in CO2 adsorption.