CN112108133B - Surface-modified polyimide aerogel and preparation method and application thereof - Google Patents

Surface-modified polyimide aerogel and preparation method and application thereof Download PDF

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CN112108133B
CN112108133B CN202011006570.3A CN202011006570A CN112108133B CN 112108133 B CN112108133 B CN 112108133B CN 202011006570 A CN202011006570 A CN 202011006570A CN 112108133 B CN112108133 B CN 112108133B
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aerogel
polyimide
polyimide aerogel
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ethanol
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CN112108133A (en
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田硕
张大龙
莫贞峰
时冉冉
姜波
高丛春
李娟�
钱凯捷
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Jinan Animal Products Quality And Safety Monitoring Center
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/26—Synthetic macromolecular compounds
    • B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
    • B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
    • B01J20/28047—Gels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Abstract

The invention discloses a surface-modified polyimide aerogel and a preparation method and application thereof, wherein the preparation method comprises the following steps: mixing polyimide aerogel with KOH solution for reaction, and performing surface modification on the polyimide aerogel; and mixing the polyimide aerogel modified by KOH with HCl solution for reaction, and carrying out secondary surface modification to obtain the polyimide aerogel with a large number of-COOH and-C = O groups on the surface. And a proper amount of C = O and-COOH functional groups are constructed on the surface, so that the surface free energy of the aerogel material is improved, the contact angle is reduced, and the wettability is improved. The PI aerogel subjected to surface modification contains a large number of hydrophilic groups such as-COOH and-C = O and can be adsorbed together with antibiotics through hydrogen bonding, so that the PI aerogel subjected to surface modification is used as an adsorbent, and the high-efficiency adsorption of the target antibiotics can be realized.

Description

Surface-modified polyimide aerogel and preparation method and application thereof
Technical Field
The invention belongs to the technical field of preparation of organic adsorption materials, and particularly relates to a surface-modified polyimide aerogel and a preparation method and application thereof.
Background
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
Aerogels are also known as "super sponges" because they have hundreds to thousands of small pores in their surface, which are ideal materials for adsorbing contaminants in water. The aerogel material has good adsorption capacity due to high porosity and large specific surface area, has good adsorption effect on water-soluble or water-insoluble substances, and can be repeatedly used without obvious change of the structure. Among a plurality of adsorbents, the polymer Polyimide (PI) aerogel is used as a novel adsorbent, and has quite remarkable advantages: good thermal stability and chemical stability, large specific surface area, rich raw material sources and simple preparation and forming process. Many PI aerogel composite materials are prepared successively, but in the experimental process, the inventor finds that the PI aerogel obtained by supercritical drying can maintain high specific surface area and pore structure, but the hydrophobic property of the PI aerogel is not beneficial to the adsorption of antibiotics. Particularly, the structures of the commonly used tetracycline antibiotics (including chlortetracycline (chlorotetracycline), oxytetracycline (oxytetracycline), tetracycline (tetracycline) and semisynthetic derivatives of methacycline, doxycycline and dimethylaminocycline) all contain a large number of hydroxyl groups and peptide bonds, but the adsorption effect of the hydrophobic PI aerogel on the antibiotics is not good.
Disclosure of Invention
Aiming at the technical problems in the prior art, the invention provides a surface-modified polyimide aerogel and a preparation method and application thereof.
In order to solve the above technical problem, one or more of the following embodiments of the present invention provide the following technical solutions:
in a first aspect, the present invention provides a method for preparing a surface-modified polyimide aerogel, comprising the steps of:
mixing polyimide aerogel with KOH solution for reaction, and performing surface modification on the polyimide aerogel;
and mixing the polyimide aerogel modified by KOH with HCl solution for reaction, and carrying out secondary surface modification to obtain the polyimide aerogel with a large number of-COOH and-C = O groups on the surface.
In a second aspect, the invention provides a polyimide aerogel prepared by the preparation method.
In a third aspect, the invention provides the use of the polyimide aerogel as an adsorbent, in particular as an antibiotic adsorbent.
Compared with the prior art, the technical scheme or the technical schemes of the invention have the following beneficial effects:
the method comprises the steps of taking 4, 4-diaminodiphenyl ether (ODA) and biphenyl tetracarboxylic dianhydride (BPDA) as reaction precursors, preparing a PI aerogel material by chemical imidization and ethanol supercritical drying technology, and constructing proper C = O and-COOH functional groups on the surface by regulating acid-base concentration and reaction time through simple and feasible acid-base corrosion modification technology, so that the surface free energy of the aerogel material is improved, the contact angle is reduced, and the wettability is improved. The PI aerogel subjected to surface modification contains a large number of hydrophilic groups such as-COOH and-C = O and can be adsorbed together with antibiotics through hydrogen bonding, so that the PI aerogel subjected to surface modification is used as an adsorbent, and the high-efficiency adsorption of the target antibiotics can be realized.
The prepared PI aerogel can realize regeneration after adsorbing a target antibiotic, and is favorable for realizing reutilization. After six times of repeated use, the adsorption amount of the aerogel on the target antibiotic can still reach 96% of the first adsorption amount.
The raw material for preparing the PI aerogel has rich source, low price, stable property and convenient recycling, is a good pollutant adsorption material, and is suitable for industrial production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are included to illustrate an exemplary embodiment of the invention and not to limit the invention.
FIG. 1 is an SEM photograph of PI aerogel obtained in example 1 of the present invention;
fig. 2 is an adsorption isotherm curve of oxytetracycline with the PI aerogel prepared in example 1.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an", and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
As introduced by the background art, in the prior art, the nonmetal polymer catalyst has the problems of low utilization rate of visible light, high recombination rate of photo-generated electrons and holes and the like.
In a first aspect, the present invention provides a method for preparing a surface-modified polyimide aerogel, comprising the steps of:
mixing polyimide aerogel with KOH solution for reaction, and performing surface modification on the polyimide aerogel;
and mixing the polyimide aerogel modified by KOH with HCl solution for reaction, and carrying out secondary surface modification to obtain the polyimide aerogel with a large number of-COOH and-C = O groups on the surface.
In some embodiments, the polyimide aerogel, KOH, and HCl mass ratio is 0.2 to 0.01 to 1.
In some embodiments, the polyimide aerogel is reacted in KOH solution for 10-120min.
Further, the mass concentration of the KOH solution is 1 to 20 weight percent.
In some embodiments, the polyimide aerogel is reacted in the HCl solution for 1-60min.
Further, the concentration of the HCl solution is 1 to 20wt%.
In some embodiments, the method further comprises a step of preparing the polyimide aerogel by using a sol-gel method and an ethanol supercritical drying technology by using a diamine monomer and a dianhydride monomer as precursors for reaction.
Further, the diamine monomer is 4, 4-diaminodiphenyl ether (ODA); the dianhydride monomer is biphenyl tetracarboxylic dianhydride (BPDA).
Further, a method for preparing polyimide aerogel by a sol-gel method specifically comprises the following steps: dissolving a diamine monomer and a dianhydride monomer in a solvent, adding a catalyst and a dehydrating agent, and aging by using a sol-gel method to prepare the PI aerogel.
Still further, the solvent is N-methylpyrrolidone (NMP).
Furthermore, the catalyst is pyridine, and the dehydrating agent is acetic anhydride.
Further, the aging treatment specifically comprises:
firstly, aging the polyimide moisture gel for 10-14h, and then soaking the polyimide moisture gel in an ethanol solution containing 70-80% by mass of N-methylpyrrolidone for 20-28h to obtain the polyimide moisture gel aged for the first time;
soaking the primarily aged polyimide moisture gel in an ethanol solution containing 20-30% by mass of NMP for 20-30h to obtain a secondarily aged polyimide moisture gel;
soaking in ethanol solution to age the polyimide moisture gel aged again for 20-30h.
Further, the drying conditions for ethanol supercritical drying are as follows: performing supercritical drying with ethanol at 230-260 deg.C and 8.0-9.8MPa, and maintaining the pressure for 1-5 hr.
In a second aspect, the invention provides a polyimide aerogel prepared by the preparation method.
In a third aspect, the invention provides the use of the polyimide aerogel as an adsorbent, in particular as an antibiotic adsorbent.
In some embodiments, the antibiotic is oxytetracycline, chlortetracycline, or tetracycline.
Furthermore, the adsorption temperature is 20-35 ℃, and the adsorption time is 2-48h.
The technical scheme of the invention is further explained by combining specific embodiments.
Example 1
(1) 1.58g of ODA was added to 25mL of NMP solution and stirred to be completely dissolved, and then 2.395g of BPDA was added and stirred to be dissolved. Then 6.15mL of acetic anhydride and 5.25mL of pyridine were added to the solution in rapid succession and stirred rapidly to form a homogeneous sol. Aging the seal for 24h, soaking in 75% NMP in ethanol solution for 24h, then in 25% NMP in ethanol solution for 24h, and finally replacing in pure ethanol solution for 24h. And drying for 2 hours at 260 ℃ by adopting an ethanol supercritical drying method to prepare the PI aerogel.
(2) And (2) placing 0.2g of the PI aerogel in the step (1) in 10g of KOH (10 wt%) solution, stirring and reacting for 30min, centrifugally washing, placing in a 60 ℃ oven for drying, then dissolving the obtained PI aerogel powder in 10g of HCl (10 wt%) solution, reacting for 10min, centrifugally washing, and then placing in a 60 ℃ oven for drying for later use.
(3) Respectively preparing terramycin standard solutions with different concentrations, weighing 2.0mg of the PI aerogel prepared in the step (2), dispersing the PI aerogel in 3mL of the terramycin solutions with different concentrations, oscillating the solution for 24 hours at 25 ℃ under the condition of 200r/min, taking supernate after high-speed centrifugation, measuring the concentration of the terramycin, wherein the maximum adsorption capacity is 24mg/g.
FIG. 1 is an SEM photograph of a PI aerogel prepared in this example; fig. 2 is an adsorption isotherm curve of the PI aerogel prepared in this example on oxytetracycline.
Example 2
(1) 1.58g of ODA was added to 25mL of NMP solution and stirred to be completely dissolved, and then 2.395g of BPDA was added and stirred to be dissolved. Then 6.15mL of acetic anhydride and 5.25mL of pyridine were added to the solution in rapid succession and stirred rapidly to form a homogeneous sol. After aging the seal for 24 hours, the seal was soaked in an ethanol solution containing 75% of NMP for 24 hours, then soaked in an ethanol solution containing 25% of NMP for 24 hours, and finally replaced in a pure ethanol solution for 24 hours. And drying for 2 hours at 260 ℃ by adopting an ethanol supercritical drying method to prepare the PI aerogel.
(2) And (2) placing 0.2g of the PI aerogel in the step (1) in 10g of KOH (10 wt%) solution, stirring and reacting for 10min, centrifugally washing, placing in a 60 ℃ oven for drying, dissolving the obtained PI aerogel powder in 10g of HCl (10 wt%) solution again, reacting for 10min, centrifugally washing, and placing in a 60 ℃ oven for drying for later use.
(3) Respectively preparing terramycin standard solutions with different concentrations, weighing 2.0mg of the PI aerogel prepared in the step (2), dispersing the PI aerogel in 3mL of the terramycin solutions with different concentrations, oscillating the solution for 24 hours at 25 ℃ under the condition of 200r/min, taking supernate after high-speed centrifugation, measuring the concentration of the terramycin, wherein the maximum adsorption capacity is 21mg/g.
Example 3
(1) 1.58g of ODA was added to 25mL of NMP solution and stirred to be completely dissolved, and then 2.395g of BPDA was added and stirred to be dissolved. Then 6.15mL of acetic anhydride and 5.25mL of pyridine were added to the solution in rapid succession and stirred rapidly to form a homogeneous sol. After aging the seal for 24 hours, the seal was soaked in an ethanol solution containing 75% of NMP for 24 hours, then soaked in an ethanol solution containing 25% of NMP for 24 hours, and finally replaced in a pure ethanol solution for 24 hours. And drying for 2 hours at 260 ℃ by adopting an ethanol supercritical drying method to prepare the PI aerogel.
(2) And (2) placing 0.2g of the PI aerogel in the step (1) in 10g of KOH (10 wt%) solution, stirring and reacting for 120min, centrifugally washing, placing in a 60 ℃ oven for drying, dissolving the obtained PI aerogel powder in 10g of HCl (10 wt%) solution again, reacting for 10min, centrifugally washing, and placing in a 60 ℃ oven for drying for later use.
(3) Respectively preparing terramycin standard solutions with different concentrations, weighing 2.0mg of the PI aerogel prepared in the step (2), dispersing the PI aerogel in 3mL of the terramycin solutions with different concentrations, oscillating the solution for 24 hours at 25 ℃ under the condition of 200r/min, taking supernate after high-speed centrifugation, measuring the concentration of the terramycin, wherein the maximum adsorption capacity is 24mg/g.
Example 4
(1) 1.58g of ODA was added to 25mL of NMP solution and stirred to be completely dissolved, and then 2.395g of BPDA was added and stirred to be dissolved. Then 6.15mL of acetic anhydride and 5.25mL of pyridine were added to the solution in rapid succession and stirred rapidly to form a homogeneous sol. Aging the seal for 24h, soaking in 75% NMP in ethanol solution for 24h, then in 25% NMP in ethanol solution for 24h, and finally replacing in pure ethanol solution for 24h. And drying for 2 hours at 260 ℃ by adopting an ethanol supercritical drying method to prepare the PI aerogel.
(2) And (2) placing 0.2g of the PI aerogel in the step (1) in 10g of KOH (10 wt%) solution, stirring and reacting for 30min, centrifugally washing, placing in a 60 ℃ oven for drying, then dissolving the obtained PI aerogel powder in 10g of HCl (10 wt%) solution, reacting for 1min, centrifugally washing, and then placing in a 60 ℃ oven for drying for later use.
(3) Respectively preparing terramycin standard solutions with different concentrations, weighing 2.0mg of the PI aerogel prepared in the step (2), dispersing the PI aerogel in 3mL of the terramycin solution with different concentrations, oscillating the PI aerogel for 24 hours at 25 ℃ at 200r/min, centrifuging the PI aerogel at a high speed, taking supernate, and determining the concentration of the terramycin, wherein the maximum adsorption capacity is 16mg/g.
Example 5
(1) 1.58g of ODA was added to 25mL of NMP solution and stirred to be completely dissolved, and then 2.395g of BPDA was added and stirred to be dissolved. Then 6.15mL of acetic anhydride and 5.25mL of pyridine were added to the solution in rapid succession and stirred rapidly to form a homogeneous sol. After aging the seal for 24 hours, the seal was soaked in an ethanol solution containing 75% of NMP for 24 hours, then soaked in an ethanol solution containing 25% of NMP for 24 hours, and finally replaced in a pure ethanol solution for 24 hours. And drying for 2 hours at 260 ℃ by adopting an ethanol supercritical drying method to prepare the PI aerogel.
(2) And (2) placing 0.2g of the PI aerogel in the step (1) in 10g of KOH (10 wt%) solution, stirring and reacting for 30min, centrifugally washing, placing in a 60 ℃ oven for drying, dissolving the obtained PI aerogel powder in 10g of HCl (10 wt%) solution again, reacting for 60min, centrifugally washing, and placing in a 60 ℃ oven for drying for later use.
(3) Respectively preparing terramycin standard solutions with different concentrations, weighing 2.0mg of the PI aerogel prepared in the step (2), dispersing the PI aerogel in 3mL of the terramycin solution with different concentrations, oscillating the PI aerogel for 24 hours at 25 ℃ at 200r/min, centrifuging the PI aerogel at a high speed, taking supernate, and determining the concentration of the terramycin, wherein the maximum adsorption capacity is 24mg/g.
Example 6
(1) 1.58g of ODA was added to 25mL of NMP solution and stirred to be completely dissolved, and then 2.395g of BPDA was added and stirred to be dissolved. Then 6.15mL of acetic anhydride and 5.25mL of pyridine were added to the solution in rapid succession and stirred rapidly to form a homogeneous sol. After aging the seal for 24 hours, the seal was soaked in an ethanol solution containing 75% of NMP for 24 hours, then soaked in an ethanol solution containing 25% of NMP for 24 hours, and finally replaced in a pure ethanol solution for 24 hours. And drying for 2 hours at 260 ℃ by adopting an ethanol supercritical drying method to prepare the PI aerogel.
(2) And (2) placing 0.2g of the PI aerogel in the step (1) in 10g of KOH (0.1 wt%) solution, stirring and reacting for 30min, centrifugally washing, placing in a 60 ℃ oven for drying, dissolving the obtained PI aerogel powder in 10g of HCl (10 wt%) solution again, reacting for 10min, centrifugally washing, and placing in a 60 ℃ oven for drying for later use.
(3) Respectively preparing terramycin standard solutions with different concentrations, weighing 2.0mg of the PI aerogel prepared in the step (2), dispersing the PI aerogel in 3mL of the terramycin solution with different concentrations, oscillating the PI aerogel for 24 hours at 25 ℃ at 200r/min, centrifuging the PI aerogel at a high speed, taking supernate, and determining the concentration of the terramycin, wherein the maximum adsorption capacity is 14mg/g.
Example 7
(1) 1.58g of ODA was added to 25mL of NMP solution and stirred to be completely dissolved, and then 2.395g of BPDA was added and stirred to be dissolved. Then 6.15mL of acetic anhydride and 5.25mL of pyridine were added to the solution in rapid succession and stirred rapidly to form a homogeneous sol. After aging the seal for 24 hours, the seal was soaked in an ethanol solution containing 75% of NMP for 24 hours, then soaked in an ethanol solution containing 25% of NMP for 24 hours, and finally replaced in a pure ethanol solution for 24 hours. And drying for 2 hours at 260 ℃ by adopting an ethanol supercritical drying method to prepare the PI aerogel.
(2) And (2) placing 0.2g of the PI aerogel in the step (1) in 10g of KOH (10 wt%) solution, stirring and reacting for 30min, centrifugally washing, placing in a 60 ℃ oven for drying, dissolving the obtained PI aerogel powder in 10g of HCl (0.1 wt%) solution again, reacting for 10min, centrifugally washing, and placing in a 60 ℃ oven for drying for later use.
(3) Respectively preparing terramycin standard solutions with different concentrations, weighing 2.0mg of the PI aerogel prepared in the step (2), dispersing the PI aerogel in 3mL of the terramycin solution with different concentrations, oscillating the PI aerogel for 24 hours at 25 ℃ at 200r/min, centrifuging the PI aerogel at a high speed, taking supernate, and determining the concentration of the terramycin, wherein the maximum adsorption capacity is 12mg/g.
Example 8
(1) 1.58g of ODA was added to 25mL of NMP solution and stirred to be completely dissolved, and then 2.395g of BPDA was added and stirred to be dissolved. Then 6.15mL of acetic anhydride and 5.25mL of pyridine were added to the solution in rapid succession and stirred rapidly to form a homogeneous sol. Aging the seal for 24h, soaking in 75% NMP in ethanol solution for 24h, then in 25% NMP in ethanol solution for 24h, and finally replacing in pure ethanol solution for 24h. And drying for 2 hours at 260 ℃ by adopting an ethanol supercritical drying method to prepare the PI aerogel.
(2) And (2) placing 0.2g of the PI aerogel in the step (1) in 10g of KOH (10 wt%) solution, stirring and reacting for 30min, centrifugally washing, placing in a 60 ℃ oven for drying, dissolving the obtained PI aerogel powder in 10g of HCl (10 wt%) solution again, reacting for 10min, centrifugally washing, and placing in a 60 ℃ oven for drying for later use.
(3) Preparing aureomycin standard solutions with different concentrations respectively, weighing 2.0mg of the PI aerogel prepared in the step (2), dispersing the PI aerogel in 3mL of aureomycin solutions with different concentrations, oscillating the solutions at 25 ℃ at 200r/min for 24h, centrifuging the solutions at a high speed, taking supernate, and determining the concentration of aureomycin, wherein the maximum adsorption capacity is 22mg/g.
Example 9
(1) 1.58g of ODA was added to 25mL of NMP solution and stirred to be completely dissolved, and then 2.395g of BPDA was added and stirred to be dissolved. Then 6.15mL of acetic anhydride and 5.25mL of pyridine were added to the solution in rapid succession and stirred rapidly to form a homogeneous sol. After aging the seal for 24 hours, the seal was soaked in an ethanol solution containing 75% of NMP for 24 hours, then soaked in an ethanol solution containing 25% of NMP for 24 hours, and finally replaced in a pure ethanol solution for 24 hours. And drying for 2 hours at 260 ℃ by adopting an ethanol supercritical drying method to prepare the PI aerogel.
(2) And (2) placing 0.2g of the PI aerogel in the step (1) in 10g of KOH (10 wt%) solution, stirring and reacting for 30min, centrifugally washing, placing in a 60 ℃ oven for drying, then dissolving the obtained PI aerogel powder in 10g of HCl (10 wt%) solution, reacting for 10min, centrifugally washing, and then placing in a 60 ℃ oven for drying for later use.
(3) Respectively preparing tetracycline standard solutions with different concentrations, weighing 2.0mg of the PI aerogel prepared in the step (2) and dispersing in 3mL of the tetracycline solutions with different concentrations, oscillating for 24h at 25 ℃ under the condition of 200r/min, taking supernate after high-speed centrifugation, determining the concentration of tetracycline, wherein the maximum adsorption capacity is 19mg/g.
Comparative example 1
(1) 1.58g of ODA was added to 25mL of NMP solution and stirred to be completely dissolved, and then 2.395g of BPDA was added and stirred to be dissolved. Then 6.15mL of acetic anhydride and 5.25mL of pyridine were added to the solution in rapid succession and stirred rapidly to form a homogeneous sol. After aging the seal for 24 hours, the seal was soaked in an ethanol solution containing 75% of NMP for 24 hours, then soaked in an ethanol solution containing 25% of NMP for 24 hours, and finally replaced in a pure ethanol solution for 24 hours. And drying for 2 hours at 260 ℃ by adopting an ethanol supercritical drying method to prepare the PI aerogel.
(2) And (3) placing 0.2g of the PI aerogel in the step (1) in a 10g KOH (10 weight percent) solution, stirring and reacting for 30min, centrifugally washing, and placing in an oven at 60 ℃ for drying for later use.
(3) Respectively preparing terramycin standard solutions with different concentrations, weighing 2.0mg of the PI aerogel prepared in the step (2), dispersing the PI aerogel in 3mL of the terramycin solutions with different concentrations, oscillating the solution at 25 ℃ for 24 hours at 200r/min, centrifuging the solution at a high speed, taking supernate, and determining the concentration of the terramycin, wherein the maximum adsorption capacity is 10mg/g.
Comparative example 2
(1) 1.58g of ODA was added to 25mL of NMP solution and stirred to be completely dissolved, and then 2.395g of BPDA was added and stirred to be dissolved. Then 6.15mL of acetic anhydride and 5.25mL of pyridine were added to the solution in rapid succession and stirred rapidly to form a homogeneous sol. Aging the seal for 24h, soaking in 75% NMP in ethanol solution for 24h, then in 25% NMP in ethanol solution for 24h, and finally replacing in pure ethanol solution for 24h. And drying for 2 hours at 260 ℃ by adopting an ethanol supercritical drying method to prepare the PI aerogel.
(2) And (3) placing 0.2g of the PI aerogel in the step (1) in 10g of HCl (10 wt%) solution, reacting for 10min, centrifugally washing, and drying in an oven at 60 ℃ for later use.
(3) Respectively preparing terramycin standard solutions with different concentrations, weighing 2.0mg of the PI aerogel prepared in the step (2), dispersing the PI aerogel in 3mL of the terramycin solution with different concentrations, oscillating the PI aerogel for 24 hours at 25 ℃ at 200r/min, centrifuging the PI aerogel at a high speed, taking supernate, and determining the concentration of the terramycin, wherein the maximum adsorption capacity is 8mg/g.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.

Claims (11)

1. A preparation method of surface-modified polyimide aerogel is characterized by comprising the following steps: the method comprises the following steps:
mixing polyimide aerogel with KOH solution for reaction, and performing surface modification on the polyimide aerogel;
mixing the polyimide aerogel modified by KOH with HCl solution for reaction, and carrying out secondary surface modification to obtain polyimide aerogel with a large number of-COOH and-C = O groups on the surface;
the preparation method of the polyimide aerogel comprises the steps of dissolving a diamine monomer and a dianhydride monomer in a solvent, adding a catalyst and a dehydrating agent, and adopting a sol-gel method, aging treatment and an ethanol supercritical drying technology to prepare the polyimide aerogel.
2. The method for preparing a surface-modified polyimide aerogel according to claim 1, characterized in that: the mass ratio of the polyimide aerogel to the KOH to the HCl is 0.01-1.
3. The method for preparing a surface-modified polyimide aerogel according to claim 1, wherein: the reaction time of the polyimide aerogel in the KOH solution is 10-120min; the concentration of the KOH solution is 1 to 20wt%.
4. The method for preparing a surface-modified polyimide aerogel according to claim 1, wherein: the reaction time of the polyimide aerogel in HCl solution is 1-60min; the concentration of the HCl solution is 1-20 wt.%.
5. The method for preparing a surface-modified polyimide aerogel according to claim 1, wherein: the diamine monomer is 4, 4-diaminodiphenyl ether; the dianhydride monomer is biphenyl tetracarboxylic dianhydride; the solvent is N-methyl pyrrolidone; the catalyst is pyridine, and the dehydrating agent is acetic anhydride.
6. The method for preparing a surface-modified polyimide aerogel according to claim 1, characterized in that: the specific method of aging treatment is as follows:
firstly, aging the polyimide moisture gel for 10-14h, and then soaking the polyimide moisture gel in an ethanol solution of N-methyl pyrrolidone with the mass percent of 70-80% for 20-28h to obtain the polyimide moisture gel aged for the first time;
soaking the primarily aged polyimide moisture gel in 20-30% N-methylpyrrolidone ethanol solution for 20-30h to obtain a secondarily aged polyimide moisture gel;
soaking in ethanol solution to age the polyimide moisture gel aged again for 20-30h.
7. The method for preparing a surface-modified polyimide aerogel according to claim 1, characterized in that: the drying conditions for ethanol supercritical drying are as follows: performing supercritical drying with ethanol at 230-260 deg.C and 8.0-9.8MPa, and maintaining the pressure for 1-5 hr.
8. A polyimide aerogel produced by the production method as set forth in any one of claims 1 to 7.
9. Use of the polyimide aerogel according to claim 8 as an adsorbent, in particular as an adsorbent for antibiotics.
10. Use according to claim 9, characterized in that: the antibiotic is oxytetracycline, chlortetracycline or tetracycline.
11. Use according to claim 10, characterized in that: the adsorption temperature is 20-35 deg.C, and the adsorption time is 2-48h.
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CN106750493B (en) * 2017-01-16 2019-05-03 东华大学 A kind of preparation method of polyimide aerogels
CN106987019B (en) * 2017-04-14 2020-05-08 北京航空航天大学 Polyimide aerogel crosslinked by surface functionalized nanoparticles and preparation method thereof
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