CN110591142A - Preparation method of graphene/polyimide composite aerogel - Google Patents
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- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1067—Wholly aromatic polyimides, i.e. having both tetracarboxylic and diamino moieties aromatically bound
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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Abstract
The invention discloses a preparation method of graphene/polyimide composite aerogel, and belongs to the technical field of materials. The preparation method mainly comprises the steps of preparing a polyamide acid aqueous solution by the aid of a quaternary ammonium salt cationic surfactant and a tertiary amine, uniformly dispersing graphene in the polyamide acid aqueous solution to obtain a graphene/polyamide acid mixed solution, and aging, freeze drying and thermal imidization to obtain the graphene/polyimide composite aerogel. The method has the advantages of simplicity, high efficiency, low equipment requirement, wide application range, environmental friendliness and low cost, can effectively solve the problem that the traditional polyimide high-performance aerogel is difficult to prepare, can be used for gas adsorption, organic matter adsorption, heat insulation materials and the like, and has high potential application value in the fields of atmospheric pollution treatment, water pollution treatment, heat insulation structural materials and the like.
Description
Technical Field
The invention belongs to the technical field of materials, relates to preparation of polymer aerogel, and particularly relates to a preparation method of graphene/polyimide composite 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, researchers develop a polyimide aerogel preparation method which is characterized in that polyamic acid is prepared into an aqueous solution, and then freeze-dried and imidized, and the method is simple and efficient, is suitable for preparing most of polyimide aerogels, and is an ideal polyimide aerogel preparation method. However, the polyamic acid aerogel has a large molecular chain flexibility and a low aerogel skeleton strength, which causes large size shrinkage of the polyamic acid aerogel, and further seriously affects the quality of the polyimide aerogel product. Graphene is a polymer made of carbon atoms in sp2The two-dimensional carbon nanomaterial composed of the hybrid track can be prepared by stripping graphite by mechanical and chemical methods, has the advantages of wide source, environmental friendliness, high rigidity and the like, and theoretically has the advantages of introducing graphene into a polyamide acid systemIt is expected to increase the strength of the polyamic acid aerogel skeleton, thereby effectively reducing the dimensional shrinkage thereof. Therefore, how to introduce graphene into a polyamic acid aqueous solution system and establish a simple, efficient and wide-application-range graphene/polyimide composite aerogel preparation method has important significance for preparing polyimide aerogel.
Disclosure of Invention
In order to solve the problems that the preparation of graphene/polyimide aerogel in the prior art is complex and can not meet the green preparation, the invention provides a preparation method of the graphene/polyimide composite aerogel, which is simple, efficient, low in equipment requirement and wide in application range.
In order to achieve the purpose, the invention adopts the following technical means:
a preparation method of graphene/polyimide composite 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;
adding dianhydride monomer, stirring until the dianhydride monomer is completely dissolved and a viscous solution is formed, and obtaining a polyamide acid aqueous solution; the addition molar ratio of the diamine monomer to the dianhydride monomer is 1: (0.95-1.05);
uniformly dispersing graphene in a polyamic acid aqueous solution to obtain a graphene/polyamic acid mixed solution, wherein the adding mass ratio of the graphene to a diamine monomer is (0.05-0.5): 1;
degassing the mixed solution, refrigerating, aging, freezing and drying to obtain the graphene/polyamic acid composite aerogel;
and carrying out thermal imidization treatment on the graphene/polyamic acid composite aerogel to obtain the graphene/polyimide composite 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 graphene is one or a mixture of several of graphene oxide, reduced graphene oxide and common graphene in any proportion.
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 preparation method of the graphene/polyimide composite aerogel comprises the steps of dissolving a diamine monomer in deionized water through a quaternary ammonium salt cationic surfactant and a tertiary amine, reacting the dissolved diamine monomer with a dianhydride monomer to obtain a polyamide acid aqueous solution, uniformly dispersing graphene in the polyamide acid aqueous solution to obtain a graphene/polyamide acid mixed aqueous solution, and preparing the polyimide aerogel from the polyamide acid aqueous solution through freeze drying and thermal imidization processes, wherein experiments show that the introduction of the graphene can effectively reduce the size shrinkage rate of the polyimide aerogel and can improve the quality of a polyimide aerogel product, and the main reason is that the polyamide acid molecular chain has high flexibility, and the introduction of the high-strength and high-modulus graphene can help to improve the skeleton strength of the aerogel so as to reduce the size shrinkage of the polyamide acid, thereby improving the quality of the polyimide aerogel product. According to the preparation method, the polyamic acid aqueous solution is prepared by the quaternary ammonium salt cationic surfactant and the tertiary amine in an auxiliary manner, and the method is suitable for the preparation of different types of polyimide aerogel without considering the dissolving performance 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 composite aerogel is difficult to prepare, so that the preparation method disclosed by the invention is widely suitable for preparing various polyimide composite aerogels of different types, and can expand the application of the polyimide aerogel in the fields of separation materials, adsorption materials, heat-insulating materials, gases, biosensors, low-dielectric-constant materials and the like.
Drawings
FIG. 1 is a diagram of example 2 of the present invention for preparing graphene/polyimide aerogel;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the polyimide aerogel obtained in example 2 of the present invention (magnification from a to c: 100, 500, 1000, respectively).
Detailed Description
The invention relates to a preparation method of graphene/polyimide composite 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 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
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;
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);
thirdly, uniformly dispersing graphene in the polyamic acid aqueous solution to prepare a graphene/polyamic acid aqueous solution;
the specific means is as follows: adding the weighed graphene into a polyamic acid aqueous solution, and stirring to form a uniform solution, thereby obtaining a graphene/polyamic acid aqueous solution; the adding mass ratio of the graphene to the diamine monomer is (0.05-0.5): 1.
and finally, placing the graphene/polyamide acid aqueous solution in a vacuum drying oven, degassing, refrigerating, aging for 2-3 days, freeze-drying to obtain graphene/polyamide acid aerogel, and dehydrating and cyclizing (thermal imidizing) in the drying oven to obtain the graphene/polyimide aerogel.
The specific means is as follows: pouring the prepared graphene/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 graphene/polyamic acid sample to obtain the graphene/polyamic acid composite aerogel, and dehydrating and cyclizing polyamic acid through heat treatment to obtain the graphene/polyimide composite aerogel.
The dehydration and cyclization process of the graphene/polyamic acid composite 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 preferred graphene/polyamide acid composite aerogel thermal imidization process is as follows: 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. The graphene can be one or a mixture of several of graphene oxide, reduced graphene oxide, common graphene and the like in any proportion.
And degassing the graphene/polyamic acid aqueous solution in a vacuum drying oven for 2-6 hours. The graphene/polyamic acid composite aerogel can be obtained by freeze-drying in any container, and a beaker or other types of glass products are preferably used as the container.
The technical scheme of the invention is explained in detail by combining the specific embodiment and the attached drawings as follows:
example 1
Preparing the graphene/polyamic acid composite 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, and then 2.18g of pyromellitic dianhydride (PMDA) is added and stirred to prepare a polyamic acid aqueous solution; secondly, adding 0.10g of graphene oxide into the polyamic acid aqueous solution, and stirring until a uniform solution, namely the graphene/polyamic acid aqueous solution, is formed; thirdly, pouring the graphene/polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain the graphene/polyamic acid composite aerogel; finally, carrying out thermal imidization treatment to obtain the graphene/polyimide composite aerogel, wherein the thermal imidization process comprises the following steps: 120 ℃ (0.5h) +150 ℃ (0.5h) +200 ℃ (1h) +250 ℃ (4 h).
Example 2
Preparing the graphene/polyamic acid composite 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, and then 2.18g of pyromellitic dianhydride (PMDA) is added and stirred to prepare a polyamic acid aqueous solution; secondly, adding 0.50g of graphene oxide into the polyamic acid aqueous solution, and stirring until a uniform solution, namely the graphene/polyamic acid aqueous solution, is formed; thirdly, pouring the graphene/polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain the graphene/polyamic acid composite aerogel; finally, carrying out thermal imidization treatment to obtain the graphene/polyimide composite aerogel, 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, the graphene-reinforced polyimide aerogel has good dimensional stability and a light weight, and when the graphene-reinforced polyimide aerogel is placed on green leaves, no significant pressure is applied to the green leaves; as can be seen from fig. 2, the graphene/polyimide in the composite aerogel mainly exists in a lamellar structure, and no obvious graphene lamellar layer is seen, which may be due to the fact that the graphene is added in a small amount and has good compatibility with polyimide, so that the graphene/polyimide is coated by the polyimide matrix in the aerogel framework.
Example 3
Preparing the graphene/polyamic acid composite 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, and then 2.18g of pyromellitic dianhydride (PMDA) is added and stirred to prepare a polyamic acid aqueous solution; secondly, adding 1.00g of graphene oxide into the polyamic acid aqueous solution, and stirring until a uniform solution, namely the graphene/polyamic acid aqueous solution, is formed; thirdly, pouring the graphene/polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain the graphene/polyamic acid composite aerogel; finally, carrying out thermal imidization treatment to obtain the graphene/polyimide composite aerogel, wherein the thermal imidization process comprises the following steps: 120 ℃ (0.5h) +150 ℃ (0.5h) +200 ℃ (1h) +250 ℃ (4 h).
Example 4
Preparing the graphene/polyamic acid composite 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, and then 2.18g of pyromellitic dianhydride (PMDA) is added and stirred to prepare a polyamic acid aqueous solution; secondly, adding 0.50g of graphene oxide into the polyamic acid aqueous solution, and stirring until a uniform solution, namely the graphene/polyamic acid aqueous solution, is formed; thirdly, pouring the graphene/polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain the graphene/polyamic acid composite aerogel; finally, carrying out thermal imidization treatment to obtain the graphene/polyimide composite aerogel, wherein the thermal imidization process comprises the following steps: 120 ℃ (0.5h) +150 ℃ (0.5h) +200 ℃ (1h) +250 ℃ (4 h).
Example 5
Preparing the graphene/polyamic acid composite 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, and then 2.18g of pyromellitic dianhydride (PMDA) is added and stirred to prepare a polyamic acid aqueous solution; secondly, adding 0.50g of graphene oxide into the polyamic acid aqueous solution, and stirring until a uniform solution, namely the graphene/polyamic acid aqueous solution, is formed; thirdly, pouring the graphene/polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain the graphene/polyamic acid composite aerogel; finally, carrying out thermal imidization treatment to obtain the graphene/polyimide composite aerogel, wherein the thermal imidization process comprises the following steps: 120 ℃ (0.5h) +150 ℃ (0.5h) +200 ℃ (1h) +250 ℃ (4 h).
Example 6
Preparing the graphene/polyamic acid composite 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, and then 2.18g of pyromellitic dianhydride (PMDA) is added and stirred to prepare a polyamic acid aqueous solution; secondly, adding 0.50g of graphene oxide into the polyamic acid aqueous solution, and stirring until a uniform solution, namely the graphene/polyamic acid aqueous solution, is formed; thirdly, pouring the graphene/polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain the graphene/polyamic acid composite aerogel; finally, carrying out thermal imidization treatment to obtain the graphene/polyimide composite aerogel, wherein the thermal imidization process comprises the following steps: 120 ℃ (1.5h) +150 ℃ (2h) +200 ℃ (2h) +250 ℃ (3 h).
Example 7
Preparing the graphene/polyamic acid composite aerogel: firstly, 1.90g 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, and then 2.18g of pyromellitic dianhydride (PMDA) is added and stirred to prepare a polyamic acid aqueous solution; secondly, adding 0.48g of graphene oxide into the polyamic acid aqueous solution, and stirring until a uniform solution, namely the graphene/polyamic acid aqueous solution, is formed; thirdly, pouring the graphene/polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain the graphene/polyamic acid composite aerogel; finally, carrying out thermal imidization treatment to obtain the graphene/polyimide composite aerogel, wherein the thermal imidization process comprises the following steps: 120 ℃ (2h) +150 ℃ (2h) +200 ℃ (2h) +250 ℃ (3 h).
Example 8
Preparing the graphene/polyamic acid composite aerogel: firstly, 2.10g 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, and then 2.18g of pyromellitic dianhydride (PMDA) is added and stirred to prepare a polyamic acid aqueous solution; secondly, adding 0.53g of graphene oxide into the polyamic acid aqueous solution, and stirring until a uniform solution, namely the graphene/polyamic acid aqueous solution, is formed; thirdly, pouring the graphene/polyamic acid aqueous solution into a mold, and then degassing, aging, freezing and drying to obtain the graphene/polyamic acid composite aerogel; finally, carrying out thermal imidization treatment to obtain the graphene/polyimide composite aerogel, wherein the thermal imidization process comprises the following steps: 120 ℃ (1.5h) +150 ℃ (1.5h) +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 (10)
1. The preparation method of the graphene/polyimide composite aerogel is characterized by comprising 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;
adding dianhydride monomer, stirring until the dianhydride monomer is completely dissolved and a viscous solution is formed, and obtaining a polyamide acid aqueous solution; the addition molar ratio of the diamine monomer to the dianhydride monomer is 1: (0.95-1.05);
uniformly dispersing graphene in a polyamic acid aqueous solution to obtain a graphene/polyamic acid mixed solution, wherein the adding mass ratio of the graphene to a diamine monomer is (0.05-0.5): 1;
degassing the mixed solution, refrigerating, aging, freezing and drying to obtain the graphene/polyamic acid composite aerogel;
and carrying out thermal imidization treatment on the graphene/polyamic acid composite aerogel to obtain the graphene/polyimide composite aerogel.
2. The preparation method of the graphene/polyimide composite aerogel according to claim 1, wherein the preparation method comprises the following steps: the diamine monomer is one or a mixture of more of 4, 4' -diaminodiphenyl ether, biphenyldiamine and p-phenylenediamine in any proportion.
3. The preparation method of the graphene/polyimide composite aerogel according to claim 1, wherein the preparation method comprises the following steps: 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 preparation method of the graphene/polyimide composite aerogel according to claim 1, wherein the preparation method comprises the following steps: the tertiary amine is one or a mixture of several of trimethylamine, triethylamine and N, N' -dimethylethanolamine in any proportion.
5. The preparation method of the graphene/polyimide composite aerogel according to claim 1, wherein the preparation method comprises the following steps: 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 preparation method of the graphene/polyimide composite aerogel according to claim 1, wherein the preparation method comprises the following steps: the graphene is one or a mixture of several of graphene oxide, reduced graphene oxide and common graphene in any proportion.
7. The preparation method of the graphene/polyimide composite aerogel according to claim 1, wherein the preparation method comprises the following steps: and the cold storage aging time of the polyamic acid aqueous solution is 2-3 days.
8. The preparation method of the graphene/polyimide composite aerogel according to claim 1, wherein the preparation method comprises the following steps: the freeze drying condition is that the pressure is less than or equal to 20Pa, and the time is 12-48 h.
9. The preparation method of the graphene/polyimide composite aerogel according to claim 1, wherein the preparation method comprises the following steps: the polyamic acid aerogel thermal imidization treatment adopts a step temperature, and the temperature is 120-250 ℃.
10. The preparation method of the graphene/polyimide composite aerogel according to claim 1, wherein the preparation method comprises the following steps: 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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| CN111218112A (en) * | 2020-03-11 | 2020-06-02 | 南京航空航天大学 | rGO/polyimide composite aerogel and preparation method and application thereof |
| CN111471212A (en) * | 2020-06-01 | 2020-07-31 | 陕西科技大学 | Chemical-coordination double-crosslinking polyimide aerogel and preparation method thereof |
| CN113088077A (en) * | 2021-03-31 | 2021-07-09 | 四川大学 | Polyimide/multi-walled carbon nanotube composite aerogel and preparation method and application thereof |
| WO2022125839A1 (en) * | 2020-12-11 | 2022-06-16 | Aspen Aerogels, Inc. | Water co-catalyst for polyimide process |
| WO2022125835A1 (en) * | 2020-12-11 | 2022-06-16 | Aspen Aerogels, Inc. | Aqueous processes for preparing polyamic acid gels, polymate gels, polyimide gels, and porous carbon materials |
| CN114854087A (en) * | 2022-05-13 | 2022-08-05 | 吉林大学 | Polyimide composite material with double heat-conducting networks and preparation method thereof |
| WO2024051826A1 (en) * | 2022-09-09 | 2024-03-14 | 中国石油化工股份有限公司 | Composite aerogel, recyclable heat-storage phase-change composite material with photothermal conversion function, and preparation methods therefor and use |
| US11932745B2 (en) | 2020-12-11 | 2024-03-19 | Aspen Aerogels, Inc. | Water co-catalyst for polyimide processes |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111218112A (en) * | 2020-03-11 | 2020-06-02 | 南京航空航天大学 | rGO/polyimide composite aerogel and preparation method and application thereof |
| CN111471212A (en) * | 2020-06-01 | 2020-07-31 | 陕西科技大学 | Chemical-coordination double-crosslinking polyimide aerogel and preparation method thereof |
| CN111471212B (en) * | 2020-06-01 | 2022-08-23 | 陕西科技大学 | Chemical-coordination double-crosslinking polyimide aerogel and preparation method thereof |
| WO2022125839A1 (en) * | 2020-12-11 | 2022-06-16 | Aspen Aerogels, Inc. | Water co-catalyst for polyimide process |
| WO2022125835A1 (en) * | 2020-12-11 | 2022-06-16 | Aspen Aerogels, Inc. | Aqueous processes for preparing polyamic acid gels, polymate gels, polyimide gels, and porous carbon materials |
| US11932745B2 (en) | 2020-12-11 | 2024-03-19 | Aspen Aerogels, Inc. | Water co-catalyst for polyimide processes |
| CN113088077A (en) * | 2021-03-31 | 2021-07-09 | 四川大学 | Polyimide/multi-walled carbon nanotube composite aerogel and preparation method and application thereof |
| CN113088077B (en) * | 2021-03-31 | 2022-05-03 | 四川大学 | Polyimide/multi-walled carbon nanotube composite aerogel and preparation method and application thereof |
| CN114854087A (en) * | 2022-05-13 | 2022-08-05 | 吉林大学 | Polyimide composite material with double heat-conducting networks and preparation method thereof |
| WO2024051826A1 (en) * | 2022-09-09 | 2024-03-14 | 中国石油化工股份有限公司 | Composite aerogel, recyclable heat-storage phase-change composite material with photothermal conversion function, and preparation methods therefor and use |
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