CN111621055A - Supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect and preparation method thereof - Google Patents

Supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect and preparation method thereof Download PDF

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CN111621055A
CN111621055A CN202010505769.4A CN202010505769A CN111621055A CN 111621055 A CN111621055 A CN 111621055A CN 202010505769 A CN202010505769 A CN 202010505769A CN 111621055 A CN111621055 A CN 111621055A
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cyclodextrin
aerogel
polyimide
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CN111621055B (en
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张和平
张忠心
程旭东
龚伦伦
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University of Science and Technology of China USTC
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    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
    • C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
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    • C08J2205/02—Foams characterised by their properties the finished foam itself being a gel or a gel being temporarily formed when processing the foamable composition
    • C08J2205/026—Aerogel, i.e. a supercritically dried gel
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    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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    • C08J2405/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2401/00 or C08J2403/00
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Abstract

The invention provides a supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect and a preparation method thereof. The invention adopts a sol-gel method, namely a host-guest complex is formed through the identification interaction of cyclodextrin and aromatic diamine supermolecule, then aromatic diacid anhydride is added to form polyamic acid, a cross-linking agent is added to form a cross-linking type polyamic acid structure, and the cross-linking type polyimide aerogel with high specific surface area and good mechanical property is obtained through imidization and drying. Compared with the prior art, the raw materials are cheap and easy to obtain, the operation is simple and convenient, and the density of the obtained aerogel is less than 0.142g/m3Meanwhile, the content of polyimide in the aerogel is reduced, and the problem of high cost of the polyimide aerogel is solved.

Description

Supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect and preparation method thereof
Technical Field
The invention belongs to the technical field of aerogels, and particularly relates to a supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect and a preparation method thereof.
Background
The aerogel is a porous solid material with a three-dimensional network structure, has the characteristics of high porosity (80-99%), high specific surface area, low thermal conductivity, low density, low dielectric constant and the like, and is a solid material with the lowest density known in the world at present. The polymer aerogel is formed by forming a three-dimensional network through an organic polymer molecular chain framework. Because the preparation process is simple, the mechanical property is good, the integrity of the block body and the aging resistance are good, the polymer aerogel gradually draws the attention of researchers.
Polyimide is used as a common engineering plastic, has excellent thermal stability, chemical stability, flame retardance and mechanical properties, and is widely applied to the fields of aviation, aerospace, microelectronics, nano, liquid crystal, separation membranes, laser and the like at present. Therefore, the preparation of the polyimide into the aerogel can improve various performances of the aerogel. Chinese patent CN105617956B forms the aerogel through compounding molybdenum disulfide nanosheet and polyamic acid salt solution, and then has prepared molybdenum disulfide/polyimide composite aerogel through the mode of thermal imidization and has been applied to the battery, has improved battery stability and security. The Chinese patent CN105968354B improves the adsorption capacity of the polyimide aerogel on carbon dioxide by introducing carboxyl on the main chain of the polyimide molecule.
Supramolecules are composed of two or more subsystem, which form an entity with a certain structure and function through intermolecular forces. Intermolecular forces within supramolecules are non-covalent, typically electrostatic, hydrogen bonding, van der waals forces, and the like. At present, supramolecules are widely used in the fields of chemical catalysis, loading, batteries, drug delivery, and the like.
In order to expand the application range of the polyimide aerogel, the polyimide aerogel needs to be further modified, which is a problem to be solved urgently.
Disclosure of Invention
In view of the above, the present invention provides a supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect and a preparation method thereof, wherein the supramolecular aerogel prepared by the method has excellent mechanical properties.
The invention provides a preparation method of a supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect, which comprises the following steps:
dissolving cyclodextrin and diamine in a mass ratio of 1: 2-20 in N-methylpyrrolidone to obtain a mixed solution;
adding aromatic dianhydride into the mixed solution, and stirring to obtain a cyclodextrin-polyamide acid solution;
and (3) reacting the cyclodextrin-polyamic acid solution with 1,3, 5-tri (4-aminophenyl) benzene, adding a dehydrating agent, uniformly stirring, aging for 22-26 h after gel is formed, sequentially soaking the obtained aging product in different solvents, and drying by supercritical carbon dioxide to obtain the supramolecular aerogel with the cyclodextrin-polyimide molecular recognition effect.
Preferably, the cyclodextrin is selected from one or more of alpha-cyclodextrin, beta-cyclodextrin and gamma-cyclodextrin;
the diamine is selected from 4, 4-diaminodiphenyl ether and/or 4,4 '-diamino-2, 2' -dimethylbiphenyl.
The aromatic dianhydride monomer is selected from 3,3',4,4' -biphenyl tetracarboxylic dianhydride;
the mass ratio of the diamine to the aromatic dianhydride is n: n +1, wherein n is the polymerization degree of the polyimide segment and is 20, 30, 40, 50 or 60.
Preferably, the dehydrating agent is selected from a mixture of acetic anhydride and pyridine;
the mass ratio of the acetic anhydride to the pyridine to the aromatic dianhydride is 7.5-8.5: 1.
Preferably, the raw materials are sequentially soaked in N-methyl pyrrolidone, N-methyl pyrrolidone/acetone with the volume ratio of 3:1, N-methyl pyrrolidone/acetone with the volume ratio of 1:3 and acetone for 22-26 h.
Preferably, the drying temperature of the supercritical carbon dioxide is 50-60 ℃, the pressure is 11.5-12.5 MPa, and the time is 46-50 h.
Preferably, the mole ratio of the 1,3, 5-tri (4-aminophenyl) benzene to the aromatic dianhydride is 1: 20-50.
The invention provides a supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect, which is prepared by the preparation method of the technical scheme.
The invention provides a preparation method of a supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect, which comprises the following steps: dissolving cyclodextrin and diamine in a mass ratio of 1: 2-20 in N-methylpyrrolidone to obtain a mixed solution; adding aromatic dianhydride into the mixed solution, and stirring to obtain a cyclodextrin-polyamide acid solution; and (3) reacting the cyclodextrin-polyamic acid solution with 1,3, 5-tri (4-aminophenyl) benzene, adding a dehydrating agent, uniformly stirring, aging for 22-26 h after gel is formed, sequentially soaking the obtained aging product in different solvents, and drying by supercritical carbon dioxide to obtain the supramolecular aerogel with the cyclodextrin-polyimide molecular recognition effect. The preparation method disclosed by the invention is prepared by interaction of cyclodextrin and polyimide, a sol-gel method and drying under a supercritical carbon dioxide condition, and the method can furthest retain the excellent mechanical properties and thermal stability of the polyimide aerogel. The experimental results show that: the specific surface area of the supramolecular aerogel is 475-536 m2The density of the mixture is 0.012-0.019 g/cm3The thermal conductivity coefficient is 0.029-0.032W/(Mk), the modulus is 3.6-9.7 MPa, and the shrinkage rate is 7.6% -15.1%.
Drawings
FIG. 1 is a picture of the appearance of an aerogel prepared in example 2 of the present invention;
FIG. 2 is an SEM image of an aerogel prepared according to example 2 of the present invention;
FIG. 3 is N of an aerogel prepared in example 4 of the present invention2An adsorption desorption curve;
fig. 4 is a water contact angle picture of the aerogel prepared in example 5 of the present invention.
Detailed Description
The invention provides a preparation method of a supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect, which comprises the following steps:
dissolving cyclodextrin and diamine in a mass ratio of 1: 2-20 in N-methylpyrrolidone to obtain a mixed solution;
adding aromatic dianhydride into the mixed solution, and stirring to obtain a cyclodextrin-polyamide acid solution;
and (3) reacting the cyclodextrin-polyamic acid solution with 1,3, 5-tri (4-aminophenyl) benzene, adding a dehydrating agent, uniformly stirring, aging for 22-26 h after gel is formed, sequentially soaking the obtained aged product in different solvents, and drying by supercritical carbon dioxide to obtain the supramolecular aerogel with the cyclodextrin-polyimide molecular recognition effect.
According to the invention, cyclodextrin is introduced into a polyimide aerogel system, and the elasticity of the aerogel is enhanced through the molecular recognition interaction of the cyclodextrin and polyimide; in addition, the mechanical stability of the aerogel is improved through the pulley effect of the cyclodextrin on the polyimide molecular chain.
According to the invention, cyclodextrin and diamine with the mass ratio of 1: 2-20 are dissolved in N-methyl pyrrolidone to obtain a mixed solution. In the present invention, the cyclodextrin is preferably selected from one or more of α -cyclodextrin (α -CD), β -cyclodextrin (β -CD) and γ -cyclodextrin (γ -CD). The diamine is preferably selected from 4, 4-diaminodiphenyl ether or 4,4 '-diamino-2, 2' -dimethylbiphenyl. The mass ratio of the N-methylpyrrolidone to the diamine is 20-50: 1.
After a mixed solution is obtained, the aromatic dianhydride is added into the mixed solution and stirred to obtain the cyclodextrin-polyamide acid solution. In the present invention, the aromatic dianhydride is preferably selected from 3,3',4,4' -biphenyltetracarboxylic dianhydride; the mass ratio of the diamine to the aromatic dianhydride is n: n +1, wherein n is the polymerization degree of the polyimide segment and is 20, 30, 40, 50 or 60. The stirring temperature is preferably room temperature, and more preferably 20-30 ℃; the stirring time is preferably 25-35 min, and more preferably 28-32 min.
After the cyclodextrin-polyamide acid solution is obtained, the cyclodextrin-polyamide acid solution reacts with 1,3, 5-tri (4-aminophenyl) benzene, then a dehydrating agent is added, the mixture is uniformly stirred, the mixture is aged for 22-26 hours after gel is formed, the obtained aged product is sequentially soaked in different solvents, and the supercritical carbon dioxide is dried, so that the supramolecular aerogel with the cyclodextrin-polyimide molecular recognition effect is obtained. In the present invention, the 1,3, 5-tris (4-aminophenyl) benzene (TAB) is used as a crosslinking agent to crosslink the polyamic acid to form a three-dimensional network structure; the crosslinker is preferably dissolved in NMP to provide a crosslinker solution, which is then mixed with the cyclodextrin-polyamic acid solution. The molar ratio of the addition amount of the cross-linking agent to the aromatic dianhydride is 1: 20-50.
Adding a cross-linking agent, uniformly stirring, and adding a dehydrating agent; the dehydrating agent is preferably selected from a mixture of acetic anhydride and pyridine; the mass ratio of the acetic anhydride to the pyridine to the aromatic dianhydride is 7.5-8.5: 1. In the specific embodiment, the acetic anhydride is preferably added firstly, the mixture is stirred for 55 to 65 seconds, then the pyridine is added, and the mixture is stirred for 55 to 65 seconds.
In the invention, N-methyl pyrrolidone/acetone with a volume ratio of 3:1, N-methyl pyrrolidone/acetone with a volume ratio of 1:3 and acetone are soaked for 22-26 h in sequence. In the specific embodiment, the soaking time is 24 h.
In the invention, the supercritical carbon dioxide drying temperature is 50-60 ℃, the pressure is 11.5-12.5 MPa, and the time is 46-50 h. In the specific embodiment, the temperature for drying the supercritical carbon dioxide is 55 ℃, and the pressure is 12 MPa. The time is 48 h.
The invention provides a supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect, which is prepared by the preparation method of the technical scheme.
In the invention, the specific surface area of the supramolecular aerogel is 475-536 m2The density of the mixture is 0.012-0.019 g/cm3The thermal conductivity coefficient is 0.029-0.032W/(Mk), the modulus is 3.6-9.7 MPa, and the shrinkage rate is 7.6% -15.1%.
In order to further illustrate the present invention, the supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect and the preparation method thereof provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1) Dissolving ODA (645mg, 3.22mmol) and alpha-cyclodextrin (627mg, 0.644mmol) in 54.7mL of N-methylpyrrolidone (NMP) to form a supramolecular molecular recognition interaction;
2) adding aromatic 3,3',4,4' -biphenyl tetracarboxylic dianhydride (BPDA 981mg,3.33mmol) into the solution, and stirring at room temperature for 30 minutes to form a cyclodextrin-polyamide acid solution with super-molecular recognition interaction;
3) dissolving a crosslinking agent 1,3, 5-tris (4-aminophenyl) benzene (TAB, 26mg) in 1 mLN-methylpyrrolidone (NMP), pouring into the solution formed in step 2), and stirring for 20 minutes;
4) adding 2.1mL of acetic anhydride into the solution, stirring for 1 minute, adding 2.2mL of pyridine, and continuing to stir for 1 minute;
5) pouring the solution into a mold, sealing, and continuing aging for 24h after gel is formed;
6) soaking the obtained gel in NMP, NMP/acetone (3/1), NMP/acetone (1/1), NMP/acetone (1/3) and acetone solvent for 24h respectively;
7) and drying the soaked gel by supercritical carbon dioxide under the condition that the drying temperature is 55 ℃ and the pressure is kept at 12MPa for 48 hours.
The aerogel obtained has a specific surface area of 525m2G, density of 0.011g/cm3The coefficient of thermal conductivity is 0.029W/(mK), the modulus is 3.7MPa, and the shrinkage rate is 15.1%.
Example 2:
1) dissolving ODA (645mg, 3.22mmol) and beta-cyclodextrin (731mg, 0.644mmol) in 54.7mL of N-methylpyrrolidone (NMP) to form a supramolecular molecular recognition interaction;
2) adding aromatic 3,3',4,4' -biphenyl tetracarboxylic dianhydride (BPDA 981mg,3.33mmol) into the solution, and stirring at room temperature for 30 minutes to form a cyclodextrin-polyamide acid solution with super-molecular recognition interaction;
3) dissolving a crosslinking agent 1,3, 5-tris (4-aminophenyl) benzene (TAB, 26mg) in 1mL of N-methylpyrrolidone (NMP), pouring into the solution formed in the step 2), and stirring for 20 minutes;
4) adding 2.1mL of acetic anhydride into the solution, stirring for 1 minute, adding 2.2mL of pyridine, and continuing to stir for 1 minute;
5) pouring the solution into a mold, sealing, and continuing aging for 24h after gel is formed;
6) soaking the obtained gel in NMP, NMP/acetone (3/1), NMP/acetone (1/1), NMP/acetone (1/3) and acetone solvent for 24h respectively;
7) and drying the soaked gel by supercritical carbon dioxide under the condition that the drying temperature is 55 ℃ and the pressure is kept at 12MPa for 48 hours.
The obtained aerogel has the specific surface area of 536 square meters/g and the density of 0.013g/cm3The coefficient of thermal conductivity is 0.030W/(mK), the modulus is 3.9MPa, and the shrinkage rate is 14.7%.
FIG. 1 is a picture of the appearance of an aerogel prepared in example 2 of the present invention; fig. 2 is an SEM image of an aerogel prepared in example 2 of the present invention.
Example 3:
1) DMBZ (6684mg, 3.22mmol) and beta-cyclodextrin (731mg, 0.644mmol) were dissolved in 54.7mL of N-methylpyrrolidone (NMP) to form supramolecular molecular recognition interactions;
2) adding aromatic 3,3',4,4' -biphenyl tetracarboxylic dianhydride (BPDA 981mg,3.33mmol) into the solution, and stirring at room temperature for 30 minutes to form a cyclodextrin-polyamide acid solution with super-molecular recognition interaction;
3) dissolving a crosslinking agent 1,3, 5-tris (4-aminophenyl) benzene (TAB, 26mg) in 1mL of N-methylpyrrolidone (NMP), pouring into the solution formed in the step 2), and stirring for 20 minutes;
4) adding 2.1mL of acetic anhydride into the solution, stirring for 1 minute, adding 2.2mL of pyridine, and continuing to stir for 1 minute;
5) pouring the solution into a mold, sealing, and continuing aging for 24h after gel is formed;
6) soaking the obtained gel in NMP, NMP/acetone (3/1), NMP/acetone (1/1), NMP/acetone (1/3) and acetone solvent for 24h respectively;
7) and drying the soaked gel by supercritical carbon dioxide under the condition that the drying temperature is 55 ℃ and the pressure is kept at 12MPa for 48 hours.
The obtained aerogel has the specific surface area of 519 square meters per gram and the density of 0.012g/cm3The coefficient of thermal conductivity is 0.030W/(mK), the modulus is 3.6MPa, and the shrinkage rate is 14.9%.
Example 4:
1) dissolving DMBZ (684mg, 3.22mmol) and alpha-cyclodextrin (627mg, 0.644mmol) in 54.7mL of N-methylpyrrolidone (NMP) to form a supramolecular molecular recognition interaction;
2) adding aromatic 3,3',4,4' -biphenyl tetracarboxylic dianhydride (BPDA 981mg,3.33mmol) into the solution, and stirring at room temperature for 30 minutes to form a cyclodextrin-polyamide acid solution with super-molecular recognition interaction;
3) dissolving a crosslinking agent 1,3, 5-tris (4-aminophenyl) benzene (TAB, 26mg) in 1mL of N-methylpyrrolidone (NMP), pouring into the solution formed in the step 2), and stirring for 20 minutes;
4) adding 2.1mL of acetic anhydride into the solution, stirring for 1 minute, adding 2.2mL of pyridine, and continuing to stir for 1 minute;
5) pouring the solution into a mold, sealing, and continuing aging for 24h after gel is formed;
6) soaking the obtained gel in NMP, NMP/acetone (3/1), NMP/acetone (1/1), NMP/acetone (1/3) and acetone solvent for 24h respectively;
7) and drying the soaked gel by supercritical carbon dioxide under the condition that the drying temperature is 55 ℃ and the pressure is kept at 12MPa for 48 hours.
The obtained aerogel has the specific surface area of 511 square meters per gram and the density of 0.014g/cm3The thermal conductivity coefficient is 0.031W/(mK), the modulus is 3.9MPa, and the shrinkage rate is 14.6%.
FIG. 3 is N of an aerogel prepared in example 4 of the present invention2Adsorption desorption curve with the abscissa as relative pressure (p/p)0) The ordinate is the volume adsorption (cm)3STP,/g); as can be seen from fig. 3: the curve belongs to type IV and is the adsorption curve of a typical mesoporous material.
Example 5:
1) dissolving DMBZ (684mg, 3.22mmol) and alpha-cyclodextrin (627mg, 0.644mmol) in 25mL of N-methylpyrrolidone (NMP) to form a supramolecular molecular recognition interaction;
2) adding aromatic 3,3',4,4' -biphenyl tetracarboxylic dianhydride (BPDA 981mg,3.33mmol) into the solution, and stirring at room temperature for 30 minutes to form a cyclodextrin-polyamide acid solution with super-molecular recognition interaction;
3) dissolving a crosslinking agent 1,3, 5-tris (4-aminophenyl) benzene (TAB, 26mg) in 1 mLN-methylpyrrolidone (NMP), pouring into the solution formed in step 2), and stirring for 20 minutes;
4) adding 2.1mL of acetic anhydride into the solution, stirring for 1 minute, adding 2.2mL of pyridine, and continuing to stir for 1 minute;
5) pouring the solution into a mold, sealing, and continuing aging for 24h after gel is formed;
6) soaking the obtained gel in NMP, NMP/acetone (3/1), NMP/acetone (1/1), NMP/acetone (1/3) and acetone solvent for 24h respectively;
7) and drying the soaked gel by supercritical carbon dioxide under the condition that the drying temperature is 55 ℃ and the pressure is kept at 12MPa for 48 hours.
The obtained aerogel has the specific surface area of 475 square meters per gram and the density of 0.019g/cm3The thermal conductivity coefficient is 0.032W/(mK), the modulus is 9.7MPa, and the shrinkage rate is 7.6%.
Fig. 4 is a water contact angle picture of the aerogel prepared in example 5 of the present invention. As can be seen from fig. 4: the aerogel had a hydrophobic angle of 85 °.
From the above embodiments, the present invention provides a method for preparing a supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect, which includes the following steps: dissolving cyclodextrin and diamine in a mass ratio of 1: 2-20 in N-methylpyrrolidone to obtain a mixed solution; adding aromatic dianhydride into the mixed solution, and stirring to obtain a cyclodextrin-polyamide acid solution; and (3) reacting the cyclodextrin-polyamic acid solution with 1,3, 5-tri (4-aminophenyl) benzene, adding a dehydrating agent, uniformly stirring, aging for 22-26 h after gel is formed, sequentially soaking the obtained aging product in different solvents, and drying by supercritical carbon dioxide to obtain the supramolecular aerogel with the cyclodextrin-polyimide molecular recognition effect. The preparation method disclosed by the invention is prepared by interaction of cyclodextrin and polyimide, a sol-gel method and drying under a supercritical carbon dioxide condition, and the method can furthest retain the excellent mechanical properties and thermal stability of the polyimide aerogel. The experimental results show that: the specific surface area of the supramolecular aerogel is 475-536 m2The density of the mixture is 0.012-0.019 g/cm3The thermal conductivity coefficient is 0.029-0.032W/(Mk), the modulus is 3.6-9.7 MPa, and the shrinkage rate is 7.6% -15.1%.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (8)

1. A preparation method of supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect comprises the following steps:
dissolving cyclodextrin and diamine in a mass ratio of 1: 2-20 in N-methylpyrrolidone to obtain a mixed solution;
adding aromatic dianhydride into the mixed solution, and stirring to obtain a cyclodextrin-polyamide acid solution;
and (3) reacting the cyclodextrin-polyamic acid solution with 1,3, 5-tri (4-aminophenyl) benzene, adding a dehydrating agent, uniformly stirring, aging for 22-26 h after gel is formed, sequentially soaking the obtained aging product in different solvents, and drying by supercritical carbon dioxide to obtain the supramolecular aerogel with the cyclodextrin-polyimide molecular recognition effect.
2. The method according to claim 1, wherein the cyclodextrin is selected from one or more of α -cyclodextrin, β -cyclodextrin and γ -cyclodextrin;
the diamine is selected from 4, 4-diaminodiphenyl ether and/or 4,4 '-diamino-2, 2' -dimethylbiphenyl.
3. The method according to claim 1, wherein the aromatic dianhydride monomer is selected from 3,3',4,4' -biphenyltetracarboxylic dianhydride;
the mass ratio of the diamine to the aromatic dianhydride is n: n +1, wherein n is the polymerization degree of the polyimide segment and is 20, 30, 40, 50 or 60.
4. The process according to claim 1, wherein the dehydrating agent is selected from a mixture of acetic anhydride and pyridine;
the mass ratio of the acetic anhydride to the pyridine to the aromatic dianhydride is 7.5-8.5: 1.
5. The preparation method according to claim 1, wherein the N-methylpyrrolidone, the N-methylpyrrolidone/acetone in a volume ratio of 3:1, the N-methylpyrrolidone/acetone in a volume ratio of 1:3, and the acetone are sequentially soaked for 22-26 hours.
6. The preparation method according to claim 1, wherein the supercritical carbon dioxide drying temperature is 50-60 ℃, the pressure is 11.5-12.5 MPa, and the time is 46-50 h.
7. The preparation method according to claim 1, wherein the molar ratio of the 1,3, 5-tris (4-aminophenyl) benzene to the aromatic dianhydride is 1:20 to 50.
8. A supramolecular aerogel with cyclodextrin-polyimide molecule recognition effect is prepared by the preparation method of any one of claims 1 to 7.
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