A carbazolyl porous polymer, a preparation method and application thereof

Abstract

The application provides a cup-carbazole-based porous polymer and a preparation method and application thereof, and belongs to the field of organic polymer materials. The cup-carbazole-based porous polymer has a multi-level pore structure, a large specific surface area, good stability, a simple polymerization process and the like, and can be applied to the fields of volatile organic pollutant adsorption and sewage treatment and the like.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of organic polymer materials, in particular to a calix[4]carbazole-based porous polymer and a preparation method and application thereof. BACKGROUND

[0002] Volatile organic compounds (VOCs) generated from industrial processes and human activities are the main cause of air pollution. VOCs include a variety of chemical substances such as aromatic hydrocarbons, alcohols, ketones and halogen-containing compounds. Many of these VOCs are not easily degradable and pose a significant risk to human health and the environment. Therefore, air treatment solutions for VOCs are increasingly attracting attention from the industry and academia.

[0003] Currently, a variety of technologies have been employed to control and treat VOCs, including catalytic oxidation, biological filtration, condensation and adsorption. Among them, adsorption technology is widely adopted due to its low cost, simple operation, high efficiency and environmental friendliness. However, traditional adsorbents such as activated carbon and zeolites have poor removal efficiency. Compared with these materials, porous organic polymers (POPs) are potential excellent candidates for VOCs adsorption due to their inherent advantages, including high porosity, controllable pore size and easy functionalization.

[0004] Incorporating macrocyclic receptors into POP networks is an effective strategy to improve their adsorption performance due to host-guest chemistry. Currently, crown ethers, calixarenes, resorcinarene calixarenes, pillararenes and calix[4]pyrroles have been successfully incorporated into POP networks and shown effectiveness in wastewater adsorption treatment. However, macrocycle-based POPs have not been used for VOCs adsorption treatment. Therefore, it is of great significance to design and synthesize a macrocycle-based POP adsorbent for VOCs treatment. SUMMARY

[0005] The present application provides a calix[4]carbazole-based porous polymer and a preparation method and application thereof. The calix[4]carbazole-based porous polymer of the present application has high stability and excellent VOCs adsorption capacity.

[0006] The present application provides a calix[4]carbazole-based porous polymer, which has a structural formula as shown in Formula I:

[0007] Formula I.

[0008] Preferably, the BET specific surface area of the calix[4]carbazole-based porous polymer is 750-1000 m 2 ·g -1 .

[0009] Preferably, the method comprises the following steps:

[0010] Mixing a compound of a structural formula shown in formula II, a compound of a structural formula shown in formula III, an inorganic base and an organic solvent to carry out a nucleophilic substitution reaction to obtain the calixarene-based porous polymer;

[0011] Formula II;

[0012] Formula III.

[0013] Preferably, the molar ratio of the compound of a structural formula shown in formula II to the compound of a structural formula shown in formula III is 1:1.5.

[0014] Preferably, the inorganic base comprises one or more of potassium carbonate, sodium carbonate, cesium carbonate, potassium bicarbonate and sodium bicarbonate.

[0015] Preferably, the molar ratio of the compound of a structural formula shown in formula II to the inorganic base is 1:6-15.

[0016] Preferably, the organic solvent comprises one or more of tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, 1,4-dioxane, N,N-dimethylformamide and N,N-dimethylacetamide.

[0017] Preferably, the solid-liquid ratio of the compound of a structural formula shown in formula II to the organic solvent is 50-100 mg:1 mL.

[0018] Preferably, the temperature of the nucleophilic substitution reaction is 80-200 DEG C, and the time is 1-48 h.

[0019] The application further provides an application of the calixarene-based porous polymer in adsorbing VOCs or sewage treatment.

[0020] The calixarene-based porous polymer has the advantages of multistage pore structure, large specific surface area, good stability, simple polymerization process and the like, the multistage pore structure can reduce mass transfer resistance, the large specific surface area can provide sufficient adsorption space, the calixarene macrocycle serves as a strong adsorption site to bring excellent adsorption performance to the polymer, and the high stability is conducive to the practical use of the polymer. BRIEF DESCRIPTION OF DRAWINGS

[0021] Figure 1 Cross-polarization / magic angle spinning of the calixarene-based porous polymer prepared for Example 1 13 C nuclear magnetic resonance spectrum;

[0022] Figure 2An infrared analysis spectrum of the carbazolyl porous polymer prepared in Example 1;

[0023] Figure 3 A thermogravimetric analysis spectrum of the carbazolyl porous polymer prepared in Example 1;

[0024] Figure 4 A nitrogen adsorption-desorption isotherm graph of the carbazolyl porous polymer prepared in Example 1 at 77K;

[0025] Figure 5 A pore size distribution graph of the carbazolyl porous polymer prepared in Example 1;

[0026] Figure 6 A scanning electron microscope graph of the carbazolyl porous polymer prepared in Example 1;

[0027] Figure 7 A VOCs adsorption amount graph of the carbazolyl porous polymer prepared in Example 1. DETAILED DESCRIPTION

[0028] The present application provides a cup carbazolyl porous polymer, having a structural formula shown in Formula I;

[0029] Formula I.

[0030] In the present application, the BET specific surface area of the cup carbazolyl porous polymer is preferably 836-883 m 2 ·g -1 .

[0031] The wavy line in Formula I represents a repeating unit.

[0032] In the present application, the BET specific surface area of the cup carbazolyl porous polymer is preferably 750-1000 m 2 ·g -1 .

[0033] The present application provides a preparation method of the cup carbazolyl porous polymer described in the above technical solution, comprising the following steps:

[0034] Mixing a compound having a structural formula shown in Formula II, a compound having a structural formula shown in Formula III, an inorganic base and an organic solvent to perform a nucleophilic substitution reaction to obtain the cup carbazolyl porous polymer;

[0035] Formula II;

[0036] Formula III.

[0037] In the present application, the mixing preferably comprises: mixing the compound of the structural formula shown in Formula II, the compound of the structural formula shown in Formula III and the organic solvent, and then mixing the obtained mixture with the inorganic base under a protective atmosphere.

[0038] In the present application, the molar ratio of the compound of the structural formula shown in Formula II to the compound of the structural formula shown in Formula III is preferably 1:1-3, and in specific embodiments of the present application, the molar ratio of the compound of the structural formula shown in Formula II to the compound of the structural formula shown in Formula III can be 1:1, 1:1.5, 1:2, 1:2.5 or 1:3.

[0039] In the present application, the molar ratio of the compound of the structural formula shown in Formula II to the inorganic base is preferably 1:6-15, and in specific embodiments of the present application, the molar ratio of the compound of the structural formula shown in Formula II to the inorganic base can be 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14 or 1:15; the inorganic base preferably comprises one or more of potassium carbonate, sodium carbonate, cesium carbonate, potassium bicarbonate and sodium bicarbonate.

[0040] In the present application, the solid-liquid ratio of the compound of the structural formula shown in Formula II to the organic solvent is preferably 50-100 mg:1 mL, and in specific embodiments of the present application, the solid-liquid ratio of the compound of the structural formula shown in Formula II to the organic solvent can be 50 mg:1 mL, 60 mg:1 mL, 70 mg:1 mL, 80 mg:1 mL, 90 mg:1 mL or 100 mg:1 mL; the organic solvent preferably comprises one or more of tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, 1,4-dioxane, N,N-dimethylformamide and N,N-dimethylacetamide.

[0041] In the present application, the temperature of the nucleophilic substitution reaction is preferably 80-200℃, and the time is preferably 1-48 h; in specific embodiments of the present application, the temperature of the nucleophilic substitution reaction can be 80℃, 100℃, 120℃, 140℃, 160℃, 180℃ or 200℃; and the time of the nucleophilic substitution reaction can be 1 h, 6 h, 12 h, 18 h, 24 h, 30 h, 36 h, 42 h or 48 h.

[0042] In the present application, after the nucleophilic substitution reaction, preferably further comprising: performing solid-liquid separation on the product obtained by the nucleophilic substitution reaction, and then performing washing, Soxhlet extraction and drying on the solid obtained by the solid-liquid separation.

[0043] In the present application, the washing preferably comprises first deionized water washing, acid solution washing and second deionized water washing in sequence.

[0044] The first deionized water washing is not specially limited in the present application, and the conventional technical solution can be adopted to wash until the washing liquid is colorless and there is no obvious white potassium carbonate solid in the crude product.

[0045] In the present application, the acid solution used for the acid solution washing preferably comprises hydrochloric acid, sulfuric acid, fluoroboric acid or acetic acid; the concentration of the acid solution is preferably 0.1-2M, and in the specific embodiment of the present application, the acid solution can be dilute hydrochloric acid with a concentration of 1M.

[0046] The acid solution washing is not specially limited in the present application, and the conventional technical solution can be adopted to remove the inorganic base in the solid.

[0047] The second deionized water washing is not specially limited in the present application, and the conventional technical solution can be adopted to wash until neutral.

[0048] In the present application, the reagent used for the Soxhlet extraction preferably comprises methanol.

[0049] The Soxhlet extraction is not specially limited in the present application, and the conventional technical solution can be adopted to extract until there is no polymer dissolved in the extraction liquid.

[0050] The present application also provides the application of the calixcarbazole-based porous polymer in adsorbing VOCs or sewage treatment.

[0051] The calixcarbazole-based porous polymer, the preparation method and the application thereof provided by the present application will be described in detail below in combination with examples, but they should not be understood as limiting the protection scope of the present application.

[0052] Example 1

[0053] The calix[3]carbazole (250mg, 0.290mmol) and tetrafluoroterephthalonitrile (87mg, 0.435mmol) were dissolved in 5mL of anhydrous DMSO, and then K2CO3 (601mg, 4.35mmol) was added under nitrogen protection. The reaction bottle was quickly placed in 150℃ for 6h. After the reaction was completed, the solid was washed with deionized water. Then 50mL of dilute hydrochloric acid (1M) was used to wash the alkali in the reaction system, and then deionized water was used for washing, followed by Soxhlet extraction with methanol for 24h, and then the product was vacuum dried at 80 o C vacuum drying, the obtained polymer yield was 98%, and the BET specific surface area was 836m 2 g -1 .

[0054] Figure 1 Cross-polarization / magic-angle spinning 13C nuclear magnetic resonance spectrum of the calixcarbazole-based porous polymer prepared in Example 1. 13 C nuclear magnetic resonance spectrum.

[0055] Depend on Figure 1 It can be seen that the most obvious peak at 154 ppm is attributed to the CO bond, indicating that the polymer was successfully synthesized according to the set synthesis route.

[0056] Figure 2 This is the infrared analysis spectrum of the carbazole-based porous polymer prepared in Example 1.

[0057] Depend on Figure 2 It can be seen that 1233 cm -1 The peak at is attributed to CO stretching vibration.

[0058] Figure 3 This is a thermogravimetric analysis spectrum of the carbazole-based porous polymer prepared in Example 1;

[0059] Depend on Figure 3 It can be seen that the polymer is at 350 o There is almost no weight loss below 80 °C, indicating that the polymer has high thermal stability.

[0060] Figure 4 This is a nitrogen adsorption-desorption isotherm diagram of the carbazole-based porous polymer prepared in Example 1 at 77K.

[0061] Depend on Figure 4 It can be seen that the polymer shows a type IV adsorption curve, and the specific surface area can be calculated to be 836m 2 / g.

[0062] Figure 5 This is the pore size distribution diagram of the carbazole-based porous polymer prepared in Example 1.

[0063] Depend on Figure 5 It can be seen that the polymer has abundant micro-mesopores. The micropore volume can be calculated to be 0.30 cm 3 / g, and the mesopore volume is 0.34 cm 3 / g.

[0064] Figure 6 This is a scanning electron microscope image of the carbazole-based porous polymer prepared in Example 1.

[0065] Depend on Figure 6 It can be seen that the polymer is a fluffy mass.

[0066] Figure 7 This is a graph showing the VOCs adsorption capacity of the carbazole-based porous polymer prepared in Example 1.

[0067] Depend on Figure 7It can be seen that the polymer has good adsorption capacity for a variety of volatile organic compounds (dichloromethane, chloroform, 1,2-dichloroethane, ethyl acetate, acetone, chlorobenzene, toluene, methanol, etc.), especially for dichloromethane and chloroform.

[0068] Example 2

[0069] The cup [3] carbazole (250 mg, 0.290 mmol) and 2,3,5,6-tetrafluoroisonicotinonitrile (77 mg, 0.435 mmol) were dissolved in 5 mL of anhydrous DMSO, and then K2CO3 (601 mg, 4.35 mmol) was added under nitrogen protection. The reaction bottle was quickly placed in a 150 o C for 6 h. After the reaction was completed, the solid was washed with deionized water. Then 50 mL of dilute hydrochloric acid (1 M) was used to wash the base in the reaction system, and then deionized water was used for washing, followed by methanol Soxhlet extraction for 24 h, and then the product was vacuum dried at 80 o C. The yield of the obtained polymer was 99%, and the BET specific surface area was 883 m 2 g -1 .

[0070] Application Example 1

[0071] Adsorption of volatile organic compounds (taking dichloromethane as an example)

[0072] After the polymer sample in Example 1 was vacuum degassed at 120°C, 50 mg of the sample was placed in a 10 mL sample bottle, and 5 mL of dichloromethane was placed in another 10 mL sample bottle. Then the two sample bottles were placed in a 500 mL glass bottle, the glass bottle was sealed, and placed in a 30°C constant temperature box for 24 h. The adsorption capacity was calculated by the weight change of the sample before and after adsorption, which was 1720 mg / g -1 .

[0073] The above only describes the preferred embodiments of the present application, and it should be noted that for ordinary skilled persons in the art, without departing from the principles of the present application, a number of improvements and refinements can be made, and these improvements and refinements should also be considered as the protection scope of the present application.

Claims

1. A calixcarbazolyl porous polymer, characterized in that: It has the structural formula shown in Formula I: Formula I; The BET specific surface area of ​​the cup-carbazolyl-based porous polymer is 750-1000 m 2 ·g -1 .

2. The method for preparing the calixcarbazolyl porous polymer according to claim 1, characterized in that: The following steps are involved: Mixing the compound represented by the structural formula of Formula II, the compound represented by the structural formula of Formula III, an inorganic base, and an organic solvent to carry out a nucleophilic substitution reaction to obtain the calixcarbazolyl-based porous polymer; Formula II; Formula III.

3. The preparation method according to claim 2, characterized in that The molar ratio of the compound represented by the structural formula of Formula II to the compound represented by the structural formula of Formula III is 1:1-3.

4. The preparation method according to claim 2, characterized in that The inorganic base includes one or more of potassium carbonate, sodium carbonate, cesium carbonate, potassium bicarbonate and sodium bicarbonate.

5. The preparation method according to claim 2 or 4, characterized in that The molar ratio of the compound of the structural formula represented by Formula II to the inorganic base is 1:6-15.

6. The preparation method according to claim 2, characterized in that The organic solvent includes one or more of tetrahydrofuran, N-methylpyrrolidone, dimethyl sulfoxide, 1,4-dioxane, N,N-dimethylformamide and N,N-dimethylacetamide.

7. The preparation method according to claim 2 or 6, characterized in that The solid-to-liquid ratio of the compound of the structural formula represented by Formula II to the organic solvent is 50-100 mg:1 mL.

8. The preparation method according to claim 2, characterized in that The temperature of the nucleophilic substitution reaction is 80-200° C., and the time is 1-48 hours.

9. Use of the calixcarbazole-based porous polymer according to claim 1 or the calixcarbazole-based porous polymer prepared by the preparation method according to any one of claims 2 to 8 in the adsorption of VOCs.

Images