CN111234300B - Porous polyimide material and preparation method thereof - Google Patents
Porous polyimide material and preparation method thereof Download PDFInfo
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- CN111234300B CN111234300B CN202010235371.3A CN202010235371A CN111234300B CN 111234300 B CN111234300 B CN 111234300B CN 202010235371 A CN202010235371 A CN 202010235371A CN 111234300 B CN111234300 B CN 111234300B
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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
- C08G73/1003—Preparatory processes
- C08G73/1035—Preparatory processes from tetracarboxylic acids or derivatives and diisocyanates
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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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/05—Elimination by evaporation or heat degradation of a liquid phase
- C08J2201/0502—Elimination by evaporation or heat degradation of a liquid phase the liquid phase being organic
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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
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
- C08J2205/05—Open cells, i.e. more than 50% of the pores are open
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2379/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing nitrogen with or without oxygen, or carbon only, not provided for in groups C08J2361/00 - C08J2377/00
- C08J2379/04—Polycondensates having nitrogen-containing heterocyclic rings in the main chain; Polyhydrazides; Polyamide acids or similar polyimide precursors
- C08J2379/08—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Abstract
The invention discloses a porous polyimide material and a preparation method thereof. The preparation method comprises the following steps: s1, adding aromatic dianhydride into a polar solvent, then adding aliphatic alcohol, and heating to react until the aromatic dianhydride is transparent; then adding a catalyst, water and a foam stabilizer, and reacting to obtain a transparent solution A; s2, adding a solvent which is immiscible with the polar solvent in the solution A into the solution A, and dispersing to obtain a modified solution A; s3, adding isocyanate into the modified solution A to obtain a mixed solution; pressurizing the mixed solution, standing and foaming; and S4, reducing the pressure, and carrying out heat treatment on the foam obtained in the S3 to obtain the polyimide porous material. In the preparation process of the invention, the air entrapped in the mixing process can be discharged from the mixed liquid, and the defect of perforation is avoided.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a porous polyimide material and a preparation method thereof.
Background
The porous polyimide foam material is one of polyimide materials, has the performances of high flame retardance, high temperature resistance, open fire resistance and the like of the polyimide materials, is a high-performance material, does not generate harmful gas in the using process compared with other types of porous materials or foam plastics, and has wide density adjustable range and performance adjustable range, wherein the low-density material is widely applied as a heat insulation and noise reduction material abroad.
At present, the industrialized preparation methods of low-density porous polyimide materials (polyimide foam materials) mainly comprise two types, one type is a two-step method of firstly preparing polyester ammonium salt powder by using aromatic dianhydride and aromatic diamine as main raw materials and then further heating and foaming, and the foam material prepared by the method has good performance and wide performance adjusting range, but the preparation process has long route, large preparation difficulty, low foaming efficiency and high product cost; the other type is a one-step method which takes aromatic dianhydride and isocyanate as main raw materials, the product performance of the porous material prepared by the method is not as good as that of a two-step foam material with the same structure, but the porous material has the outstanding advantages which are not obtained by the two-step method, such as short preparation route, capability of preparing both soft foam materials and hard foam materials, easiness in industrialization and scale production and low product cost.
CN101402743A discloses a one-step method for preparing polyimide foam, which comprises mixing aromatic dianhydride, low molecular alcohol, catalyst, surfactant, etc. in proportion in a polar solvent to form a solution of foam precursor, mixing with isocyanate for foaming, and further performing microwave treatment and heat treatment to obtain polyimide foam.
CN104829835A discloses an improved one-step method for preparing polyimide foam, which firstly utilizes aromatic dianhydride to react with fatty alcohol in polar solvent, and mixes the derivative with foam stabilizer, catalyst and water and other auxiliary agents to obtain foaming component A, different from other prior arts, component B in the patent is the reaction product of polybasic aromatic anhydride and isocyanate. And reacting the white material with the black material, and further performing heat treatment to obtain the polyimide foam.
The foam prepared by the method is a soft foam material, and CN102127225A discloses a method for preparing hard foam by a one-step method, which mainly comprises the steps of injecting mixed liquid A and liquid B into a mold, sealing, shaping in microwave and imidizing. The mould in the method needs to resist high pressure, and the foam prepared by the method is easy to crack due to the discharge of a large amount of gas when the mould is opened.
CN106146840A discloses a preparation method of polyimide foam, which comprises placing a mold into a pressure vessel, mixing the mixed solution a and solution B, injecting into the mold, closing the pressure vessel, filling gas, maintaining pressure, taking out after a certain period of time, heating to remove the solvent and perform imidization.
The above reactions all have certain defects, and it is difficult to avoid introducing air into the system during the mixing process, thereby forming uneven-sized pores, or a perforation phenomenon, i.e., pores crossing the upper and lower surfaces appear on the foam sheet, which is often unacceptable to users, and this also adversely affects the properties of the foam and the image of the foam, affecting the foam yield.
Disclosure of Invention
In order to solve at least one technical problem, the invention provides a porous polyimide material and a preparation method thereof; in the preparation process of the invention, the air entrapped in the mixing process can be discharged from the mixed liquid, thereby avoiding the defects.
In order to achieve the purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a porous polyimide material, which comprises the following steps:
s1, adding aromatic dianhydride into a polar solvent, then adding aliphatic alcohol, and heating to react until the aromatic dianhydride is transparent; then adding a catalyst, water and a foam stabilizer, and reacting to obtain a transparent solution A;
s2, adding a solvent which is immiscible with the polar solvent in the solution A into the solution A, and dispersing to obtain a modified solution A;
s3, adding isocyanate into the modified solution A to obtain a mixed solution; pressurizing the mixed solution, standing and foaming;
and S4, reducing the pressure, and carrying out heat treatment on the foam obtained in the S3 to obtain the polyimide porous material.
Preferably, the aromatic dianhydride includes 3,3', 4' -benzophenone tetracarboxylic dianhydride, 1,2,4, 5-pyromellitic dianhydride, 3',4,4' -diphenyl ether tetracarboxylic dianhydride, bisphenol A type diether dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, and 2,3', 4' -biphenyl tetracarboxylic dianhydride.
Preferably, the polar solvent in S1 is dimethylformamide or dimethylacetamide.
Preferably, the fatty alcohol in S1 is ethanol.
Preferably, the catalyst in S1 is a tertiary amine-based catalyst or an organotin-based catalyst; such as triethanolamine.
The foam stabilizer is a silicone oil foam stabilizer, such as one of DC193, AK8805 and the like.
Preferably, the heating temperature in S1 is 50-100 ℃ and the time is 0.5-3 h.
Preferably, the mass concentration of the solution A in the S1 is 15-50%. The mass concentration of the solution A refers to the mass concentration of the aromatic dianhydride in the solution A. The dosage of each raw material in the solution A can be regulated according to the mass concentration routine of the solution A; the invention is not limited in this regard.
Preferably, the solvent immiscible with the polar solvent in the liquid A in the S2 is an alkane solvent; the addition amount is 10-100% of the mass of the solution A.
Preferably, the alkane solvent is one or a combination of more than two of n-heptane, n-hexane, isooctane and pentane.
Preferably, the method further comprises the following steps after the dispersion in the S2: standing for defoaming, and cooling to 15 ℃ to obtain modified liquid A.
Preferably, the isocyanate in S3 is a polyphenyl polymethylene polyisocyanate (PAPI), or a combination of one or both of toluene diisocyanate and 4,4' -diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate (PAPI).
Preferably, the adding amount of the isocyanate in S3 is 50-110% of the mass of the liquid A.
Preferably, in S3, the pressurization is to 0.1MPa to 20MPa; the standing foaming time is 0.5h-5h, and the temperature is 0 ℃ to 20 ℃.
Preferably, the temperature of the heat treatment in S4 is 100-300 ℃ and the time is 2-12 h.
Preferably, the heat treatment in S4 is performed in an oven.
Preferably, the average density of the polyimide porous material obtained in S4 is 15kg/m 3 -500kg/m 3 The aperture ratio is 90-99%.
The invention also provides a polyimide porous material obtained by the preparation method.
Preferably, the average density of the polyimide porous material is 15kg/m 3 -500kg/m 3 The aperture ratio is 90-99%.
Compared with the prior art, the preparation method of the polyimide porous material provided by the invention has the following advantages:
1) When the solution A is mixed with the immiscible solvent, a large amount of air can be mixed in through mechanical stirring, when the solution A is placed still, bubbles can float upwards due to low density, if the viscosity is low enough, the bubbles float upwards and do not gel, the pore diameter of the formed porous material is uniform, otherwise, the pore diameter of the bubbles is larger than that of CO when the hydrocarbon solvent or the gel is formed 2 The pores generated during the expansion cause the defect of large pores, thereby affecting the yield of products. Because of the specific preparation formula and process of the invention, the added alkane solvent is not soluble with dimethyl formamide and dimethyl acetamide, and the solvents are used as pore-foaming agents, the viscosity of the A liquid in the invention is small, the wrapped gas is easier to float before the system gels, and the alkane solvent is slowly separated from the foam basically during the gelling and is used as a gas flow station during the pressure relief; in the traditional preparation method, a part of bubbles always have high viscosity and fast gelation, so that the bubbles can not be discharged from the mixed solution, and the foam material with uniform cells and no macropores can not be prepared.
2) The density of the foam in the invention is convenient to adjust, the density of the final porous material can be adjusted by reaction pressure and the content of the added alkane solvent, and the density of the liquid A with the same concentration is lower when the content of the added hydrocarbon solvent is higher.
3) The polyimide porous material prepared by the preparation method has good temperature resistance and flame retardance.
Detailed Description
In order to more clearly illustrate the invention, the invention is further described below in connection with preferred embodiments. It is to be understood by persons skilled in the art that the following detailed description is illustrative and not restrictive, and is not to be taken as limiting the scope of the invention.
Example 1
The embodiment provides a preparation method of a polyimide porous material, which comprises the following steps:
a. and (3) synthesis of solution A: taking 4kg of dimethylformamide, adding 0.8kg of 3,3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), heating to 70 ℃, adding 100g of ethanol, stirring at constant temperature for 2.5h, then adding 80g of water, adding 6g of catalyst triethanolamine and 64g of silicone oil AK8805 after the system is clarified, uniformly stirring, cooling to room temperature to obtain solution A with the mass concentration of 15.8%, and filling the solution A into a solution A barrel.
b. Taking 100g of the solution A, adding 50g of n-hexane into the solution A, dispersing at a high speed, standing for 1h for defoaming, and cooling to 15 ℃ to obtain a modified solution A for later use.
c. 50g of PAPI (trademark PM 200) at the temperature of 15 ℃ is added into the modified solution A, and the mixture is uniformly mixed and poured into a pressure kettle. Then quickly pressurizing to 1MPa, and stably maintaining the pressure for 3 hours.
The reason for cooling to 15 ℃ in b and c is that the reaction rate is too fast at high temperature, and the gas release is slowed down due to the cooling to reduce the reaction rate.
d. Taking the prepared porous polyimide material out of the pressure kettle, then vacuumizing at 100 ℃ for 2h, vacuumizing at 150 ℃ for 2h, then heating to 250 ℃, and continuously drying for 3h.
The density of the obtained porous polyimide material is 150kg/m 3 The porosity was 92%, the oxygen index was 35%, and the compressive strength was 1.7MPa.
Example 2
The embodiment provides a preparation method of a polyimide porous material, which comprises the following steps:
a. and (3) synthesis of solution A: the solution A synthesized in example 1 was used.
b. And taking 100g of the solution A, adding 80g of n-hexane into the solution A, dispersing at a high speed, cooling to 15 ℃, standing for 0.5h, and defoaming to obtain a modified solution A for later use.
c. 50g of PAPI (trademark PM 200) at 15 ℃ is added into the modified solution A, and the mixture is uniformly mixed and poured into a pressure kettle. Then quickly pressurizing to 0.8MPa, and stably maintaining the pressure for 3h.
d. Taking the prepared porous polyimide material out of the pressure kettle, vacuumizing at 100 ℃ for 2h, vacuumizing at 150 ℃ for 2h, heating to 250 ℃, and continuously drying for 3h.
The density of the obtained porous polyimide material is 120kg/m 3 The porosity was 95%, the oxygen index was 35%, and the compressive strength was 1.3MPa.
Example 3
The embodiment provides a preparation method of a polyimide porous material, which comprises the following steps:
a. and (3) synthesis of solution A: taking 1kg of dimethylformamide, adding 0.872kg of pyromellitic dianhydride (PMDA) into the dimethylformamide, heating to 80 ℃, adding 150g of ethanol, stirring at constant temperature for 2.5h, then adding 40g of water, adding 3g of catalyst triethanolamine and 8805 g of silicone oil AK after the system is clarified, cooling to room temperature after stirring uniformly to obtain 41.6% solution A, and filling the solution A into a solution A barrel.
b. And (3) taking 100g of the liquid A, adding 40g of n-hexane into the liquid A, dispersing at a high speed, cooling to 10 ℃, standing for 0.5h, and defoaming to obtain a modified liquid A for later use.
c. 110g of PAPI (brand PM 200) at 10 ℃ is added into the modified solution A, and the mixture is uniformly mixed and poured into a pressure kettle. Then quickly pressurizing to 1.2MPa, and stably maintaining the pressure for 3 hours.
d. Taking the prepared porous polyimide material out of the pressure kettle, then vacuumizing for 2h at 100 ℃, vacuumizing for 2h at 150 ℃, then heating to 270 ℃, and continuously drying for 3h.
The density of the obtained porous polyimide material is 230kg/m 3 The aperture ratio is 97%, the oxygen index is 40%, and the compressive strength is 2.44MPa.
Example 4
The embodiment provides a preparation method of a polyimide porous material, which comprises the following steps:
a. and (3) synthesis of solution A: the solution a synthesized in example 3 was used;
b. taking 100g of the liquid A, adding 80g of n-hexane into the liquid A, dispersing at a high speed, cooling to 10 ℃, standing for 0.5h, and defoaming to obtain a modified liquid A for later use.
c. 100g of PAPI (trademark PM 200) at 10 ℃ is added into the modified solution A, and the mixture is uniformly mixed and poured into a pressure kettle. Then quickly pressurizing to 1.2MPa, and stably maintaining the pressure for 3h.
d. Taking the prepared porous polyimide material out of the pressure kettle, then vacuumizing for 2h at 100 ℃, vacuumizing for 2h at 150 ℃, then heating to 270 ℃, and continuously drying for 3h.
The density of the obtained porous polyimide material is 183kg/m 3 The open porosity was 98%, the oxygen index was 37%, and the compressive strength was 2.05MPa.
Example 5
The embodiment provides a preparation method of a polyimide porous material, which comprises the following steps:
a. and (3) synthesis of solution A: taking 2kg of dimethylformamide, adding 1.6kg of 3,3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) into the dimethylformamide, heating to 80 ℃, adding 200g of ethanol, stirring at constant temperature for 2.5h, then adding 100g of water, adding 12g of catalyst triethanolamine and 120g of silicone oil AK8805 after a system is clarified, uniformly stirring, cooling to room temperature to obtain a solution A with the concentration of 39.7%, and filling the solution A into a solution A barrel.
b. Taking 100g of the solution A, adding 50g of n-hexane into the solution A, dispersing at a high speed, standing for 1h for defoaming, and cooling to 15 ℃ to obtain a modified solution A for later use.
c. 80g of PAPI (trademark PM 200) at the temperature of 15 ℃ is added into the modified solution A, and the mixture is uniformly mixed and poured into a pressure kettle. Then quickly pressurizing to 5MPa, and stably maintaining the pressure for 3 hours.
d. Taking the prepared porous polyimide material out of the pressure kettle, vacuumizing at 100 ℃ for 2h, vacuumizing at 150 ℃ for 2h, heating to 250 ℃, and continuously drying for 3h.
The density of the obtained porous polyimide material is 380kg/m 3 The aperture ratio is 99%, the oxygen index is 45%, and the compressive strength is 8.05MPa.
Example 6
The embodiment provides a preparation method of a polyimide porous material, which comprises the following steps:
a. and (3) synthesis of solution A: the solution a described in example 5 was used.
b. And adding 80g of n-hexane into 100g of the solution A, dispersing at a high speed, standing for 1h for defoaming, and cooling to 15 ℃ to obtain a modified material A for later use.
c. 100g of PAPI (trademark PM 200) at 15 ℃ is added into the modified solution A, and the mixture is uniformly mixed and poured into a pressure kettle. Then quickly pressurizing to 5MPa, and stably maintaining the pressure for 3h.
d. Taking the prepared porous polyimide material out of the pressure kettle, vacuumizing at 100 ℃ for 2h, vacuumizing at 150 ℃ for 2h, heating to 250 ℃, and continuously drying for 3h.
The density of the obtained porous polyimide material is 310kg/m 3 The porosity was 98%, the oxygen index was 43%, and the compressive strength was 7.52MPa.
Example 7
The embodiment provides a preparation method of a polyimide porous material, which comprises the following steps:
a. and (3) synthesis of solution A: taking 2kg of dimethylformamide, adding 1kg of pyromellitic dianhydride (PMDA) into the dimethylformamide, heating to 80 ℃, adding 150g of ethanol, stirring at constant temperature for 2.5h, then adding 80g of water, adding 6g of catalyst triethanolamine and 8805 g of silicone oil after a system is clarified, cooling to room temperature after uniform stirring to obtain a liquid A with the concentration of 30.3%, and filling the liquid A into a liquid A barrel.
b. And adding 40g of pentane into 100g of the solution A, dispersing at a high speed, cooling to 10 ℃, standing for 0.5h, and defoaming to obtain modified solution A for later use.
c. 80g of PAPI (trademark PM 200) with the temperature of 10 ℃ is poured into the pressure kettle after being evenly mixed at the temperature of the modified A liquid. Then quickly pressurizing to 5MPa, and stably maintaining the pressure for 3h.
d. Taking the prepared porous polyimide material out of the pressure kettle, vacuumizing at 100 ℃ for 2h, vacuumizing at 150 ℃ for 2h, heating to 270 ℃, and continuously drying for 3h.
The density of the obtained porous polyimide material is 260kg/m 3 The porosity was 97%, the oxygen index was 40%, and the compressive strength was 5.47MPa.
It should be understood that the above-mentioned embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention, and it will be obvious to those skilled in the art that other variations or modifications may be made on the basis of the above description, and all embodiments may not be exhaustive, and all obvious variations or modifications may be included within the scope of the present invention.
Claims (14)
1. The preparation method of the porous polyimide material is characterized by comprising the following steps of:
s1, adding aromatic dianhydride into a polar solvent, then adding aliphatic alcohol, and heating to react until the mixture is transparent; adding a catalyst, water and a foam stabilizer, and reacting to obtain a transparent solution A; the polar solvent is dimethylformamide or dimethylacetamide, and the fatty alcohol is ethanol;
s2, adding an alkane solvent which is immiscible with the polar solvent in the solution A into the solution A, and dispersing to obtain a modified solution A;
s3, adding isocyanate into the modified solution A to obtain a mixed solution; pressurizing the mixed solution, standing and foaming;
the isocyanate is polyphenyl polymethylene polyisocyanate, or the combination of one or two of toluene diisocyanate and 4,4' -diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate;
and S4, reducing the pressure, and carrying out heat treatment on the foam obtained in the S3 to obtain the polyimide porous material.
2. The method according to claim 1, wherein the aromatic dianhydride comprises 3,3', 4' -benzophenone tetracarboxylic dianhydride, 1,2,4, 5-pyromellitic dianhydride, 3',4,4' -diphenyl ether tetracarboxylic dianhydride, bisphenol A type diether dianhydride, 3', 4' -biphenyl tetracarboxylic dianhydride, and 2,3', 4' -biphenyl tetracarboxylic dianhydride.
3. The production method according to claim 1, wherein the catalyst in S1 is a tertiary amine-based catalyst or an organotin-based catalyst;
the foam stabilizer is a silicone oil foam stabilizer, including DC193 or AK8805.
4. The method according to claim 1, wherein the heating in S1 is performed at a temperature of 50 ℃ to 100 ℃ for 0.5h to 3h.
5. The preparation method according to claim 1, wherein the mass concentration of the solution A in S1 is 15-50%.
6. The preparation method of claim 1, wherein the addition amount of the alkane solvent immiscible with the polar solvent in the solution A in the S2 is 10-100% of the mass of the solution A.
7. The method according to claim 1, wherein the alkane solvent is one or a combination of two or more selected from the group consisting of n-heptane, n-hexane, isooctane and pentane.
8. The method of claim 1, wherein the step of dispersing in S2 further comprises: standing for defoaming, and cooling to 15 ℃ to obtain modified liquid A.
9. The preparation method of claim 1, wherein the amount of the isocyanate added in S3 is 50 to 110% by mass of the solution a.
10. The production method according to claim 1, wherein in S3, the pressurization is pressurization to 0.1MPa to 20MPa; the standing and foaming time is 0.5-5 h, and the temperature is 0-20 ℃.
11. The method according to claim 1, wherein the heat treatment in S4 is performed at a temperature of 100 ℃ to 300 ℃ for 2h to 12h.
12. The method according to claim 1, wherein the average density of the porous polyimide material obtained in S4 is 15kg/m 3 -500 kg/m 3 The aperture ratio is 90-99%.
13. A polyimide porous material obtained by the production method described in any one of claims 1 to 12.
14. The porous polyimide material according to claim 13, wherein the porous polyimide material has an average density of 15kg/m 3 -500 kg/m 3 The aperture ratio is 90-99%.
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| CN103254565A (en) * | 2013-06-04 | 2013-08-21 | 上海海事大学 | Preparation method of toughened modified phenolic foams |
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| CN107286343A (en) * | 2016-04-05 | 2017-10-24 | 中国科学院理化技术研究所 | A kind of Halogen composite flame-proof Polyimide foams and preparation method thereof |
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