KR20150117900A - Nanoporous microspherical polyimide aerogel and method for manufacturing the same - Google Patents

Nanoporous microspherical polyimide aerogel and method for manufacturing the same Download PDF

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KR20150117900A
KR20150117900A KR1020140043636A KR20140043636A KR20150117900A KR 20150117900 A KR20150117900 A KR 20150117900A KR 1020140043636 A KR1020140043636 A KR 1020140043636A KR 20140043636 A KR20140043636 A KR 20140043636A KR 20150117900 A KR20150117900 A KR 20150117900A
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polyimide
dianhydride
manufacturing
nanoporous
present
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KR1020140043636A
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한학수
권진욱
김진영
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연세대학교 산학협력단
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
    • C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
    • 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
    • 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
    • C08J9/0004—Use of compounding ingredients, the chemical constitution of which is unknown, broadly defined, or irrelevant
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L79/00—Compositions 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 C08L61/00 - C08L77/00
    • C08L79/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08L79/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
    • 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 present invention relates to a nanoporous microspherical polyimide aerogel and a manufacturing method thereof. When using the manufacturing method of the polyimide aerogel according to an embodiment of the present invention, it is possible to manufacture in a low-temperature process and thus possible to save time and energy compared to an existing manufacturing method. In addition, the manufacturing method of the present invention ensures reduction in manufacturing expenses and to manufacture spherical polyimide aerogels which are in micro size and uniform particles, and has nano-sized pores, excellent chemical stability, and insulating, absorbing, and desorbing properties. The spherical polyimide aerogels can be applied to various fields including insulation materials, a drug-delivery medium, and a catalyst support due to its outstanding physical characteristics.

Description

TECHNICAL FIELD The present invention relates to a nanoporous micro spherical polyimide aerogel and a method of manufacturing the same.

The present invention relates to a nanoporous microsphere polyimide aerogel and a method of manufacturing the same. More particularly, the present invention relates to a polyamic acid precursor composition which is manufactured into an aerogel form and has excellent chemical stability, adiabatic and desorption characteristics, The present invention relates to a spherical polyimide aerogel having micro-sized uniform particles and a method for producing the same.

A variety of studies have been conducted since the discovery of aerogels in the 1930s. The most common form of silica aerogels is the aerosol field and building insulation, medical equipment such as long-term storage and transportation of the body, And an electric insulating film having a low dielectric constant, and is an ultra-light new material having a wide range of applications such as energy, environment, electric, electronic, space and medical fields.

However, in order to produce silica aerogels having excellent physical properties, micropores must not be destroyed. To prevent this, silica airgel is dried using supercritical carbon dioxide. However, such a supercritical drying method requires a high pressure and a high temperature, thus posing a risk of safety accidents. Moreover, there is a disadvantage in that there is a difficulty in continuous processing due to the limitation of the size of the autoclave vessel and a manufacturing cost is high.

 In order to solve such a problem, studies have been made on manufacturing aerogels using various raw materials (Patent Document 1 and Patent Document 2), and various attempts have been made to produce aerogels using polymers in particular. 3)

Polyimide resin is a state-of-the-art chemical material with high heat resistance, low dielectric strength and high strength. It has a chemical structure that can not be decomposed even at high temperatures of 400 ° C or higher. It is thin and has excellent flexibility. It is widely used as a core material in industries such as IT, automobile, semiconductor and display. NASA and the like have developed an airgel sheet using polyimide. However, there is a limit to the types of polyimide used in the production method, and the supercritical carbon dioxide drying method is used to increase the production cost, and the airgel is used as a drug delivery medium and a catalyst carrier , It is necessary to develop a new type of polyimide aerogels because it is advantageous to make them into a particle form instead of a sheet form in order to use it as an insulating material.

   Therefore, if a spherical polyimide aerogels are used that are micro-sized and homogeneous particles having nano-size pores that can replace silica aerogels by using low-temperature processes using polyimide materials having excellent physical properties, silica airgel and sheet form It is expected that the disadvantages of polyimide aerogels can be solved.

Korean Patent Laid-Open No. 10-2012-0103646 Korean Patent Publication No. 10-2010-0098905 U.S. Patent No. 7,074,880

An object of the present invention is to provide a nano-porous micro-spherical polyimide aerogel which is uniform micro-sized particles having nano-sized pores and excellent in chemical stability, heat insulation and adsorption / desorption properties, and a method for producing the same.

In order to solve the above problems,

There is provided a nanoporous microsphere polyimide aerogel comprising a polyimide polymer having a repeating unit represented by any of the following formulas (1) to (3).

[Chemical Formula 1]

Figure pat00001

(2)

Figure pat00002

(3)

Figure pat00003

In the above Formulas 1 to 3,

Ar 1 , Ar 1 and Ar 2 are at least one aromatic selected from the following structural formulas 1 to 6, and Ar ', Ar' 1 and Ar ' 2 are at least one aromatic selected from the following structural formulas 7 to 12;

n is an integer satisfying 50? n? 10000, m is an integer satisfying 25? m? 10000, and 1 is an integer satisfying 25?

Figure pat00004
Figure pat00005
Figure pat00006

Figure pat00007
Figure pat00008
Figure pat00009

Figure pat00010
Figure pat00011
Figure pat00012

Figure pat00013
Figure pat00014
Figure pat00015

The molar ratio m: 1 between each repeating unit in the polyimide polymer having the repeating unit represented by the above formula (2) or (3) may be 0.5: 9.5 to 9.5: 0.5.

In order to solve the above problems,

In the method for producing a nano-porous microsphere polyimide aerogel comprising a polyimide polymer having a repeating unit represented by any one of the above formulas (1) to (3)

(a) synthesizing a polyamic acid precursor by reacting an aromatic dianhydride with an aromatic diamine in an organic polar solvent;

(b) placing the polyamic acid precursor in a heat-resistant container of an autoclave, sealing the container with a nonsolvent between the autoclave and the heat-resistant container;

(c) curing stepwise at 200 to 350 ° C after the sealing, and drying the nanoporous microspheres of the polyimide aerogels.

The concentration of the solid content of the polyamic acid precursor synthesized in the step (a) may be 5 to 50% by weight based on the total solution.

In the step (a), the organic polar solvent may be any one selected from N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc) and dimethylformamide (DMF).

In step (a), the aromatic dianhydride may be 4,4 '- (hexafluoroisopropylidene) diphthalic dianhydride (6FDA), pyromellitic dianhydride (PMDA), 3,3' Benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic dianhydride (ODPA) 3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride (DSDA).

In step (a), the aromatic diamine may be 2,2'-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (AHHFP), 4,4'- ODA), 3,4'-oxydianiline (3,4'-ODA), 1,4-phenylenediamine (1,4-PDA), 4,4'- DDS) and diaminophenylmethane (MDA).

In step (b), the nonsolvent may be acetone or ethyl acetate.

Other details of the embodiments of the present invention are included in the following detailed description.

By using the manufacturing method of the nanoporous micro spherical polyimide aerogels according to the embodiment of the present invention, it is possible to manufacture by the low-temperature process, which saves time and energy compared to the conventional manufacturing method, And spherical polyimide aerogels having micro-sized uniform particles having nano-sized pores and excellent chemical stability, heat insulation, and desorption / desorption characteristics can be produced. The nanoporous micro spherical polyimide aerogels can be applied to various fields such as a heat insulating material, a drug delivery medium and a catalyst carrier due to their excellent physical properties.

1 is a graph showing a result of thermogravimetric analysis of a nanoporous microsphere polyimide aerogel using a polyamic acid precursor according to an embodiment of the present invention.
FIG. 2 illustrates Particle size sidetribution of a nanoporous microsphere polyimide airgel according to an embodiment of the present invention.
FIG. 3 is a photograph of a nano-porous micro-spherical polyimide airgel according to an embodiment of the present invention, taken using an SEM.
FIG. 4 is a photograph of a nano-sized pore on the surface of a nano-porous micro-spherical polyimide airgel according to an embodiment of the present invention, using SEM.
5 is a graph showing specific surface area and porosity of nano-porous micro spherical polyimide aerogels according to an embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

A polyimide aerogel according to an embodiment of the present invention includes a polymer having nano-sized micropores, and is a micrometer-sized spherical particle.

The polyamic acid precursor according to an embodiment of the present invention reacts with amine groups of diamines at both ends of the dianhydride to form a polyamic acid precursor in a solution state as shown in Reaction Scheme 1 below, 2 to form a polyimide polymer through a dehydration condensation reaction.

<Reaction Scheme 1>

Figure pat00016

Figure pat00017

Figure pat00018

<Reaction Scheme 2>

Figure pat00019

Figure pat00020

Figure pat00021

The nanoporous microspheroidal polyimide aerogels according to the present invention may include a polyimide polymer prepared using a polyamic acid precursor and having a repeating unit represented by any of the following formulas (1) to (3).

[Chemical Formula 1]

Figure pat00022

(2)

Figure pat00023

(3)

Figure pat00024

In the above Formulas 1 to 3,

Specific examples of Ar 1 , Ar 1 and Ar 2 may be selected from the following Structural Formulas 1 to 6, but are not limited thereto.

Specific examples of Ar ', Ar' 1 and Ar ' 2 may be selected from the following structural formulas 7 to 12, but are not limited thereto.

n is an integer satisfying 50? n? 10000, m is an integer satisfying 25? m? 10000, and 1 is an integer satisfying 25?

Figure pat00025
Figure pat00026
Figure pat00027

Figure pat00028
Figure pat00029
Figure pat00030

Figure pat00031
Figure pat00032
Figure pat00033

Figure pat00034
Figure pat00035
Figure pat00036

The method for producing a nanoporous microsphere polyimide aerogel comprising a polyimide polymer having a repeating unit represented by any one of the above formulas (1) to (3)

(a) synthesizing a polyamic acid precursor by reacting an aromatic dianhydride with an aromatic diamine in an organic polar solvent;

(b) placing the polyamic acid precursor in a heat-resistant container of an autoclave, sealing the container with a nonsolvent between the autoclave and the heat-resistant container;

(c) stepwise curing at 200 to 350 DEG C after the sealing, and then drying.

The molar ratio m: 1 between the respective repeating units in the polyimide polymer containing the repeating units represented by the above formulas (2) to (3) is preferably 0.5: 9.5 to 9.5: 0.5.

The concentration of the solid content of the polyamic acid precursor is preferably 5 to 50 wt% based on the total solution.

The organic polar solvent is preferably any one selected from N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc) and dimethylformamide (DMF), but is not limited thereto.

Wherein the aromatic dianhydride is selected from the group consisting of 4,4 '- (hexafluoroisopropylidene) diphthalic dianhydride (6FDA), pyromellitic dianhydride (PMDA), 3,3', 4,4'-benzophenonetetracar (BTDA), 4,4'-oxydiphthalic dianhydride (ODPA) and 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA) , 4'-diphenylsulfone tetracarboxylic acid dianhydride (DSDA), but the present invention is not limited thereto.

The aromatic diamine may be selected from the group consisting of 2,2'-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (AHHFP), 4,4'-oxydianiline 4'-oxydianiline (3,4'-ODA), 1,4-phenylenediamine (1,4-PDA), 4,4'- Aminophenylmethane (MDA), but is not limited thereto.

The nonsolvent may be any liquid having a low vaporization temperature, but it is more preferably acetone or ethyl acetate.

The polyimide aerogels are preferably prepared by adding the polyamic acid precursor and nonsolvent to an autoclave, then sealing, curing stepwise at 200 to 350 ° C, and then drying. In particular, 45 to 75 minutes at 70 to 90 DEG C, 20 to 40 minutes at 130 to 170 DEG C, 20 to 40 minutes at 180 to 220 DEG C, 20 to 40 minutes at 230 to 250 DEG C, 100 to 140 minutes at 320 to 380 DEG C It is preferable to cure it stepwise and then dry it.

The size of the polyimide aerogels according to an embodiment of the present invention may be 3.5 to 5.5 탆, but is not limited thereto.

The polyimide aerogels may have a specific surface area of 90 to 120 m &lt; 2 &gt; / g and a porosity of 80 to 90%, but the present invention is not limited thereto.

Hereinafter, specific examples, production examples, test examples, evaluation examples, etc. according to the present invention will be described in detail. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Manufacturing example  : Polyamic acid  Preparation of precursor

The following Reaction Scheme 3 shows a schematic procedure for synthesizing a polyamic acid precursor as a preferred embodiment of the present invention. 0.801 g (3 mmol) of 4,4'-oxydianiline was placed in a 50 ml Erlenmeyer flask, and 10 ml of NMP as a polar solvent was added thereto, followed by stirring until dissolution. Then, 0.873 g (3 mmol) of the same molar amount of pyromellitic dianhydride was added, and the mixture was stirred at 0 ° C. under a nitrogen atmosphere for 24 hours.

<Reaction Scheme 3>

Figure pat00037
Figure pat00038

Figure pat00039

Figure pat00040

Example  : Manufacture of nano-porous micro spherical polyimide aerogels

The following Scheme 4 shows a schematic procedure for preparing a nanoporous microsphere polyimide aerogel using a polyamic acid precursor as a preferred embodiment of the present invention. The polyamic acid composition synthesized in the Preparation Example was immersed in a heat-resistant container of an autoclave, and then acetone was placed between the autoclave and the heat-resistant container. Then, the mixture was heated in an oven at 80 ° C. for 1 hour, at 150 ° C. for 30 minutes, , Curing stepwise at 250 ° C for 30 minutes and 350 ° C for 2 hours to synthesize a polyimide polymer in the form of an airgel. Afterwards, the airgel was dried in a vacuum oven at 80 DEG C for 24 hours in order to collect aerosols, thereby obtaining micro-sized spherical polyimide aerogels having nano-sized pores.

<Reaction Scheme 4>

Figure pat00041

Figure pat00042

Figure pat00043

Test Example . Thermogravimetric analysis ( Thermogravimetric 분석 )

In order to confirm the thermal stability of the high-performance nanoporous microspheroidal polyimide aerogels using the polyamic acid precursor of the present invention, thermogravimetric analysis was performed to measure the mass change with heating from room temperature to 800 ° C.

1 is a graph showing a result of thermogravimetric analysis of a nanoporous microsphere polyimide aerogel using a polyamic acid precursor according to an embodiment of the present invention. From these results, it was confirmed that the thermal properties of the nanoporous micro spherical polyimide aerogels of the present invention exhibit considerably high thermal stability even at high temperatures. It can be confirmed that the nanoporous micro spherical polyimide aerogels of the present invention have remarkably excellent thermal stability when the 1% weight loss temperature is 520 ° C and the 5% weight loss temperature is 580 ° C.

Test Example . dynamic Light scattering  Photometer ( dynamic light scattering )

The particle size of the nanoporous microsphere polyimide aerogels using the polyamic acid precursor of the present invention was measured and analyzed using a dynamic light scattering photometer to determine the fluidity between the polymer chains.

FIG. 2 illustrates Particle size sidetribution of a nanoporous microsphere polyimide airgel according to an embodiment of the present invention. From these results, it can be seen that the size of the nanoporous microsphere polyimide aerogels according to the present invention is 3.5 to 5.5 micrometers, and has uniform particles, and it can be deduced that the particles are uniform.

Evaluation example

FIG. 3 is a photograph of a nano-porous micro-spherical polyimide airgel according to an embodiment of the present invention, taken using an SEM. As a result, the nanoporous microsphere polyimide aerogels of the present invention have micro-micrometer size and have spherical uniform particles.

FIG. 4 is a photograph of a nano-sized pore on the surface of a nano-porous microsphere polyimide airgel according to an embodiment of the present invention, using SEM. 5 is a graph showing specific surface area and porosity of nano-porous micro spherical polyimide aerogels according to an embodiment of the present invention. As a result, the nanoporous micro spherical polyimide aerogels of the present invention have a high porosity of 80 to 90% and a wide specific surface area of 90 to 120 m &lt; 2 &gt; / g.

Claims (9)

A nanoporous microsphere polyimide aerogel comprising a polyimide polymer having a repeating unit represented by any one of the following formulas (1) to (3).
[Chemical Formula 1]
Figure pat00044

(2)
Figure pat00045

(3)
Figure pat00046

In the above Formulas 1 to 3,
Ar 1 , Ar 1 and Ar 2 are at least one aromatic selected from the following structural formulas 1 to 6, and Ar ', Ar' 1 and Ar ' 2 are at least one aromatic selected from the following structural formulas 7 to 12;
n is an integer satisfying 50? n? 10000, m is an integer satisfying 25? m? 10000, and 1 is an integer satisfying 25?
Figure pat00047
Figure pat00048
Figure pat00049

Figure pat00050
Figure pat00051
Figure pat00052

Figure pat00053
Figure pat00054
Figure pat00055

Figure pat00056
Figure pat00057
Figure pat00058
 The method according to claim 1,
Wherein the molar ratio m: l of each repeating unit in the polyimide polymer having the repeating unit represented by the above formula (2) or (3) is 0.5: 9.5 to 9.5: 0.5. (a) synthesizing a polyamic acid precursor by reacting an aromatic dianhydride with an aromatic diamine in an organic polar solvent;
(b) placing the polyamic acid precursor in a heat-resistant container of an autoclave, sealing the container with a nonsolvent between the autoclave and the heat-resistant container;
(c) curing stepwise at 200 to 350 DEG C after the sealing, and then drying the nanoporous microspheres according to claim 1. The method of claim 3,
A polyimide polymer having a repeating unit represented by the above general formula (2) or (3) according to claim 1, wherein the molar ratio m: l of each repeating unit in the polyimide polymer is 0.5: 9.5 to 9.5: A method of manufacturing a midairgel. The method of claim 3,
Wherein the concentration of the solid content of the polyamic acid precursor synthesized in the step (a) is 5 to 50% by weight based on the total weight of the polyamic acid precursor. The method of claim 3,
Wherein the organic polar solvent in step (a) is any one selected from the group consisting of N-methylpyrrolidone (NMP), N, N-dimethylacetamide (DMAc) and dimethylformamide (DMF) Of the polyimide aerogels. The method of claim 3,
The aromatic dianhydride of step (a) may be selected from the group consisting of 4,4 '- (hexafluoroisopropylidene) diphthalic dianhydride (6FDA), pyromellitic dianhydride (PMDA), 3,3'4,4'- Benzophenone tetracarboxylic dianhydride (BTDA), 3,3 ', 4,4'-biphenyltetracarboxylic dianhydride (BPDA), 4,4'-oxydiphthalic dianhydride (ODPA) 3 ', 4,4'-diphenylsulfone tetracarboxylic acid dianhydride (DSDA). 3. The method of claim 1, wherein the polyimide aerogels are selected from the group consisting of 3', 4,4'-diphenylsulfone tetracarboxylic dianhydride (DSDA). The method of claim 3,
The aromatic diamine of step (a) may be selected from the group consisting of 2,2'-bis (3-amino-4-hydroxyphenyl) -hexafluoropropane (AHHFP), 4,4'- ODA), 3,4'-oxydianiline (3,4'-ODA), 1,4-phenylenediamine (1,4-PDA), 4,4'- DDS) and diaminophenylmethane (MDA). &Lt; RTI ID = 0.0 &gt; 11. &lt; / RTI &gt; The method of claim 3,
Wherein the nonsolvent of step (b) is acetone or ethyl acetate. The method of claim 1, wherein the nonsolvent is acetone or ethyl acetate.
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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170115943A (en) * 2016-04-08 2017-10-18 연세대학교 산학협력단 Micro-pored polyimide sponge and method for preparation of the same
CN109265726A (en) * 2018-07-06 2019-01-25 四川大学 A kind of polyimide aerogels granular materials and preparation method thereof
CN111508365A (en) * 2020-05-07 2020-08-07 深圳市华星光电半导体显示技术有限公司 Flexible display panel and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170115943A (en) * 2016-04-08 2017-10-18 연세대학교 산학협력단 Micro-pored polyimide sponge and method for preparation of the same
CN109265726A (en) * 2018-07-06 2019-01-25 四川大学 A kind of polyimide aerogels granular materials and preparation method thereof
CN109265726B (en) * 2018-07-06 2021-05-28 四川大学 Polyimide aerogel particle material and preparation method thereof
CN111508365A (en) * 2020-05-07 2020-08-07 深圳市华星光电半导体显示技术有限公司 Flexible display panel and preparation method thereof

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