CN110606979A - Green preparation method of polyimide aerogel - Google Patents
Green preparation method of polyimide aerogel Download PDFInfo
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- CN110606979A CN110606979A CN201910900522.XA CN201910900522A CN110606979A CN 110606979 A CN110606979 A CN 110606979A CN 201910900522 A CN201910900522 A CN 201910900522A CN 110606979 A CN110606979 A CN 110606979A
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- 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
- C08J9/28—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
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- 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
- 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
- C08J2201/048—Elimination of a frozen liquid phase
- C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
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- 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
Abstract
The invention discloses a green preparation method of polyimide aerogel, belonging to the technical field of materials. According to the invention, diamine monomers are dissolved in deionized water mainly through quaternary ammonium salt cationic surfactant and tertiary amine, then diamine aqueous solution and dianhydride are reacted to obtain polyamide acid aqueous solution, and the polyamide acid aqueous solution is aged, freeze-dried and thermally imidized to obtain polyimide aerogel.
Description
Technical Field
The invention belongs to the technical field of materials, relates to preparation of polymer aerogel, and particularly relates to a green preparation method of polyimide aerogel.
Background
Aerogel is a highly dispersed solid material, mainly composed of a nanoporous network structure with pores obtained by aggregation of colloidal particles (or polymer molecules) filled with gaseous dispersion medium, usually prepared by wet gel, and is a three-dimensional porous nanomaterial in which the liquid component is replaced by gas during drying of wet gel and the gel network is still maintained. The special continuous three-dimensional network structure enables the aerogel to show unique properties in the aspects of heat, mechanics, acoustics, optics, electricity and the like, so that the aerogel attracts attention in the fields of separation materials, adsorption materials, heat insulation materials, gas and biological sensors, low dielectric constant materials and the like.
Polyimide is a polymer containing imide rings in a molecular main chain structural unit, has extremely outstanding thermal oxygen stability, dielectric property, environmental aging resistance, radiation resistance, chemical solvent resistance, mechanical strength and the like, is one of polymer materials with the best comprehensive performance at present, and is also one of ideal materials for preparing polymer aerogel. The polyimide aerogel is prepared by the following method: firstly, preparing polyamic acid (polyimide precursor) from dianhydride and diamine monomers; then, chemical imidization is to convert the polyamic acid solution into polyimide gel; finally, the polyimide gel is placed in supercritical CO2Drying to obtain the aerogel. However, this method requires high polyimide solubility, and requires soluble polyimide to prepare polyimide gel, which results in that most insoluble polyimides cannot be used to prepare aerogel by this method. In recent years, a method for assisting a water-soluble polyimide precursor (polyamic acid) with a cosolvent provides a new idea for preparing a polyimide aerogel, namely, the polyamic acid aerogel is prepared by a polyamic acid aqueous solution freeze drying method and then is subjected to thermal imidization to obtain the polyimide aerogel. The method is simple and efficient, is suitable for preparing most of polyimide aerogel, and is an ideal polyimide aerogel preparation method. However, the traditional polyamic acid is usually prepared by reacting a diamine monomer and a dianhydride monomer in a strong polar aprotic organic solvent, so that the environmental friendliness is poor, the preparation cost is high, and the solvent of the polyamic acid solution needs to be replaced by water in a manner of precipitation and cosolvent-assisted dissolution, so that the preparation steps are relatively complicated. Therefore, how to directly prepare the polyamic acid by adopting an aqueous solution system and prepare the polyimide aerogel on the basis of the polyamic acid is beneficial to improving the environmental friendliness, reducing the preparation cost and simplifying the preparation steps, thereby realizing the green and simple preparation of the polyimide aerogel.
Disclosure of Invention
In order to solve the problems that the preparation of the polyimide aerogel in the prior art is complex and can not meet the green preparation, the invention provides a simple and efficient green preparation method of the polyimide aerogel, the equipment requirement is low and the application range is wide.
In order to achieve the purpose, the invention adopts the following technical means:
a green preparation method of polyimide aerogel comprises the following steps:
stirring diamine monomer, tertiary amine and quaternary ammonium salt cationic surfactant in deionized water to form a uniform solution; the addition molar ratio of the quaternary ammonium salt cationic surfactant to the diamine monomer is (0.03-0.04): 1, the addition molar ratio of the tertiary amine to the diamine monomer is (0.05-0.08): 1;
and adding a dianhydride monomer, stirring until the dianhydride monomer is completely dissolved to form a viscous solution, and obtaining a polyamic acid aqueous solution, wherein the adding molar ratio of the diamine monomer to the dianhydride monomer is 1: (0.95-1.05);
degassing a polyamic acid aqueous solution, refrigerating, aging, freezing and drying to obtain a polyamic acid aerogel;
and carrying out thermal imidization treatment on the polyamic acid aerogel to obtain the polyimide aerogel.
Preferably, the diamine monomer is one or a mixture of more of 4, 4' -diaminodiphenyl ether, diphenyldiamine and p-phenylenediamine in any proportion.
Preferably, the dianhydride monomer is one or a mixture of more of pyromellitic anhydride, hexafluoro dianhydride and 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride in any proportion.
Preferably, the tertiary amine is one or a mixture of several of trimethylamine, triethylamine and N, N' -dimethylethanolamine in any proportion.
Preferably, the quaternary ammonium salt cationic surfactant is one of dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide and hexadecyl trimethyl ammonium bromide.
Preferably, the refrigeration aging time of the polyamic acid aqueous solution is 2-3 days.
Preferably, the freeze drying condition is that the pressure is less than or equal to 20Pa, and the time is 12-48 h.
Preferably, the polyamic acid aerogel thermal imidization treatment adopts a step temperature, and the temperature is 120-250 ℃.
Preferably, the thermal imidization treatment temperature is: the treatment time is 0.5-2 h at 120 ℃, 0.5-2 h at 150 ℃, 0.5-2 h at 200 ℃ and 2-4 h at 250 ℃.
Compared with the prior art, the invention has the following advantages:
the green preparation method of the polyimide aerogel comprises the steps of dissolving a diamine monomer in deionized water through a quaternary ammonium salt cationic surfactant and tertiary amine, reacting the dissolved diamine monomer with a dianhydride monomer to obtain a polyamic acid aqueous solution, and then preparing the polyimide aerogel from the polyamic acid aqueous solution through freeze drying and thermal imidization processes. Experiments show that direct preparation of the polyamic acid aqueous solution can be effectively realized by adopting a reaction mode of the diamine monomer aqueous solution and the dianhydride monomer, so that green and simple preparation of the polyimide aerogel is realized, and meanwhile, the preparation cost is reduced. The method comprises the steps of forming a diamine monomer aqueous solution through the action of a quaternary ammonium salt cationic surfactant and a tertiary amine, further reacting with a dianhydride monomer to prepare a polyamic acid aqueous solution, wherein the method is characterized in that the tertiary amine is dissolved in water under the action of the quaternary ammonium salt cationic surfactant, the tertiary amine in the aqueous solution reacts with the diamine monomer to form a diamine monomer aqueous solution, and then the diamine monomer reacts with the dianhydride monomer in the aqueous solution to prepare the polyamic acid aqueous solution. The method is suitable for preparing different types of polyimide aerogel, and does not need to consider the solubility of polyimide; meanwhile, the aqueous solution freeze drying is simple and easy to implement, has low requirements on equipment, has the advantages of simplicity, high efficiency, low requirements on the equipment, wide application range and environmental friendliness, and can effectively avoid the problem that the traditional polyimide high-performance aerogel is difficult to prepare, so that the preparation method disclosed by the invention is widely suitable for preparing various polyimide aerogels of different types, and can expand the application of the polyimide aerogels in the fields of separation materials, adsorption materials, heat-insulating materials, gases, biosensors, low-dielectric-constant materials and the like.
Drawings
FIG. 1 is an IR spectrum of a polyimide aerogel prepared in example 6 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph (magnifications from a to c are:. times.60,. times.200, and. times.350) of the polyimide aerogel obtained in example 6 of the present invention.
Detailed Description
The invention relates to a green preparation method of polyimide aerogel, which specifically comprises the following steps:
firstly, dissolving a diamine monomer in deionized water under the action of tertiary amine and quaternary ammonium salt cationic surfactant to prepare a diamine monomer aqueous solution;
the specific means is as follows: and (3) carrying out ultrasonic treatment on the single-neck flask, the beaker, the mold, the magneton and the like by using absolute ethyl alcohol, removing surface impurities, and drying for later use. Placing weighed diamine, tertiary amine and quaternary ammonium salt cationic surfactant into a single-neck flask with magnetons, adding deionized water, and stirring until the diamine is completely dissolved to obtain a diamine monomer aqueous solution; the addition molar ratio of the quaternary ammonium salt cationic surfactant to the diamine monomer is (0.03-0.04): 1. the addition molar ratio of the tertiary amine to the diamine monomer is (0.05-0.08): 1.
secondly, pouring dianhydride into a diamine monomer aqueous solution for reaction to prepare a polyamic acid aqueous solution;
the specific means is as follows: slowly adding weighed dianhydride into a diamine monomer aqueous solution, and stirring at room temperature for 1-24 h to obtain a polyamide acid aqueous solution; the addition molar ratio of the diamine monomer to the dianhydride monomer is 1: (0.95-1.05).
And finally, placing the polyamide acid aqueous solution in a vacuum drying oven, degassing, refrigerating and aging for 2-3 days, freezing and drying to obtain polyamide acid aerogel, and dehydrating and cyclizing (thermal imidizing) in the drying oven to obtain the polyimide aerogel.
The specific means is as follows: pouring the prepared polyamic acid aqueous solution into a mold, and then placing the mold in a vacuum drying oven to degas for 2 hours; placing the mold filled with the aqueous solution in a refrigerating chamber of a refrigerator for refrigerating for 2-3 days, and then freezing until the solution is completely frozen; and (3) freezing and drying the frozen polyamic acid sample to obtain polyamic acid aerogel, and performing heat treatment to dehydrate and cyclize the polyamic acid to obtain the polyimide aerogel.
Wherein, the dehydration and cyclization process of the polyamic acid aerogel adopts step temperature, and the temperature range is 120-250 ℃. Comprehensively considering, the polyamide acid thermal imidization mechanism and the morphology and performance of the aerogel, and the optimal polyamide acid aerogel thermal imidization process comprises the following steps: 120 ℃ (0.5-2 h) +150 ℃ (0.5-2 h) +200 ℃ (0.5-2 h) +250 ℃ (0.5-4 h).
The diamine monomer can be one or a mixture of several diamines such as commercially available 4,4 '-diaminodiphenyl ether, 4' -diaminobiphenyl, p-phenylenediamine and the like in any proportion. The dianhydride monomer can be one or a mixture of a plurality of dianhydrides such as commercially available pyromellitic dianhydride, hexafluoro dianhydride, 3 ', 4, 4' -benzophenonetetracarboxylic dianhydride and the like in any proportion. The reaction time of the diamine monomer and the dianhydride monomer in the aqueous solution is 1-24 h.
The tertiary amine can be one or a mixture of more of commercially available tertiary amines such as trimethylamine, triethylamine, N' -dimethylethanolamine and the like in any proportion. The quaternary ammonium salt cationic surfactant is one of dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide and the like.
And degassing the polyamic acid aqueous solution in a vacuum drying oven for 2-6 h. The polyamic acid aerogel can be obtained by freeze-drying in any container, preferably a beaker or other type of glass article.
The technical scheme of the invention is explained in detail by combining the specific embodiment and the attached drawings as follows:
example 1
Preparing polyimide aerogel: firstly, 2.00g of 4, 4' -diaminodiphenyl ether (ODA), 0.08g of dodecyl trimethyl ammonium chloride and 0.07mL of triethylamine are dissolved in 50mL of deionized water; secondly, adding 2.18g of pyromellitic dianhydride (PMDA) and stirring to prepare a polyamic acid aqueous solution; thirdly, pouring the polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain polyamic acid aerogel; finally, obtaining the polyimide aerogel through thermal imidization treatment, wherein the thermal imidization process comprises the following steps: 120 ℃ (0.5h) +150 ℃ (0.5h) +200 ℃ (1h) +250 ℃ (4 h).
Example 2
Preparing polyimide aerogel: firstly, 2.00g of 4, 4' -diaminodiphenyl ether (ODA), 0.08g of dodecyl trimethyl ammonium chloride and 0.11mL of triethylamine are dissolved in 50mL of deionized water; secondly, adding 2.18g of pyromellitic dianhydride (PMDA) and stirring to prepare a polyamic acid aqueous solution; thirdly, pouring the polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain polyamic acid aerogel; finally, obtaining the polyimide aerogel through thermal imidization treatment, wherein the thermal imidization process comprises the following steps: 120 ℃ (0.5h) +150 ℃ (0.5h) +200 ℃ (1h) +250 ℃ (4 h).
Example 3
Preparing polyimide aerogel: firstly, 2.00g of 4, 4' -diaminodiphenyl ether (ODA), 0.10g of dodecyl trimethyl ammonium chloride and 0.08mL of triethylamine are dissolved in 50mL of deionized water; secondly, adding 2.18g of pyromellitic dianhydride (PMDA) and stirring to prepare a polyamic acid aqueous solution; thirdly, pouring the polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain polyamic acid aerogel; finally, obtaining the polyimide aerogel through thermal imidization treatment, wherein the thermal imidization process comprises the following steps: 120 ℃ (0.5h) +150 ℃ (0.5h) +200 ℃ (1h) +250 ℃ (4 h).
Example 4
Preparing polyimide aerogel: firstly, 2.00g of 4, 4' -diaminodiphenyl ether (ODA), 0.10g of dodecyl trimethyl ammonium chloride and 0.11mL of triethylamine are dissolved in 50mL of deionized water; secondly, adding 2.18g of pyromellitic dianhydride (PMDA) and stirring to prepare a polyamic acid aqueous solution; thirdly, pouring the polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain polyamic acid aerogel; finally, obtaining the polyimide aerogel through thermal imidization treatment, wherein the thermal imidization process comprises the following steps: 120 ℃ (0.5h) +150 ℃ (0.5h) +200 ℃ (1h) +250 ℃ (4 h).
Example 5
Preparing polyimide aerogel: firstly, 1.9g of 4, 4' -diaminodiphenyl ether (ODA), 0.08g of dodecyl trimethyl ammonium chloride and 0.09mL of triethylamine are dissolved in 50mL of deionized water; secondly, adding 2.18g of pyromellitic dianhydride (PMDA) and stirring to prepare a polyamic acid aqueous solution; thirdly, pouring the polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain polyamic acid aerogel; finally, obtaining the polyimide aerogel through thermal imidization treatment, wherein the thermal imidization process comprises the following steps: 120 ℃ (0.5h) +150 ℃ (0.5h) +200 ℃ (1h) +250 ℃ (4 h).
Example 6
Preparing polyimide aerogel: firstly, 2.0g of 4, 4' -diaminodiphenyl ether (ODA), 0.09g of dodecyl trimethyl ammonium chloride and 0.09mL of triethylamine are dissolved in 50mL of deionized water; secondly, adding 2.18g of pyromellitic dianhydride (PMDA) and stirring to prepare a polyamic acid aqueous solution; thirdly, pouring the polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain polyamic acid aerogel; finally, obtaining the polyimide aerogel through thermal imidization treatment, wherein the thermal imidization process comprises the following steps: 120 ℃ (0.5h) +150 ℃ (0.5h) +200 ℃ (1h) +250 ℃ (4 h).
As can be seen from FIG. 1, 1780cm-1、1725cm-1、1375cm-1And 730cm-1An imide ring characteristic absorption peak appears nearby, and an obvious amic acid characteristic absorption peak is not seen, which indicates that the polyamic acid is completely imidized; from fig. 2, it can be seen that the prepared sample mainly comprises a polyimide sheet structure on the microscopic scale, and a large number of micropores exist between sheets, and the conclusion of fig. 1 is combined to show that the polyimide aerogel is effectively prepared by adopting the method.
Example 7
Preparing polyimide aerogel: firstly, 2.1g of 4, 4' -diaminodiphenyl ether (ODA), 0.09g of dodecyl trimethyl ammonium chloride and 0.10mL of triethylamine are dissolved in 50mL of deionized water; secondly, adding 2.18g of pyromellitic dianhydride (PMDA) and stirring to prepare a polyamic acid aqueous solution; thirdly, pouring the polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain polyamic acid aerogel; finally, obtaining the polyimide aerogel through thermal imidization treatment, wherein the thermal imidization process comprises the following steps: 120 ℃ (0.5h) +150 ℃ (0.5h) +200 ℃ (1h) +250 ℃ (4 h).
Example 8
Preparing polyimide aerogel: firstly, 2.0g of 4, 4' -diaminodiphenyl ether (ODA), 0.12g of hexadecyl trimethyl ammonium bromide and 0.10mL of triethylamine are dissolved in 50mL of deionized water; secondly, adding 2.18g of pyromellitic dianhydride (PMDA) and stirring to prepare a polyamic acid aqueous solution; thirdly, pouring the polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain polyamic acid aerogel; finally, obtaining the polyimide aerogel through thermal imidization treatment, wherein the thermal imidization process comprises the following steps: 120 ℃ (0.5h) +150 ℃ (0.5h) +200 ℃ (1h) +250 ℃ (4 h).
Example 9
Preparing polyimide aerogel: firstly, 2.0g of 4, 4' -diaminodiphenyl ether (ODA), 0.11g of hexadecyltrimethylammonium chloride and 0.10mL of triethylamine are dissolved in 50mL of deionized water; secondly, adding 2.18g of pyromellitic dianhydride (PMDA) and stirring to prepare a polyamic acid aqueous solution; thirdly, pouring the polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain polyamic acid aerogel; finally, obtaining the polyimide aerogel through thermal imidization treatment, wherein the thermal imidization process comprises the following steps: 120 ℃ (1.5h) +150 ℃ (1.5h) +200 ℃ (0.5h) +250 ℃ (3 h).
Example 10
Preparing polyimide aerogel: firstly, 2.0g of 4, 4' -diaminodiphenyl ether (ODA), 0.10g of hexadecyltrimethylammonium chloride and 0.10mL of triethylamine are dissolved in 50mL of deionized water; secondly, adding 2.18g of pyromellitic dianhydride (PMDA) and stirring to prepare a polyamic acid aqueous solution; thirdly, pouring the polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain polyamic acid aerogel; finally, obtaining the polyimide aerogel through thermal imidization treatment, wherein the thermal imidization process comprises the following steps: 120 ℃ (2h) +150 ℃ (2h) +200 ℃ (2h) +250 ℃ (3 h).
Example 11
Preparing polyimide aerogel: firstly, 2.0g of 4,4 '-diaminodiphenyl ether (ODA), 0.09g of dodecyl trimethyl ammonium chloride and 0.07mL of N, N' -dimethylethanolamine are dissolved in 50mL of deionized water; secondly, adding 2.18g of pyromellitic dianhydride (PMDA) and stirring to prepare a polyamic acid aqueous solution; thirdly, pouring the polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain polyamic acid aerogel; finally, obtaining the polyimide aerogel through thermal imidization treatment, wherein the thermal imidization process comprises the following steps: 120 ℃ (1h) +150 ℃ (1h) +200 ℃ (0.5h) +250 ℃ (2 h).
The foregoing is only a preferred embodiment of the present invention, and it should be noted that those skilled in the art can make various improvements and modifications without departing from the principle of the present invention, and these improvements and modifications should also be construed as the protection scope of the present invention.
Claims (9)
1. The green preparation method of the polyimide aerogel is characterized by comprising the following steps of:
stirring diamine monomer, tertiary amine and quaternary ammonium salt cationic surfactant in deionized water to form a uniform solution; the addition molar ratio of the quaternary ammonium salt cationic surfactant to the diamine monomer is (0.03-0.04): 1, the addition molar ratio of the tertiary amine to the diamine monomer is (0.05-0.08): 1;
and adding a dianhydride monomer, stirring until the dianhydride monomer is completely dissolved to form a viscous solution, and obtaining a polyamic acid aqueous solution, wherein the adding molar ratio of the diamine monomer to the dianhydride monomer is 1: (0.95-1.05);
degassing a polyamic acid aqueous solution, refrigerating, aging, freezing and drying to obtain a polyamic acid aerogel;
and carrying out thermal imidization treatment on the polyamic acid aerogel to obtain the polyimide aerogel.
2. The green preparation method of polyimide aerogel according to claim 1, characterized in that: the diamine monomer is one or a mixture of more of 4, 4' -diaminodiphenyl ether, biphenyldiamine and p-phenylenediamine in any proportion.
3. The green preparation method of polyimide aerogel according to claim 1, characterized in that: the dianhydride monomer is one or a mixture of more of pyromellitic anhydride, hexafluoro dianhydride and 3,3 ', 4, 4' -benzophenone tetracarboxylic dianhydride in any proportion.
4. The green preparation method of polyimide aerogel according to claim 1, characterized in that: the tertiary amine is one or a mixture of several of trimethylamine, triethylamine and N, N' -dimethylethanolamine in any proportion.
5. The green preparation method of polyimide aerogel according to claim 1, characterized in that: the quaternary ammonium salt cationic surfactant is one of dodecyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium chloride, dodecyl trimethyl ammonium bromide and hexadecyl trimethyl ammonium bromide.
6. The green preparation method of polyimide aerogel according to claim 1, characterized in that: and the cold storage aging time of the polyamic acid aqueous solution is 2-3 days.
7. The green preparation method of polyimide aerogel according to claim 1, characterized in that: the freeze drying condition is that the pressure is less than or equal to 20Pa, and the time is 12-48 h.
8. The green preparation method of polyimide aerogel according to claim 1, characterized in that: the polyamic acid aerogel thermal imidization treatment adopts a step temperature, and the temperature is 120-250 ℃.
9. The green preparation method of polyimide aerogel according to claim 8, characterized in that: the thermal imidization treatment temperature is as follows: the treatment time is 0.5-2 h at 120 ℃, 0.5-2 h at 150 ℃, 0.5-2 h at 200 ℃ and 2-4 h at 250 ℃.
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| US11932745B2 (en) | 2020-12-11 | 2024-03-19 | Aspen Aerogels, Inc. | Water co-catalyst for polyimide processes |
| WO2023277357A1 (en) * | 2021-06-29 | 2023-01-05 | 한국화학연구원 | Polyamic acid aqueous solution composition |
| CN113637215A (en) * | 2021-09-30 | 2021-11-12 | 福州大学 | In-situ doped heat-resistant heat-insulating polyimide aerogel and preparation method thereof |
| CN113637215B (en) * | 2021-09-30 | 2022-04-19 | 福州大学 | In-situ doped heat-resistant heat-insulating polyimide aerogel and preparation method thereof |
| CN114479079A (en) * | 2022-02-07 | 2022-05-13 | 军事科学院系统工程研究院军需工程技术研究所 | Polyimide aerogel and preparation method thereof |
| CN115746385A (en) * | 2022-11-24 | 2023-03-07 | 华东理工大学 | Polyimide foam material and preparation method thereof |
| CN115746385B (en) * | 2022-11-24 | 2023-10-24 | 华东理工大学 | Polyimide foam material and preparation method thereof |
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