CN112358649A - Polyimide foam/aerogel composite material and preparation method thereof - Google Patents

Polyimide foam/aerogel composite material and preparation method thereof Download PDF

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CN112358649A
CN112358649A CN202011127707.0A CN202011127707A CN112358649A CN 112358649 A CN112358649 A CN 112358649A CN 202011127707 A CN202011127707 A CN 202011127707A CN 112358649 A CN112358649 A CN 112358649A
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polyimide foam
polyimide
foam
composite material
solution
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CN112358649B (en
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马晶晶
赵一搏
吴文敬
酒永斌
曹巍
滕冲
刘凯
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Aerospace Research Institute of Materials and Processing Technology
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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
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C08J9/42—Impregnation with macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/113—Silicon oxides; Hydrates thereof
    • C01B33/12—Silica; Hydrates thereof, e.g. lepidoic silicic acid
    • C01B33/14—Colloidal silica, e.g. dispersions, gels, sols
    • C01B33/157—After-treatment of gels
    • C01B33/158—Purification; Drying; Dehydrating
    • C01B33/1585—Dehydration into aerogels
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/36—After-treatment
    • C08J9/40—Impregnation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
    • C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
    • C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors

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  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
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  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)

Abstract

The invention provides a polyimide foam/aerogel composite material and a preparation method thereof, wherein the preparation method comprises the following steps: soaking the polyimide foam in a polyimide precursor solution, taking out the polyimide foam, and then spin-drying the polyimide foam to obtain polyimide foam dip-coated with the polyimide precursor solution; vacuum pouring a silicon dioxide sol solution into the dried polyimide foam, and aging and hydrophobizing to obtain a wet gel filled polyimide foam composite material; then the mixture is subjected to solvent replacement, drying and high-temperature treatment to obtain the product with the density of 30-200 kg/m3And a polyimide foam/silica aerogel composite material having a thermal conductivity of 0.0175 to 0.036W/m.K. In the invention, after the membrane pretreatment, the aerogel collagen is subjected toThe composite material is filled in the polyimide foam, so that the problems of weak binding force with a polyimide foam film, easy falling off from a composite foam system and powder falling are solved, and the heat conductivity and the density of the composite material are effectively reduced while the sound absorption performance of the open-cell material is ensured.

Description

Polyimide foam/aerogel composite material and preparation method thereof
Technical Field
The invention belongs to the technical field of light heat-insulating materials, and particularly relates to a polyimide foam/aerogel composite material and a preparation method thereof.
Background
Polyimide (PI) foam plastic has excellent performances of high and low temperature resistance of-250-450 ℃, light weight, sound absorption and noise reduction, radiation resistance, flame resistance, low smoke generation, harmless gas release and the like, and becomes a key material for heat insulation, interlayer, sound insulation, shock resistance, insulation and the like in advanced fields of aerospace, national defense, construction, microelectronics and the like; wherein the soft open-cell polyimide foam such as solimide series foam is widely applied to the field of heat insulation and sound absorption of various foreign ships. However, the problem of random movement of gas molecules and increase of gas convection heat transfer under the condition of large temperature difference is also brought about by the high open-cell ratio of the flexible open-cell foam, and the thermal conductivity of the foam is high and is usually more than or equal to 0.036W/mK, which limits the application of the foam in the technical field of heat insulation.
Aerogel is a porous nano material, and is the lightest solid material with the best heat insulation performance in the world at present. The silica aerogel has a high specific surface area (400-1500 m)2A/g), a high porosity (80-99.8%), a low density (0.003-0.6 g/cm)3) And low thermal conductivity (0.013-0.038W/m.K), and the most typical aerogel material is a silicon dioxide aerogel material, the porous material has small pore diameter and average pore diameter of 20-50 nm, has excellent heat preservation performance and normal-temperature thermal conductivity of 0.011-0.021W/m.K, and simultaneously, as the main component is SiO2And has excellent heat resistance. However, the aerogel is large in brittleness and easy to separate when used alone, cannot be directly used as a heat insulation material, and is often required to be compounded with other materials for use. With the continuous reduction of preparation cost, the aerogel/fiber composite material has been widely applied to the field of high-performance heat insulation materials, and the typical composite material is formed by compounding aerogel and fiber/fiber felt, such as rock wool and glass fiberCeramic fibers, etc., to produce aerogel blankets, panels, or other forms of aerogel composites. CN111304910A, a composite of ceramic fiber mat compounded silica aerogel, CN109336545A discloses a fiber/aerogel composite, which has good heat insulating properties and excellent high and low temperature service properties.
However, the above materials have two main problems, high density and easy powder falling, and the density of the current aerogel/fiber felt composite material is generally more than 200kg/m3It is inconvenient to use and cut.
The chinese patent CN109535714A reports a method for preparing aerogel composite polyimide foam by mixing aerogel materials with polyimide precursor foaming matrix to improve the temperature resistance of foam, however, in the process of mixing aerogel materials with polymer, the phenomena of aerogel hole blockage and thermal insulation failure are easily generated, and meanwhile, the foam foaming process is affected by aerogel particles, the uniformity of cells is reduced and the cells are easily cracked. Chinese patents CN110183198A, CN109265734A and other patents report methods for filling silica aerogel into polyimide foam in situ, and the methods are easy to prepare, however, since silica aerogel belongs to inorganic materials and is light in weight, the silica aerogel is weak in bonding force with a polyimide foam film, and is easy to fall off from a composite foam system, the powder falling phenomenon occurs, and the use of the composite material is influenced.
Disclosure of Invention
In order to overcome the defects in the prior art, the inventor of the invention has conducted intensive research and provides a polyimide foam/aerogel composite material and a preparation method thereof.
The technical scheme provided by the invention is as follows:
in a first aspect, a method of preparing a polyimide foam/aerogel composite, comprises:
step (1), soaking polyimide foam in a polyimide precursor solution, taking out the polyimide foam, and then spin-drying the polyimide foam to obtain polyimide foam dip-coated with the polyimide precursor solution;
step (2), vacuum pouring a silicon dioxide sol solution into the spin-dried polyimide foam, and carrying out aging and hydrophobization treatment to obtain a wet gel filled polyimide foam composite material;
and (3) carrying out solvent replacement and drying on the wet gel filled polyimide foam composite material, and then treating for 0.5-4 h at 250-400 ℃ to obtain the polyimide foam/silicon dioxide aerogel composite material.
In a second aspect, the polyimide foam/aerogel composite material is prepared by the preparation method of the polyimide foam/aerogel composite material in the first aspect, and the density of the polyimide foam/aerogel composite material is 30-200 kg/m3The thermal conductivity is 0.0175 to 0.036W/mK.
According to the polyimide foam/aerogel composite material and the preparation method thereof provided by the invention, the following beneficial effects are achieved:
(1) according to the invention, a polyimide precursor solution is used as an adhesive to be positioned between polyimide foam and aerogel, and finally used as an adhesive to improve the bonding force between aerogel particles and the polyimide foam, a layer of polyimide film is designed on the surface of silica aerogel generated in situ, the polyimide film is used as a continuous phase between the polyimide foam film and the silica aerogel, and the silica aerogel and the polyimide foam film are well bonded together by utilizing the same polarity between the same chemical structures, so that a composite foam material with good interface bonding is obtained; finally, the heat conductivity coefficient of the polyimide foam is effectively reduced, the heat insulation performance is improved, and the problem that silicon dioxide aerogel powder is easy to fall is solved;
(2) according to the invention, the silicon dioxide aerogel is filled into the soft open-cell polyimide foam cells in situ, so that the defects of high density and easy powder falling of the fibrofelt/aerogel composite material are overcome, the defect of easy powder falling of the traditional foam/aerogel composite material is also overcome, and the prepared composite material is ensured to have good heat-insulating property;
(3) the method adopted by the invention can control the content of aerogel in the foam system by controlling the concentration of the precursor solution, so as to control the final density of the composite foam, and the prepared foam composite material has the advantages of excellent comprehensive performance, excellent heat insulation performance and good construction performance.
Detailed Description
The features and advantages of the present invention will become more apparent and appreciated from the following detailed description of the invention.
The invention provides a polyimide foam/silicon dioxide aerogel composite material, which comprises the following components in percentage by weight:
step (1), soaking polyimide foam in a polyimide precursor solution, taking out the polyimide foam, and drying the polyimide foam by spin-drying to obtain polyimide foam dip-coated with the polyimide precursor solution;
step (2), vacuum pouring a silicon dioxide sol solution into the spin-dried polyimide foam, and carrying out aging and hydrophobization treatment to obtain a wet gel filled polyimide foam composite material;
and (3) carrying out solvent replacement and drying on the wet gel filled polyimide foam composite material, and then treating for 0.5-4 h at 250-400 ℃ to obtain the polyimide foam/silicon dioxide aerogel composite material.
In a preferred embodiment of the present invention, in the step (1), the polyimide foam has a density of 6 to 100kg/m3Preferably 6 to 20kg/m3(ii) a The aperture ratio is 90 to 99 percent, preferably 95 to 99 percent.
In a preferred embodiment of the present invention, in step (1), the polyimide precursor solution for dip-coating the polyimide foam is at least one of a polyamic acid solution or a polyester ammonium salt solution, and the mass concentration of the polyimide precursor solution is 5 to 40%; the polyanhydride and polyamine raw materials used by the polyimide precursor solution and the polyimide foam are the same.
Further, the aromatic dianhydride used in the polyimide precursor solution is selected from any one or a combination of 1,2,4, 5-pyromellitic dianhydride, 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride, 3,3',4,4' -benzophenone tetracarboxylic dianhydride, bisphenol a type diphenyl ether dianhydride, 3,3',4,4' -biphenyl tetracarboxylic dianhydride, or 2,3,3',4' -biphenyl tetracarboxylic dianhydride.
Further, the aromatic diamine used in the polyimide precursor solution is selected from any one of meta-phenylenediamine (m-PDA), 4' -diaminodiphenyl ether (4,4' -ODA), 3,4' -diaminodiphenyl ether (3, 4' -ODA), 4' -diaminobenzophenone (4,4' -DABP), 3, 4-diaminobenzophenone (3, 4-DABP), 4' -diaminodiphenyl sulfone (4,4' -DDS), or 4,4' -diaminodiphenyl Methane (MDA), or a combination thereof.
In a preferred embodiment of the present invention, in the step (1), the polyimide precursor solution is prepared as follows: reacting aromatic dianhydride in a tetrahydrofuran/methanol mixed solvent for 3-6 h, wherein the mass concentration of the solution is 5% -40%, then adding aromatic diamine, and continuously reacting for 3-5 h to form a uniform solution, wherein the molar ratio of the aromatic dianhydride to the aromatic diamine is 1:1 to 2.
In a preferred embodiment of the present invention, the specific implementation manner of the step (1) comprises: soaking the whole polyimide foam in the polyimide precursor solution, taking out the polyimide foam after the polyimide precursor solution is completely filled with the foam, and throwing off the polyimide precursor solution on a centrifugal machine, wherein the whole process is carried out in a normal-temperature environment.
In a preferred embodiment of the present invention, in the step (2), the silica sol solution is prepared as follows: mixing ethyl orthosilicate, water and ethanol according to a molar ratio of 1:1.2: 4-60, adding (such as 0.01M) dilute hydrochloric acid solution into the mixture, and uniformly stirring the mixture to obtain a sol precursor; then adding (such as 0.1M) dilute ammonia solution into the mixed solution to control the pH value of the system to be 7-8, and obtaining the silica sol solution.
In a preferred embodiment of the present invention, in the step (2), the vacuum degree of the vacuum casting is-0.01 MPa to-0.1 MPa; the aging temperature is between room temperature and 60 ℃, and the aging time is 24-48 h; the hydrophobizing agent adopted in the hydrophobizing treatment is trimethyl chlorosilane, and the mass concentration of the hydrophobizing agent is 5-20%.
In a preferred embodiment of the present invention, in the step (3), the solvent used for the solvent replacement is cyclohexane, and the number of replacements is not less than two;
the drying is normal pressure drying, the temperature for normal pressure drying is room temperature-60 ℃, and the drying time is about 3-7 days.
According to a second aspect of the present invention, there is provided a polyimide foam/aerogel composite material prepared by the method for preparing the polyimide foam/aerogel composite material according to the first aspect, wherein the density of the polyimide foam/aerogel composite material is 30 to 200kg/m3The thermal conductivity is 0.0175-0.036W/m.K, the foam material has good strength and is not easy to break, and the polyimide precursor solution soaked into the pores can play a good interface bonding role between the silica aerogel and the foam, so that the problems of weak bonding force and easy powder falling between the directly filled silica aerogel and the polyimide foam film are solved.
Examples
Example 1
Polyimide foam: 3,3',4,4' -benzophenone tetracarboxylic dianhydride/4, 4' -diaminodiphenyl ether is used as a main raw material, and the Tg: 255 ℃, density: 7kg/m3The coefficient of thermal conductivity: 0.043W/m.K, and the aperture ratio is 98 percent.
(1) Reacting 64.4g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride in 800g of tetrahydrofuran/100 g of methanol mixed solvent at 60 ℃ for 4h, then adding 40g of 4,4' -diaminodiphenyl ether to continue reacting for 3h to form uniform polyester ammonium salt solution for later use;
(2) soaking polyimide foam of 20cm multiplied by 2.5cm in a polyester ammonium salt solution, then drying for 3min by a drying machine, and taking out for later use;
(3) uniformly mixing ethyl orthosilicate, water and ethanol according to a molar ratio of 1:1.2:5, adding a certain amount of 0.01M dilute hydrochloric acid solution, adjusting the pH value of the solution to be 2, and uniformly stirring to obtain sol precursor sol; then adding a certain amount of 0.1M ammonia water solution, and adjusting the pH value of the system to 7 to obtain silicon dioxide sol;
(4) placing the treated polyimide foam in a container, and performing vacuum infusion on silica sol by adopting a vacuum degree of-0.02 MPa; standing at room temperature for 24h, continuing aging at 40 ℃ for 48h, and then performing hydrophobization treatment by adopting trimethylchlorosilane with the mass fraction of 15%; after 2 times of cyclohexane replacement, drying for about 7 days at normal temperature and normal pressure; and then treating the mixture for 3 hours at a high temperature of 250 ℃ in an oven to obtain the composite foam material.
The aerogel-filled composite polyimide foam composite obtained in this example had a density of 155kg/m3The normal temperature thermal conductivity is 0.019W/m.K.
Example 2
Polyimide foam: 3,3',4,4' -benzophenone tetracarboxylic dianhydride/4, 4' -diaminodiphenyl ether is used as a main raw material, and the Tg: 255 ℃, density: 7kg/m3The coefficient of thermal conductivity: 0.043W/m.K, and the aperture ratio is 98 percent.
(1) Reacting 64.4g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride in 800g of tetrahydrofuran/100 g of methanol mixed solvent at 60 ℃ for 4h, then adding 40g of 4,4' -diaminodiphenyl ether to continue reacting for 3h to form uniform polyester ammonium salt solution for later use;
(2) soaking polyimide foam of 20cm multiplied by 2.5cm in a polyester ammonium salt solution, then drying for 3min by a drying machine, and taking out for later use;
(3) uniformly mixing ethyl orthosilicate, water and ethanol according to a molar ratio of 1:1.2:6.5, adding a certain amount of dilute hydrochloric acid solution with the concentration of 0.01M, adjusting the pH value of the solution to be, and uniformly stirring to obtain sol precursor sol; then adding a certain amount of 0.1M ammonia water solution, and adjusting the pH value of the system to 7 to obtain silicon dioxide sol;
(4) placing the treated polyimide foam in a container, and performing vacuum infusion on silica sol by adopting a vacuum degree of-0.04 MPa; standing at room temperature for 24h, continuing aging at 40 ℃ for 48h, and then performing hydrophobization treatment by adopting trimethylchlorosilane with the mass fraction of 15%; after 2 times of cyclohexane replacement, drying for about 7 days at normal temperature and normal pressure; and then treating the mixture for 2 hours at a high temperature of 250 ℃ in an oven to obtain the composite foam material.
The aerogel-filled composite polyimide foam composite obtained in this example had a density of 105kg/m3The thermal conductivity at room temperature was 0.0175W/mK.
Example 3
Polyimide foam: 3,3',4,4' -benzophenone tetracarboxylic dianhydride/4, 4' -diaminodiphenyl ether is used as a main raw material, and the Tg: 255 ℃, density: 15kg/m3The coefficient of thermal conductivity: 0.038W/mK, and an aperture ratio of 99%.
(1) Reacting 64.4g of 3,3',4,4' -benzophenone tetracarboxylic dianhydride in 800g of tetrahydrofuran/100 g of methanol mixed solvent at 60 ℃ for 4h, then adding 40g of 4,4' -diaminodiphenyl ether to continue reacting for 3h to form uniform polyester ammonium salt solution for later use;
(2) soaking polyimide foam of 20cm multiplied by 2.5cm in a polyester ammonium salt solution, then drying for 3min by a drying machine, and taking out for later use;
(3) uniformly mixing ethyl orthosilicate, water and ethanol according to a molar ratio of 1:1.2:10, adding a certain amount of 0.01M dilute hydrochloric acid solution, adjusting the pH value of the solution to be 2, and uniformly stirring to obtain sol precursor sol; then adding a certain amount of 0.1M ammonia water solution, and adjusting the pH value of the system to 7 to obtain silicon dioxide sol;
(4) placing the treated polyimide foam in a container, and performing vacuum infusion on silica sol by adopting a vacuum degree of-0.04 MPa; standing at room temperature for 24h, continuing aging at 40 ℃ for 48h, and then performing hydrophobization treatment by adopting trimethylchlorosilane with the mass fraction of 15%; after 2 times of cyclohexane replacement, drying for about 7 days at normal temperature and normal pressure; and then treating the mixture for 2 hours at a high temperature of 250 ℃ in an oven to obtain the composite foam material.
The density of the aerogel-filled composite polyimide foam composite obtained in this example was 95kg/m3The thermal conductivity at room temperature was 0.022W/mK.
Example 4
Polyimide foam: the preparation method is characterized in that 2,3,3',4' -biphenyl tetracarboxylic dianhydride/p-phenylenediamine is used as a main raw material, the Tg of the material is 410 ℃, and the density: 8kg/m3The coefficient of thermal conductivity: 0.045W/m.K, and the aperture ratio is 99 percent.
(1) Reacting 58.8g of 2,3,3',4' -biphenyltetracarboxylic dianhydride in a mixed solvent of 700g of tetrahydrofuran and 100g of methanol at 60 ℃ for 4h, adding 40g of p-phenylenediamine, and continuously reacting for 3h to form a uniform polyesterammonium salt solution for later use;
(2) soaking polyimide foam of 20cm multiplied by 2.5cm in a polyester ammonium salt solution, then drying for 3min by a drying machine, and taking out for later use;
(3) uniformly mixing ethyl orthosilicate, water and ethanol according to a molar ratio of 1:1.2:30, adding a certain amount of 0.01M dilute hydrochloric acid solution, adjusting the pH value of the solution to be 2, and uniformly stirring to obtain sol precursor sol; then adding a certain amount of 0.1M ammonia water solution, and adjusting the pH value of the system to 7 to obtain silicon dioxide sol;
(4) placing the treated soft polyimide foam into a mold, and performing vacuum infusion on silicon dioxide sol by adopting a vacuum degree of-0.05 MPa; standing at room temperature for 24h, continuing aging at 40 ℃ for 48h, and then performing hydrophobization treatment by adopting trimethylchlorosilane with the mass fraction of 15%; after 2 times of cyclohexane replacement, drying for about 7 days at normal temperature and normal pressure; then the mixture is treated for 2 hours at a high temperature of 230 ℃ in an oven to obtain the composite foam material.
The aerogel-filled composite polyimide foam composite obtained in this example had a density of 56kg/m3The thermal conductivity at room temperature was 0.030W/mK.
Example 5
Polyimide foam: using 2,3,3',4' -biphenyl tetracid dianhydride/p-phenylenediamine as main raw materialMaterial, material Tg:410 ℃, density: 8kg/m3The coefficient of thermal conductivity: 0.045W/m.K, and the aperture ratio is 99 percent.
(1) Reacting 58.8g of 2,3,3',4' -biphenyltetracarboxylic dianhydride in a mixed solvent of 700g of tetrahydrofuran and 100g of methanol at 60 ℃ for 4h, adding 40g of p-phenylenediamine, and continuously reacting for 3h to form a uniform polyesterammonium salt solution for later use;
(2) soaking polyimide foam of 20cm multiplied by 2.5cm in a polyester ammonium salt solution, then drying for 3min by a drying machine, and taking out for later use;
(3) uniformly mixing ethyl orthosilicate, water and ethanol according to a molar ratio of 1:1.2:50, adding a certain amount of 0.01M dilute hydrochloric acid solution, adjusting the pH value of the solution to be 2, and uniformly stirring to obtain sol precursor sol; then adding a certain amount of 0.1M ammonia water solution, and adjusting the pH value of the system to 7 to obtain silicon dioxide sol;
(4) placing the treated soft polyimide foam into a mold, and performing vacuum infusion on silicon dioxide sol by adopting a vacuum degree of-0.1 MPa; standing at room temperature for 24h, continuing aging at 40 ℃ for 48h, and then performing hydrophobization treatment by adopting trimethylchlorosilane with the mass fraction of 15%; after 2 times of cyclohexane replacement, drying for about 7 days at normal temperature and normal pressure; then the mixture is treated for 2 hours at a high temperature of 230 ℃ in an oven to obtain the composite foam material.
The aerogel-filled composite polyimide foam composite obtained in this example had a density of 25kg/m3The thermal conductivity at room temperature was 0.033W/m.K.
The invention has been described in detail with reference to specific embodiments and illustrative examples, but the description is not intended to be construed in a limiting sense. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Those skilled in the art will appreciate that those matters not described in detail in the present specification are well known in the art.

Claims (10)

1. A preparation method of a polyimide foam/aerogel composite material is characterized by comprising the following steps:
step (1), soaking polyimide foam in a polyimide precursor solution, taking out the polyimide foam, and then spin-drying the polyimide foam to obtain polyimide foam dip-coated with the polyimide precursor solution;
step (2), vacuum pouring a silicon dioxide sol solution into the spin-dried polyimide foam, and carrying out aging and hydrophobization treatment to obtain a wet gel filled polyimide foam composite material;
and (3) carrying out solvent replacement and drying on the wet gel filled polyimide foam composite material, and then treating for 0.5-4 h at 250-400 ℃ to obtain the polyimide foam/silicon dioxide aerogel composite material.
2. The method according to claim 1, wherein in the step (1), the density of the polyimide foam is 6 to 100kg/m3(ii) a The aperture ratio is 90-99%.
3. The preparation method according to claim 1, wherein in the step (1), the polyimide precursor solution for dip-coating the polyimide foam is at least one of a polyamic acid solution or a polyester ammonium salt solution, and the mass concentration of the polyimide precursor solution is 5-40%;
the polyanhydride and polyamine raw materials used by the polyimide precursor solution and the polyimide foam are the same.
4. The method according to claim 3, wherein the polyanhydride used in the polyimide precursor solution is an aromatic dianhydride selected from any one of 1,2,4, 5-pyromellitic dianhydride, 3,3',4,4' -diphenyl ether tetracarboxylic dianhydride, 3,3',4,4' -benzophenone tetracarboxylic dianhydride, bisphenol A-type diphenyl ether dianhydride, 3,3',4,4' -biphenyl tetracarboxylic dianhydride, and 2,3,3',4' -biphenyl tetracarboxylic dianhydride, or a combination thereof.
5. The method according to claim 3, wherein the polyamine used in the polyimide precursor solution is an aromatic diamine selected from any one of or a combination of m-phenylenediamine, 4' -diaminodiphenyl ether, 3,4' -diaminodiphenyl ether, 4' -diaminobenzophenone, 3, 4-diaminobenzophenone, 4' -diaminodiphenyl sulfone, and 4,4' -diaminodiphenyl methane.
6. The method according to claim 3, wherein the polyimide precursor solution is prepared as follows: reacting aromatic dianhydride in a tetrahydrofuran/methanol mixed solvent for 3-6 h, wherein the mass concentration of the solution is 5% -40%, and then adding aromatic diamine to continuously react for 3-5 h to form a uniform solution; preferably, the molar ratio of the aromatic dianhydride to the aromatic diamine is 1:1 to 2.
7. The method according to claim 1, wherein the silica sol solution is prepared as follows in the step (2): mixing ethyl orthosilicate, water and ethanol according to a molar ratio of 1:1.2: 4-60, adding a dilute hydrochloric acid solution, and uniformly stirring to obtain a sol precursor; then adding a dilute ammonia solution to control the pH value of the system to be 7-8, and obtaining the silica sol solution.
8. The production method according to claim 1, wherein in the step (2), the vacuum degree of the vacuum casting is from-0.01 MPa to-0.1 MPa; and/or
The aging temperature of the aging is room temperature-60 ℃, and the aging time is 24-48 h; and/or
The hydrophobizing agent adopted in the hydrophobizing treatment is trimethyl chlorosilane, and the mass concentration of the hydrophobizing agent is 5-20%.
9. The production method according to claim 1, wherein in the step (3), the solvent used for the solvent substitution is cyclohexane, and the number of the substitution is not less than two; and/or
The drying is normal pressure drying, the temperature for normal pressure drying is room temperature-60 ℃, and the drying time is 3-7 days.
10. A polyimide foam/aerogel composite material, characterized by being prepared by the method for preparing a polyimide foam/aerogel composite material as claimed in any one of claims 1 to 9, wherein the density of the polyimide foam/aerogel composite material is 30 to 200kg/m3The thermal conductivity is 0.0175 to 0.036W/mK.
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CN113943463A (en) * 2021-12-02 2022-01-18 惠州优比贝柠科技股份有限公司 Closed bubble type structural pipe and preparation method thereof
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