CN108384047A - A kind of transparent, High Strength Polyimide aeroge and preparation method thereof - Google Patents
A kind of transparent, High Strength Polyimide aeroge and preparation method thereof Download PDFInfo
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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
- C08J9/286—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 the liquid phase being a solvent for the monomers but not for the resulting macromolecular composition, i.e. macroporous or macroreticular polymers
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- 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
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- 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
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- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
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Abstract
A kind of transparent, High Strength Polyimide aeroge of present invention offer and preparation method thereof, belongs to nano-porous materials and thermal isolation technique field.The preparation method, including：Aromatic triamine monomer is reacted in a solvent with dianhydride monomer dissolving, until reaction system is fully transparent；Dehydrating agent is added into transparent system, stirs and deaeration, subsequent stand forms gel；The gel is obtained into polyimide aerogels through solvent displacement, drying process.The polyimide aerogels that the present invention obtains have low-density (density 0.08g/cm3~0.3g/cm3), high-specific surface area (specific surface area be more than 200m2/ g), high intensity (young's modulus in compression be more than 10MPa), the characteristics such as lower thermal conductivity, high thermal stability (thermal degradation temperature is more than 400 DEG C) and the high grade of transparency (transmitance is more than 50%).
Description
Technical field
The present invention relates to a kind of transparent, High Strength Polyimide aeroges and preparation method thereof, belong to nano-porous materials
And thermal isolation technique field.
Background technology
Aeroge is a kind of nano material with continuous and open pore structure, and it is most light, heat-insulated to be that the current world improves quality
The best solid material of performance.Aeroge has high-specific surface area (400~1500m2/ g), high porosity (80~99.8%),
Low-density (0.003~0.6g/cm3) and the features such as lower thermal conductivity (0.013~0.038W/m continuous and), make its heat-insulation and heat-preservation,
The fields such as acoustic impedance coupling, absorption, filtering, catalyst carrier, pharmaceutical carrier have broad application prospects.So far,
It is prepared for various types of aeroges, including aerosil (CN102424538A through passing through chemical crosslink technique；
CN102633269A), chitosan aeroge (CN102417606A), carbon aerogels (CN102423668A；CN102430369A)、
Metal oxide and its composite aerogel (CN102513041A), multielement composite aerogel (CN102584010A), graphene
With carbon nanotube aerogel (CN102674315A), titania aerogel (CN102671587A) etc..Above-mentioned aeroge
Mechanical strength is weak, brittleness is big, and inflammable, not radiation hardness etc., therefore is badly in need of invention excellent in mechanical performance, while having excellent resistance to
The aeroge of the performances such as radiation, weatherability, fire-retardant, to realize application of the aeroge in aerospace and civil field.
Polyimides is a kind of organic polymer that main chain contains imide ring, has high mechanical strength, thermal stability good
And the advantages that wear-resistant.Either as structural material or functional material, significant superiority is adequately recognized
Know.In recent years, the research of polyimide aerogels has attracted much attention, compared with other polymer aerogels, polyimide aerogels
With the unique property such as excellent strength, rigid adjustable, high temperature resistant, resistance to extremely low temperature, radiation hardness, fire-retardant, therefore from 2006
Just extensive concern has been obtained since (USP7074880,2006) invention.Just because of this, U.S. NASA is in polyimide aerogels system
Standby and application aspect carries out numerous studies (document ACS Appl.Mater.Interfaces, 2012,4,536-544).However,
Traditional polyimide aerogels typically exhibit certain color and luster, are unable to reach transparency as silica aerogel.Therefore, gather
Although acid imide aeroge can solve the brittleness of silica aerogel, the transparency is lost simultaneously, certain to transparency requirement
High occasion can not substitute silica aerogel, prepare the polyimide aerogels of the high grade of transparency and become urgently to be resolved hurrily and important ask
One of topic.On the other hand, the porous structure of aeroge make its under external force be easy be collapsed be closed, to lose it is excellent every
The features such as hot property, huge specific surface area, high porosity, therefore, preparing has the rigid pore structure for resisting ambient pressure
The major issue solved is needed in aeroge and polyimide aerogels application.
Invention content
For deficiency in the prior art, it is a primary object of the present invention to propose a kind of transparent, High Strength Polyimide
Aeroge and preparation method thereof, to obtain with low-density, high-specific surface area, lower thermal conductivity, high thermal stability and the high grade of transparency
Etc. features aeroge.
To realize that aforementioned invention purpose, the technical solution adopted by the present invention are as follows：
A kind of preparation method of polyimide aerogels, includes the following steps：
Step 1 reacts aromatic triamine monomer with dianhydride monomer dissolving in a solvent, until reaction system is complete
All-transparent；
Dehydrating agent is added in step 2, the transparent system obtained to step 1, stirs and deaeration, subsequent stand forms gel；
The gel is obtained polyimide aerogels by step 3 through solvent displacement, drying process.
In an alternative embodiment, in step 1, amino and acid anhydrides in the aromatic triamine monomer and dianhydride monomer
Molar ratio is 1：1-1.05；The total mass concentration of the aromatic triamine monomer and dianhydride monomer in the solvent is 0.05
~0.3g/mL.
In an alternative embodiment, reacted at 0-180 DEG C in step 1.
In an alternative embodiment, aromatic triamine monomer described in step 1 is 4,4', 4 "-three amido triphenylmenthanes；Institute
It is at least one of 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides or pyromellitic dianhydride to state dianhydride monomer.
In an alternative embodiment, the solvent is n,N-Dimethylformamide, n,N-dimethylacetamide, dimethyl Asia
At least one of sulfone or N-Methyl pyrrolidone；Dehydrating agent described in step 2 is pyridine, triethylamine, acetic anhydride, methyl pyrrole
At least one of pyridine, chloroacetic chloride, thionyl chloride, the halide of phosphorus or Dicyclohexylcarbodiimide.
In an alternative embodiment, the quality of dehydrating agent described in step 2 is dianhydride monomer quality described in step 1
1~10 times.
In an alternative embodiment, the deaeration described in step 2 includes：It is carried out by ultrasound or decompression method at 0-180 DEG C
Deaeration.
In an alternative embodiment, the solvent displacement described in step 3 includes：
The gel is washed at least twice using solvent described in step 1, is then set with methanol, ethyl alcohol or acetone
Gel is changed, displacement number is no less than twice；The drying, including：
It is freeze-dried 2-10h under conditions of temperature≤20 DEG C, vacuum degree≤500Pa；Or
It is 40-250 DEG C in temperature using carbon dioxide, ethyl alcohol or methanol as supercritical fluid, the item of pressure >=8MPa
Supercritical drying, drying time 2-10h are carried out under part.
Polyimide aerogels prepared by the above method.
In an alternative embodiment, the polyimide aerogels, young's modulus in compression is more than 10MPa, transmitance is more than
50%.
Compared with prior art, the present invention has the advantages that：
Using aromatic triamine monomer and dianhydride monomer as raw material in the embodiment of the present invention, pass through polycondensation, chemical amidation
Method prepares wet gel, and since aromatic triamine has trifunctional, and dicarboxylic anhydride is rigidity, and what is formed after the two reaction is wet solidifying
Glue has cellular molecular network structure, makes molecular structure rigidity reinforced, meanwhile, under external force, honeycomb structure is advantageous
In uniform unloading pressure, stress concentration point is reduced, to increase the macro strength of material；The formula system can reduce colloidal sol
The size of grain, the skeleton unit size for forming gel network is less than visible wavelength, therefore realizes the saturating of polyimide aerogels
Brightization；Polyimide aerogels prepared by this method have low-density (density 0.08g/cm3~0.3g/cm3), high-ratio surface
(specific surface area is more than 200m to product2/ g), lower thermal conductivity, high thermal stability (thermal degradation temperature be more than 400 DEG C) and the high grade of transparency it is (saturating
50%) it crosses rate and is more than the characteristics such as.
Description of the drawings
Fig. 1 is obtained the scanning electron microscope (SEM) photograph of polyimide aerogels by the embodiment of the present invention 1；
Fig. 2 is the reaction principle schematic diagram of the embodiment of the present invention 1.
Specific implementation mode
Further detailed description is done to the present invention with reference to the accompanying drawings and examples：
An embodiment of the present invention provides a kind of transparent, High Strength Polyimide aeroge preparation methods, including following step
Suddenly：
Step 1, according to a certain amount of proportioning, aromatic triamine monomer and dianhydride monomer dissolving are contracted in a solvent
Poly- reaction, until reaction system is fully transparent；
Specifically, it in the embodiment of the present invention, is preferably reacted under stirring, it is fully transparent to system when reacting
Afterwards, it is ensured that any solid impurity is free of in system；
In the embodiment of the present invention, the solvent is n,N-Dimethylformamide (DMF), n,N-dimethylacetamide
(DMAc), at least one of dimethyl sulfoxide (DMSO) (DMSO) or N-Methyl pyrrolidone (NMP)；The aromatic triamine monomer is excellent
Select 4,4', 4 "-three amido triphenylmenthanes (TAPM)；The dianhydride monomer preferably 3,3 ', 4,4 '-benzophenone tetracarboxylic dianhydrides
(BTDA) or at least one of pyromellitic dianhydride (PMDA)；
In the embodiment of the present invention, the molar ratio of amino and acid anhydrides is 1 in the aromatic triamine monomer and dianhydride monomer：
1-1.05 has preferable intensity with the aeroge ensured；The aromatic triamine monomer and dianhydride monomer are described
Total concentration in solvent is 0.05~0.3g/mL, is come into full contact with reactant, and reaction efficiency is improved.It is preferred that at 0-180 DEG C into
Row reaction.
Dehydrating agent is added in step 2, the transparent system obtained to step 1 and carries out chemical amidation process, stirs simultaneously deaeration,
It then stands and forms gel；
In the embodiment of the present invention, the preferred pyridine of the dehydrating agent, triethylamine, acetic anhydride, picoline, chloroacetic chloride, chlorination
At least one of sulfoxide, the halide of phosphorus or Dicyclohexylcarbodiimide；The quality of the dehydrating agent is preferably institute in step 1
State dianhydride monomer quality 1~10 times.In the embodiment of the present invention, the deaeration includes：At 0-180 DEG C by ultrasound or
Decompression method carries out deaeration.
Specifically, in the present embodiment, preferred 0-180 DEG C of gel-forming temperature；
The gel is obtained polyimide aerogels by step 3 through solvent displacement, drying process.
Specifically, in the embodiment of the present invention, solvent displacement includes：Using identical with solvent described in step 1
Solvent washs the gel at least twice, to remove unreacted monomer and dehydrating agent, after having washed, with methanol, second
Alcohol or acetone replace gel, and displacement number is no less than twice；
Specifically, the drying, including：It is freeze-dried 2- under conditions of temperature≤20 DEG C, vacuum degree≤500Pa
10h；Or be 40-250 DEG C in temperature using carbon dioxide, ethyl alcohol or methanol as supercritical fluid, the item of pressure >=8MPa
Supercritical drying, drying time 2-10h are carried out under part.
The embodiment of the present invention additionally provides the polyimide aerogels of above method preparation.The aeroge has low-density
(density 0.08g/cm3~0.3g/cm3), high-specific surface area (specific surface area be more than 200m2/ g), lower thermal conductivity, high heat stability
Property the characteristics such as (thermal degradation temperature be more than 400 DEG C) and the high grade of transparency (transmitance is more than 50%), stronger extraneous press can be resisted
Power, and meet requirement of each field to aeroge transparency.
It is several specific embodiments of the present invention below, the raw materials used embodiment of the present invention is commercial product：
Embodiment 1
(1) synthesis of polyimides wet gel：
10mmol TAPM are taken, are substantially dissolved in 60ml anhydrous DMFs, 10.5mmol is added under stirring later
BTDA, in 0 DEG C of stirring to being completely dissolved, solution viscosity increases, and forms polyamic acid, reaction system is fully transparent at this time；Then
(mass ratio of acetic anhydride and triethylamine is 1 to the mixed liquor of addition 80mmol acetic anhydrides and triethylamine：1) it, quickly stirs 10 minutes
Afterwards, ultrasonic deaeration 30 minutes；Acquired solution is finally formed into gel after 0 DEG C of standing, about 5h.
(2) the solvent displacement of gel：
The gel of formation is placed in the DMF of 5 times of volumes, changes within every 12 hours a DMF, after displacement 2 times, then with 5 times of bodies
Long-pending ethyl alcohol carries out solvent displacement, changes an ethyl alcohol within every 5 hours, polyimides alcogel is obtained after 2 days.
(3) drying of wet gel：
Alcogel after displacement is dried into 6h by Supercritical Ethanol at 245 DEG C, 8MPa, obtains clear polyimides gas
Gel.
Through characterizations such as BET isothermal adsorptions, SEM, contact angles, it was demonstrated that the transparent high-strength polyimides airsetting that the present embodiment obtains
Glue has nano-porous structure, the scanning electron micrograph of this polyimide aerogels referring to Fig. 1, reaction principle referring to figure
2, other physical parameters such as specific surface area, mechanical strength etc. refer to table 1.
Embodiment 2
(1) synthesis of polyimides wet gel：
11mmol TAPM are taken, is substantially dissolved in the anhydrous DMSO of 100ml, 11mmol is added under stirring later
PMDA, in 40 DEG C of stirrings to being completely dissolved, solution viscosity increases, and forms polyamic acid, reaction system is fully transparent at this time；Then
(mass ratio of acetic anhydride and triethylamine is 1 to the mixed liquor of addition 80mmol acetic anhydrides and triethylamine:1) it, quickly stirs 5 minutes
Afterwards, ultrasonic deaeration 10 minutes；Acquired solution is finally formed into gel after 40 DEG C of standings, about 5h.
(2) the solvent displacement of gel：
The gel of formation is placed in the DMSO of 2 times of volumes, changes within every 12 hours a DMSO, after replacing 3 times, then with 2 times
The methanol of volume carries out solvent displacement, changes a methanol within every 5 hours, polyimides alcogel is obtained after 2 days.
(3) drying of wet gel：
Alcogel after displacement is dried into 6h by supercritical methanol at 245 DEG C, 9MPa, obtains clear polyimides gas
Gel.
Through characterizations such as BET isothermal adsorptions, SEM, contact angles, it was demonstrated that the transparent high-strength polyimides airsetting that the present embodiment obtains
There is glue nano-porous structure, other physical parameters such as specific surface area, mechanical strength of this polyimide aerogels etc. to refer to
Table 1.
Embodiment 3
(1) synthesis of polyimides wet gel：
12mmol TAPM are taken, is substantially dissolved in the anhydrous NMP of 200ml, 12.2mmol is added under stirring later
BTDA, in 80 DEG C of stirrings to being completely dissolved, solution viscosity increases, and forms polyamic acid, reaction system is fully transparent at this time；Then
(mass ratio of acetic anhydride and triethylamine is 1 to the mixed liquor of addition 100mmol acetic anhydrides and triethylamine:1), stirring after five minutes, surpasses
Sound deaeration 20 minutes；Acquired solution is finally formed into gel after 80 DEG C of standings, about 5h.
(2) the solvent displacement of gel：
The gel of formation is placed in the NMP of 3 times of volumes, changes within every 12 hours a NMP, after displacement 2 times, then with 3 times of bodies
Long-pending acetone carries out solvent displacement, changes an acetone within every 10 hours, polyimides ketone gel is obtained after 2 days.
(3) drying of wet gel：
Acetone gel after displacement is dried into 8h by supercritical carbon dioxide at 42 DEG C, 8MPa, obtains transparent gather
Acid imide aeroge.Through characterizations such as BET isothermal adsorptions, SEM, contact angles, it was demonstrated that the transparent high-strength polyamides that the present embodiment obtains is sub-
There is amine aeroge nano-porous structure, physical parameter such as specific surface area, mechanical strength of this polyimide aerogels etc. please join
It is shown in Table 1.
Embodiment 4
(1) synthesis of polyimides wet gel：
12mmol TAPM are taken, is substantially dissolved in the anhydrous NMP of 300ml, 12.6mmol is added under stirring later
PMDA, in 100 DEG C of stirrings to being completely dissolved, solution viscosity increases, and forms polyamic acid, reaction system is fully transparent at this time；With
(mass ratio of acetic anhydride and pyridine is 1 to the mixed liquor of addition 100mmol acetic anhydrides and/pyridine afterwards：1) it, quickly stirs 5 minutes
Afterwards, ultrasonic deaeration 20 minutes；Acquired solution is finally formed into gel after 100 DEG C of standings, about 5h.
(2) the solvent displacement of gel：
The gel of formation is placed in the NMP of 6 times of volumes, changes within every 12 hours a NMP, after displacement 2 times, then with 6 times of bodies
Long-pending acetone carries out solvent displacement, changes an acetone within every 5 hours, polyimides ketone gel is obtained after 2 days.
(3) drying of wet gel：
Ketone gel after displacement is dried into 8h by supercritical carbon dioxide at 42 DEG C, 10MPa, it is sub- to obtain transparent polyamides
Amine aeroge.
Through characterizations such as BET isothermal adsorptions, SEM, contact angles, it was demonstrated that the transparent high-strength polyimides airsetting that the present embodiment obtains
There is glue nano-porous structure, other physical parameters such as specific surface area, mechanical strength of this polyimide aerogels etc. to refer to
Table 1.
Embodiment 5
(1) synthesis of polyimides wet gel：
15mmol TAPM are taken, is substantially dissolved in the anhydrous NMP of 400ml, 15mmol is added under stirring later
BTDA, in 150 DEG C of stirrings to being completely dissolved, solution viscosity increases, and forms polyamic acid, reaction system is fully transparent at this time；With
(mass ratio of acetic anhydride and triethylamine is 1 to the mixed liquor of addition 100mmol acetic anhydrides and triethylamine afterwards：1), quickly 5 points of stirring
Zhong Hou, ultrasonic deaeration 20 minutes；Acquired solution is finally formed into gel after 150 DEG C of standings, about 4h.
(2) the solvent displacement of gel：
The gel of formation is placed in the NMP of 2 times of volumes, changes a NMP for every eight hours, after displacement 3 times, then with 2 times of volumes
Acetone carry out solvent displacement, change an acetone within every 10 hours, polyimides ketone gel obtained after 2 days.
(3) drying of wet gel：
Ketone gel after displacement is freeze-dried 6h in 15 DEG C, 15Pa, obtains clear polyimides aeroge.
Through characterizations such as BET isothermal adsorptions, SEM, contact angles, it was demonstrated that the transparent high-strength polyimides airsetting that the present embodiment obtains
There is glue nano-porous structure, other physical parameters such as specific surface area, mechanical strength of this polyimide aerogels etc. to refer to
Table 1.
Embodiment 6
(1) synthesis of polyimides wet gel：
14mmol TAPM are taken, is substantially dissolved in the anhydrous DMAc of 400ml, 14mmol is added under stirring later
BTDA, in 180 DEG C of stirrings to being completely dissolved, solution viscosity increases, and forms polyamic acid, reaction system is fully transparent at this time；With
(mass ratio of acetic anhydride and pyridine is 1 to the mixed liquor of addition 90mmol acetic anhydrides and pyridine afterwards：1) after, quickly stirring 8 minutes,
Ultrasonic deaeration 20 minutes；Acquired solution is finally formed into gel after 180 DEG C of standings, about 4h.
(2) the solvent displacement of gel：
The gel of formation is placed in the DMAc of 2 times of volumes, changes a DMAc for every eight hours, after displacement 3 times, then with 2 times of bodies
Long-pending acetone carries out solvent displacement, changes within every 10 hours an acetone, and polyimides ketone gel is obtained after replacing 4 times.
(3) drying of wet gel：
Ketone gel after displacement is freeze-dried 6h at 15 DEG C, 15Pa, obtains clear polyimides aeroge.
Through characterizations such as BET isothermal adsorptions, SEM, contact angles, it was demonstrated that the transparent high-strength polyimides airsetting that the present embodiment obtains
There is glue nano-porous structure, other physical parameters such as specific surface area, mechanical strength of this polyimide aerogels etc. to refer to
Table 1.
The polyimide aerogels provided various embodiments of the present invention are tested for the property, and test result is shown in Table 1：
The performance parameter of institute's polyimide aerogels in 1 embodiment 1-6 of table
The above, best specific implementation mode only of the invention, but scope of protection of the present invention is not limited thereto,
Any one skilled in the art in the technical scope disclosed by the present invention, the change or replacement that can be readily occurred in,
It should be covered by the protection scope of the present invention.
The content that description in the present invention is not described in detail belongs to the known technology of professional and technical personnel in the field.
Claims (10)
1. a kind of transparent, High Strength Polyimide aeroge preparation method, which is characterized in that include the following steps：
Step 1 reacts aromatic triamine monomer with dianhydride monomer dissolving in a solvent, until reaction system is completely saturating
It is bright；
Dehydrating agent is added in step 2, the transparent system obtained to step 1, stirs and deaeration, subsequent stand forms gel；
The gel is obtained polyimide aerogels by step 3 through solvent displacement, drying process.
2. the preparation method of polyimide aerogels according to claim 1, which is characterized in that in step 1, the fragrance
The molar ratio of amino and acid anhydrides is 1 in race's Triamine monomer and dianhydride monomer：1-1.05；The aromatic triamine monomer and diacid
Total mass concentration of the anhydride monomer in the solvent is 0.05~0.3g/mL.
3. the preparation method of polyimide aerogels according to claim 1 or 2, which is characterized in that in 0- in step 1
It is reacted at 180 DEG C.
4. the preparation method of polyimide aerogels according to claim 1, which is characterized in that fragrant described in step 1
Race's Triamine monomer is 4,4', 4 "-three amido triphenylmenthanes；The dianhydride monomer is 3,3 ', 4,4 '-benzophenone tetracarboxylics two
At least one of acid anhydride or pyromellitic dianhydride.
5. the preparation method of polyimide aerogels according to claim 1, which is characterized in that the solvent is N, N- bis-
At least one of methylformamide, DMAC N,N' dimethyl acetamide, dimethyl sulfoxide (DMSO) or N-Methyl pyrrolidone；Institute in step 2
It is pyridine, triethylamine, acetic anhydride, picoline, chloroacetic chloride, thionyl chloride, the halide of phosphorus or dicyclohexyl carbon to state dehydrating agent
At least one of acid imide.
6. the preparation method of polyimide aerogels according to claim 1 or 5, which is characterized in that taken off described in step 2
The quality of aqua is 1~10 times of dianhydride monomer quality described in step 1.
7. the preparation method of polyimide aerogels according to claim 1, which is characterized in that the deaeration described in step 2
Including：Deaeration is carried out by ultrasound or decompression method at 0-180 DEG C.
8. the preparation method of polyimide aerogels according to claim 1, which is characterized in that the solvent described in step 3
Displacement includes：
The gel is washed at least twice using solvent described in step 1, then uses methanol, ethyl alcohol or acetone displacement solidifying
Glue, displacement number is no less than twice；The drying, including：
It is freeze-dried 2-10h under conditions of temperature≤20 DEG C, vacuum degree≤500Pa；Or
It it is 40-250 DEG C in temperature, under conditions of pressure >=8MPa using carbon dioxide, ethyl alcohol or methanol as supercritical fluid
Carry out supercritical drying, drying time 2-10h.
9. the polyimide aerogels prepared by any one of claim 1-8 the methods.
10. polyimide aerogels according to claim 9, which is characterized in that young's modulus in compression be more than 10MPa, thoroughly
It crosses rate and is more than 50%.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483994A (en) * | 2019-08-01 | 2019-11-22 | 航天材料及工艺研究所 | A kind of silica enhancing polyimide aerogels micro mist and preparation method thereof |
| CN111440516A (en) * | 2020-04-16 | 2020-07-24 | 江苏斯迪克新材料科技股份有限公司 | Protective film with antibacterial function |
| CN116041950A (en) * | 2022-12-15 | 2023-05-02 | 武汉纺织大学 | Nanometer foam material and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110483994A (en) * | 2019-08-01 | 2019-11-22 | 航天材料及工艺研究所 | A kind of silica enhancing polyimide aerogels micro mist and preparation method thereof |
| CN110483994B (en) * | 2019-08-01 | 2022-01-04 | 航天材料及工艺研究所 | Silicon oxide reinforced polyimide aerogel micro powder and preparation method thereof |
| CN111440516A (en) * | 2020-04-16 | 2020-07-24 | 江苏斯迪克新材料科技股份有限公司 | Protective film with antibacterial function |
| CN116041950A (en) * | 2022-12-15 | 2023-05-02 | 武汉纺织大学 | Nanometer foam material and preparation method and application thereof |
| CN116041950B (en) * | 2022-12-15 | 2024-05-24 | 武汉纺织大学 | Nanometer foam material and preparation method and application thereof |
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| CN108384047B (en) | 2021-02-09 |
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