Aromatic amide molecular cage material and preparation method and application thereof

Abstract

The present invention discloses an aromatic amide molecular cage material and a preparation method and application thereof, belonging to the technical field of porous organic functional materials. The present invention uses oligomeric aromatic amide diamine monomers and tetraphenylethylene derivative tetraaldehyde monomers as raw materials, synthesizes intermediates through imine condensation reaction, and then reduces them through a reducing agent to finally prepare an aromatic amide molecular cage material with a large specific surface area; the synthesis method adopts a one-pot method, which can save time and resources and improve the yield. The prepared aromatic amide molecular cage material exhibits excellent adsorption performance for carbon dioxide under standard atmospheric pressure, and can be applied to fields such as selective gas adsorption and separation of carbon dioxide or efficient carbon capture and fixation.

Description

Technical Field

[0001] The invention belongs to the technical field of porous organic functional materials, and specifically relates to an aromatic amide molecular cage material and a preparation method and application thereof. Background Art

[0002] Adsorbents are indispensable products in modern industry. Adsorption technology has become a key separation method in petrochemical, biochemical and pharmaceutical chemicals. The research on adsorption separation technology is combined with various industries and the improvement of human health and environmental quality. In the future, as the scale of various industries continues to grow, the market demand for adsorption separation materials will also increase. Therefore, it is necessary to further explore the structure and properties of adsorption materials.

[0003] Porous materials have structural characteristics such as relatively large specific surface area, customizable pore structure, and modifiable pore environment, and have great potential in gas adsorption. Currently, representative porous materials can be roughly divided into three categories: inorganic porous materials, such as porous carbon materials and molecular sieve materials; inorganic-organic hybrid porous materials, such as metal-organic framework materials (MOFs) and metal-organic coordination cages (MOCs); organic porous materials, such as porous organic polymers (POPs), covalent organic framework materials (COFs), and porous organic molecular cages (POCs). The structural characteristics of porous organic molecular cages (POCs) materials include: they do not contain metals, are organic small molecules with clear structures, can be synthesized in a modular and customized manner, have inherent three-dimensional cavities, are easy to dissolve and process, and can be precisely functionalized and modified. They are ideal research platforms for creating high-performance adsorption and separation materials. Summary of the invention

[0004] In view of the above-mentioned prior art, the present invention discloses an aromatic amide molecular cage material and a preparation method thereof, and the material can be applied to the preparation of selective gas adsorption separation materials by utilizing its pore structure.

[0005] In order to achieve the above object, the technical solution adopted by the present invention is: to provide an aromatic amide molecular cage material and a preparation method thereof, the structural formula of the aromatic amide molecular cage material is as follows:

[0006]

[0007] The preparation method thereof comprises the following steps:

[0008] S1: Adding oligoaromatic amide diamine monomer 1, tetraphenylethylene derivative tetraaldehyde monomer 2 and solvent into a reaction container, the structures of oligoaromatic amide diamine monomer 1 and tetraphenylethylene derivative tetraaldehyde monomer 2 are as follows:

[0009]

[0010] S2: Under heating and stirring conditions, the reaction is kept warm for 60 to 70 hours to obtain an imine intermediate. The structure of the imine intermediate is shown below:

[0011]

[0012] S3: Add reducing agent solution into the reaction container and keep the temperature to react for 40 to 50 hours to obtain aromatic amide molecular cage material.

[0013] On the basis of the above technical solution, the present invention can also be improved as follows:

[0014] Furthermore, in step S1, the usage ratio of the oligoaromatic amide diamine monomer 1, the tetraphenylethylene derivative tetraaldehyde monomer 2 and the solvent is: 0.024-0.028 mmol: 0.011-0.015 mmol: 8-12 mL.

[0015] Furthermore, the solvent is dichloromethane.

[0016] Furthermore, the heating temperature in step S2 is 35-45°C.

[0017] Furthermore, the solute of the reducing agent solution is sodium cyanoborohydride; the molar ratio of sodium cyanoborohydride to the oligomeric aromatic amide diamine monomer 1 is 0.024-0.028:0.38-0.40.

[0018] Furthermore, the solvent of the reducing agent solution is methanol; and the concentration of the reducing agent solution is 0.19-0.2 mol / L.

[0019] Furthermore, the reaction temperature in step S3 is 18-22°C.

[0020] The invention discloses an aromatic amide molecular cage material prepared by the preparation method.

[0021] The invention also discloses the use of aromatic amide molecular cage materials in preparing carbon dioxide selective gas adsorption separation materials or high-efficiency carbon capture and fixation materials.

[0022] The beneficial effects of the present invention are:

[0023] 1. The present invention adopts a one-pot process, the preparation method is simple, and the reaction conditions are relatively mild.

[0024] 2. The three-dimensional cavity of the molecular cage material prepared in the present invention has an alkaline secondary amine (-NH-) action site inside, which increases the adsorption performance of CO2 through chemical adsorption; the secondary amine (-NH-) in the molecular structure can hydrogen bond with CO2 to promote the adsorption of CO2; the amide bond (-CONH-) pre-organized by the intramolecular hydrogen bond will form a carbonyl action site pointing to the inside of the cavity, and the oxygen atom on the carbonyl group has a lone electron pair, which can interact with CO2 through the dipole-quadrupole moment to form a synergistic adsorption site, thereby promoting the adsorption of CO2; this molecular cage material has a benzene ring structure, and the benzene ring is an electron-rich group that can interact with CO2 through the dipole-π interaction to increase the adsorption performance of CO2.

[0025] 3. The aromatic amide molecular cage material of the present invention has a higher specific surface area.

[0026] 4. The adsorption capacity of the aromatic amide molecular cage material for CO2 under standard atmospheric pressure and 298K can reach 56cm 3 / g; at 298K, the adsorption selectivity for N2 is 1972.

[0027] 5. The aromatic amide molecular cage material of the present invention can be used to prepare CO2 selective gas adsorption separation materials or high-efficiency carbon capture and fixation materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 This is a hydrogen nuclear magnetic resonance spectrum of the aromatic amide molecular cage material prepared in Example 1 of the present invention;

[0029] Figure 2 This is the carbon NMR spectrum of the aromatic amide molecular cage material prepared in Example 1 of the present invention;

[0030] Figure 3 This is a high-resolution mass spectrum of the aromatic amide molecular cage material prepared in Example 2 of the present invention;

[0031] Figure 4 The adsorption and desorption curve of CO2 of the aromatic amide molecular cage material prepared in Example 1 of the present invention;

[0032] Figure 5 This is a micropore size distribution diagram of the aromatic amide molecular cage material prepared in Example 1 of the present invention;

[0033] Figure 6 This is a fitting analysis diagram of the adsorption selectivity of the aromatic amide molecular cage material prepared in Example 1 of the present invention for CO2 and N2. DETAILED DESCRIPTION

[0034] The specific implementation modes of the present invention are described in detail below with reference to the embodiments.

[0035] Example 1

[0036] An aromatic amide molecular cage, the structural formula of which is as follows:

[0037]

[0038] In this embodiment, the aromatic amide molecular cage is prepared by the following steps:

[0039] 0.026 mmol of oligomeric aromatic amide diamine monomer 1 and 0.013 mmol of tetraphenylethylene derivative tetraaldehyde monomer 2 were added to a 25 mL round-bottom flask. The structures of the oligomeric aromatic amide diamine monomer 1 and the tetraphenylethylene derivative tetraaldehyde monomer 2 are shown below:

[0040]

[0041] The round-bottom flask was fixed on a heating magnetic stirrer device, and 10 mL of dry dichloromethane was added, and the raw materials were dissolved by stirring. Then the temperature was raised to 40°C, and the mixture was stirred and reacted for 72 hours. During the reaction, a yellow precipitate was precipitated. After 72 hours of reaction, the yellow precipitate no longer increased, and a reaction solution containing an imine intermediate was obtained. The structure of the imine intermediate is shown below:

[0042]

[0043] 0.39mmol sodium cyanoborohydride was dissolved in 2mL methanol, and the sodium cyanoborohydride solution was added to the reaction solution, stirred and mixed evenly, and then kept warm and stirred at 20°C for 48h. During the reaction, the yellow precipitate gradually dissolved, and after 48h of reaction, the color of the solution changed from yellow to light green. After stopping the reaction, the reaction solution was distilled under reduced pressure to remove the low boiling point solvent, and 30mL of anhydrous methanol was added to the obtained crude product to precipitate an insoluble solid crude product. The crude product was then washed twice by solid-liquid extraction, and the filtrate was removed by vacuum filtration. The residue was thermally dissolved with 10mL of CH2Cl2 / MeOH (20 / 1, v / v) mixed solution, and then 30mL of anhydrous methanol was added for re-precipitation. The residue was filtered under reduced pressure, and the residue was rinsed with 30mL of anhydrous ether to obtain a pure aromatic amide molecular cage.

[0044] Example 2

[0045] An aromatic amide molecular cage, the structural formula of which is as follows:

[0046]

[0047] In this embodiment, the aromatic amide molecular cage is prepared by the following steps:

[0048] 0.024 mmol of oligomeric aromatic amide diamine monomer 1 and 0.011 mmol of tetraphenylethylene derivative tetraaldehyde monomer 2 were added to a 25 mL round-bottom flask. The structures of the oligomeric aromatic amide diamine monomer 1 and the tetraphenylethylene derivative tetraaldehyde monomer 2 are shown below:

[0049]

[0050] The round-bottom flask was fixed on a heating magnetic stirrer device, and 8 mL of dry dichloromethane was added. The raw materials were dissolved by stirring, and then the temperature was raised to 35°C. The mixture was stirred and reacted for 65 hours. A yellow precipitate was precipitated during the reaction. After 65 hours of reaction, the yellow precipitate no longer increased, and a reaction solution containing an imine intermediate was obtained. The structure of the imine intermediate is shown below:

[0051]

[0052] 0.38mmol sodium cyanoborohydride was dissolved in 2mL methanol, and the sodium cyanoborohydride solution was added to the reaction solution, stirred and mixed evenly, and then kept warm and stirred at 18°C ​​for 40h. During the reaction, the yellow precipitate gradually dissolved, and after 40h of reaction, the color of the solution changed from yellow to light green. After stopping the reaction, the reaction solution was distilled under reduced pressure to remove the low boiling point solvent, and 30mL of anhydrous methanol was added to the obtained crude product to precipitate an insoluble solid crude product. The crude product was then washed twice by solid-liquid extraction, and the filtrate was removed by vacuum filtration. The filter residue was thermally dissolved with 10mL of CH2Cl2 / MeOH (20 / 1, v / v) mixed solution, and then 30mL of anhydrous methanol was added for re-precipitation. The filter residue was filtered under reduced pressure, and the filter residue was rinsed with 30mL of anhydrous ether to obtain a pure aromatic amide molecular cage.

[0053] Example 3

[0054] An aromatic amide molecular cage, the structural formula of which is as follows:

[0055]

[0056] In this embodiment, the aromatic amide molecular cage is prepared by the following steps:

[0057] 0.028 mmol of oligomeric aromatic amide diamine monomer 1 and 0.015 mmol of tetraphenylethylene derivative tetraaldehyde monomer 2 were added to a 25 mL round-bottom flask. The structures of the oligomeric aromatic amide diamine monomer 1 and the tetraphenylethylene derivative tetraaldehyde monomer 2 are shown below:

[0058]

[0059] The round-bottom flask was fixed on a heating magnetic stirrer device, and 12 mL of dry dichloromethane was added and stirred to dissolve the raw materials. Then the temperature was raised to 45°C and stirred for 60 hours. During the reaction, a yellow precipitate was precipitated. After 60 hours of reaction, the yellow precipitate no longer increased, and a reaction solution containing an imine intermediate was obtained. The structure of the imine intermediate is shown below:

[0060]

[0061] 0.4mmol sodium cyanoborohydride was dissolved in 2mL methanol, and the sodium cyanoborohydride solution was added to the reaction solution, stirred and mixed evenly, and then the mixture was stirred and reacted at 20°C for 50h. During the reaction, the yellow precipitate gradually dissolved, and after 50h of reaction, the color of the solution changed from yellow to light green. After stopping the reaction, the reaction solution was distilled under reduced pressure to remove the low boiling point solvent, and 30mL of anhydrous methanol was added to the obtained crude product to precipitate an insoluble solid crude product. The crude product was then washed twice by solid-liquid extraction, and the filtrate was removed by vacuum filtration. The residue was thermally dissolved with 10mL of CH2Cl2 / MeOH (20 / 1, v / v) mixed solution, and then 30mL of anhydrous methanol was added for re-precipitation. The residue was filtered under reduced pressure, and the residue was rinsed with 30mL of anhydrous ether to obtain a pure aromatic amide molecular cage.

[0062] Test example

[0063] 1. Structural test

[0064] The aromatic amide molecular cage material prepared in Example 1 was characterized by nuclear magnetic resonance. 1 The HNMR results are as follows Figure 1 As shown, (400MHz, CDCl3, 298K), δ9.90 (s, 8H), 9.17 (s, 4H), 8.32~8.23 (m, 8H), 7.59 (d, J=7.9H z, 16H), 7.44 (t, J=8.9Hz, 32H), 7.20 (d, J=8.0Hz, 16H), 6.79 (d, J=8.7Hz, 8H), 6.56 (s, 4H ), 6.39 (d, J=8.8Hz, 8H), 4.32 (s, 16H), 4.20~4.07 (m, 16H), 3.83 (s, 24H), 2.05 (dd, J=11. 7, 5.5Hz, 8H), 1.55 (q, J=6.9Hz, 26H), 1.49~1.33 (m, 64H), 0.92 (dt, J=25.2, 7.1Hz, 48H); 13 CNMR test results are as follows Figure 2As shown, (100MHz, CDCl3, 298K), δ162.69, 160.50, 142.82, 141.55, 139.82, 138.85, 138.29, 132.00, 128.78, 128.50, 127.19, 126.37, 115.91, 108.11, 106.79, 72.96, 56.12, 38.79, 30.26, 29.78, 29.02, 23.68, 23.09, 14.05, 10.72. The high-resolution mass spectrometry isotope peak distribution experiment and simulation comparison of the aromatic amide molecular cage material prepared in Example 2 show that C 260 H 288 N 16 O 24 [M+2H] 2+ The mass-to-charge ratio was estimated to be 2011.0976, and the HRMS results were as follows Figure 3 As shown, a molecular ion peak with a mass-to-charge ratio of 2011.6155 can be found in the figure.

[0065] 2. Gas adsorption and desorption experiments

[0066] The sample prepared in Example 1 was first activated at 50°C under vacuum for 12 h, and then tested using a QuantachromeNova 4000e gas adsorption analyzer (Quantachrome Instruments, USA). The CO2 adsorption-desorption isotherms of the sample were tested at 195K, 273K and 298K in the pressure range of 0 to 1.0 bar by the volumetric method. The results are as follows: Figure 4 As shown; under the temperature conditions of 77K and 298K, the N2 adsorption-desorption isotherms were tested in the pressure range of 0 to 1.0 bar by the volume method.

[0067] The specific surface area and pore size distribution data were calculated from the CO2 adsorption-desorption isotherm data at 195 K, as shown in Figure 5 As shown in Figure 2, the specific surface area is calculated by the multi-point method. The specific surface area of ​​the aromatic amide molecular cage material under solid conditions is 722.6 m 2 / g, the pore size distribution was calculated by the Barrett-Joyner-Halenda (BJH) method, and the micropore size distribution was calculated by the Horvath-Kawazoe (HK) method, and the pore size was about 0.5nm; then the adsorption selectivity of the hydrogen-bonded aromatic amide molecular cage to CO2 and N2 was analyzed based on Henry's law (slope method). The results are as follows Figure 6 As shown, the adsorption selectivity for nitrogen is predicted to be 1972 at 298K.

Claims

1. An aromatic amide molecular cage material, characterized in that: The structural formula of the aromatic amide molecular cage material is as follows: 。 2. The method for preparing the aromatic amide molecular cage material according to claim 1, characterized in that: The following steps are involved: S1: Adding an oligoaromatic amide diamine monomer 1, a tetraphenylethylene derivative tetraaldehyde monomer 2 and a solvent into a reaction container, wherein the structures of the oligoaromatic amide diamine monomer 1 and the tetraphenylethylene derivative tetraaldehyde monomer 2 are as follows: ； S2: Under heating and stirring conditions, the reaction is kept warm for 60 to 70 hours to obtain an imine intermediate, the structure of which is shown below: ； S3: Add a reducing agent solution into the reaction container and keep the temperature to react for 40 to 50 hours to obtain the aromatic amide molecular cage material.

3. The preparation method according to claim 2, characterized in that: In step S1, the usage ratio of the oligoaromatic amide diamine monomer 1, the tetraphenylethylene derivative tetraaldehyde monomer 2 and the solvent is: 0.024-0.028 mmol: 0.011-0.015 mmol: 8-12 mL.

4. The preparation method according to claim 2 or 3, characterized in that: The solvent is dichloromethane.

5. The preparation method according to claim 2, characterized in that: The heating temperature in step S2 is 35-45°C.

6. The preparation method according to claim 2, characterized in that: The solute of the reducing agent solution is sodium cyanoborohydride; the molar ratio of the sodium cyanoborohydride to the oligomeric aromatic amide diamine monomer 1 is 0.024-0.028:0.38-0.

40.

7. The preparation method according to claim 6, characterized in that: The solvent of the reducing agent solution is methanol; the concentration of the reducing agent solution is 0.19-0.2 mol / L.

8. The preparation method according to claim 2, characterized in that: The reaction temperature in step S3 is 18-22°C.

9. Use of the aromatic amide molecular cage material according to claim 1 in the preparation of carbon dioxide selective gas adsorption separation materials or high-efficiency carbon capture and fixation materials.

Images