CN111234300A - Porous polyimide material and preparation method thereof - Google Patents
Porous polyimide material and preparation method thereof Download PDFInfo
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- CN111234300A CN111234300A CN202010235371.3A CN202010235371A CN111234300A CN 111234300 A CN111234300 A CN 111234300A CN 202010235371 A CN202010235371 A CN 202010235371A CN 111234300 A CN111234300 A CN 111234300A
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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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
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 mixture is transparent; adding a catalyst, water and a foam stabilizer, and reacting to obtain a transparent solution A; s2, adding a solvent 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, and standing for 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 is to mix aromatic dianhydride, low molecular alcohol, catalyst, surfactant, etc. in proportion in a polar solvent to form a solution of foam precursor, then mix with isocyanate for foaming, and further perform microwave treatment and heat treatment to obtain polyimide foam.
CN104829835A discloses an improved one-step method for preparing polyimide foam, which comprises reacting aromatic dianhydride with aliphatic alcohol in polar solvent, mixing the derivative with foam stabilizer, catalyst and water to obtain foaming component a, wherein component B 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 in the method is a soft foam material, and CN102127225A discloses a method for preparing a hard foam by a one-step method, which is mainly characterized in that mixed liquid A and liquid B are injected into a mould, then the mould is sealed, and the mould is shaped and imidized in microwave. 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 mixture is transparent; adding a catalyst, water and a foam stabilizer, and reacting to obtain a transparent solution A;
s2, adding a solvent 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, and standing for 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 one or a combination of two or more of 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 1,2,4, 5-pyromellitic dianhydride, 3',4,4' -diphenyl ether tetracarboxylic dianhydride, bisphenol a type diether dianhydride, 3',4,4' -biphenyl tetracarboxylic dianhydride, and 2,3',4,4' -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 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 adjusted according to the mass concentration 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 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 step of S2 further comprises, after dispersion: standing for defoaming, and cooling to 15 ℃ to obtain modified liquid A.
Preferably, the isocyanate in S3 is 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 a pressure of 0.1MPa to 20 MPa; 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/m3-500kg/m3The 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/m3-500kg/m3The 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 kept 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 formed2The pores generated during the expansion cause the defect of large pores, thereby affecting the yield of the product. Due to the inventionThe liquid A has low viscosity, the entrapped gas is easier to float up before the system gels, and the alkane solvent is slowly separated from the foam basically during the gelling and serves as a gas flow station channel 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',4,4' -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 silicone oil AK 880564 g after a 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 PM200) 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 h.
The reason for reducing the temperature in b and c to 15 ℃ is that the reaction speed is too fast at high temperature, and the gas release is slowed down because of the reduction of the reaction speed due to the temperature reduction.
d. And 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 3 h.
The density of the obtained porous polyimide material is 150kg/m3The porosity was 92%, the oxygen index was 35%, and the compressive strength was 1.7 MPa.
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 PM200) 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 0.8MPa, and stably maintaining the pressure for 3 h.
d. And 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 3 h.
The density of the obtained porous polyimide material is 120kg/m3The porosity was 95%, the oxygen index was 35%, and the compressive strength was 1.3 MPa.
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 silicone oil AK 880532 g after the system is clarified, uniformly stirring, cooling to room temperature to obtain a solution A with the concentration of 41.6%, and filling the solution A into a solution A barrel.
b. And (3) taking 100g of the solution A, adding 40g of n-hexane into the solution A, dispersing at a high speed, cooling to 10 ℃, standing for 0.5h, and defoaming to obtain a modified solution A for later use.
c. 110g of PAPI (brand PM200) 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 h.
d. And 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 3 h.
The density of the obtained porous polyimide material is 230kg/m3The aperture ratio is 97%, the oxygen index is 40%, and the compressive strength is 2.44 MPa.
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. and taking 100g of the solution A, adding 80g of n-hexane into the solution A, dispersing at a high speed, cooling to 10 ℃, standing for 0.5h, and defoaming to obtain a modified solution A for later use.
c. 100g of PAPI (trademark PM200) 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 h.
d. And 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 3 h.
The density of the obtained porous polyimide material is 183kg/m3The porosity was 98%, the oxygen index was 37%, and the compressive strength was 2.05 MPa.
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',4,4' -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 silicone oil AK 8805120 g after the system is clarified, uniformly stirring, cooling to room temperature to obtain 39.7% solution A, 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 PM200) 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 h.
d. And 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 3 h.
The density of the obtained porous polyimide material is 380kg/m3The aperture ratio is 99%, the oxygen index is 45%, and the compressive strength is 8.05 MPa.
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 PM200) 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 h.
d. And 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 3 h.
The density of the obtained porous polyimide material is 310kg/m3The open porosity was 98%, oxygenIndex 43% and compressive strength 7.52 MPa.
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 silicone oil AK 880560 g after a system is clarified, cooling to room temperature after stirring uniformly to obtain a solution A with the concentration of 30.3%, and filling the solution A into a solution 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 PM200) with the temperature of 10 ℃ is poured into an autoclave after being mixed evenly at the temperature of the modified A liquid. Then quickly pressurizing to 5MPa, and stably maintaining the pressure for 3 h.
d. And 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 3 h.
The density of the obtained porous polyimide material is 260kg/m3The porosity was 97%, the oxygen index was 40%, and the compressive strength was 5.47 MPa.
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 (10)
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;
s2, adding a solvent 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, and standing for foaming;
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 production method according to claim 1, wherein the aromatic dianhydride comprises one or a combination of two or more of 3,3',4,4' -benzophenone tetracarboxylic dianhydride, 1,2,4, 5-pyromellitic dianhydride, 3',4,4' -diphenyl ether tetracarboxylic dianhydride, bisphenol a type diether dianhydride, 3',4,4' -biphenyl tetracarboxylic dianhydride, and 2,3',4,4' -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;
the foam stabilizer is a silicone oil foam stabilizer and comprises DC193 or AK 8805.
3. The method according to claim 1, wherein the heating in S1 is performed at a temperature of 50 ℃ to 100 ℃ for 0.5h to 3 h.
4. The preparation method according to claim 1, wherein the mass concentration of the solution A in the S1 is 15-50%.
5. The method according to claim 1, wherein the solvent immiscible with the polar solvent in the liquid a in 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.
6. 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.
7. The method according to claim 1, wherein the isocyanate in S3 is polyphenyl polymethylene polyisocyanate, or a combination of one or both of toluene diisocyanate and 4,4' -diphenylmethane diisocyanate and polyphenyl polymethylene polyisocyanate;
preferably, the adding amount of the isocyanate in S3 is 50-110% of the mass of the solution A;
preferably, in S3, the pressurization is to a pressure of 0.1MPa to 20 MPa; 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.
8. The production method according to claim 1, wherein the average density of the polyimide porous material obtained in S4 is 15kg/m3-500kg/m3The aperture ratio is 90-99%.
9. A polyimide porous material obtained by the production method according to any one of claims 1 to 8.
10. The porous polyimide material according to claim 9, wherein the porous polyimide material has an average density of 15kg/m3-500kg/m3The aperture ratio is 90-99%.
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| CN101402743A (en) * | 2008-11-25 | 2009-04-08 | 北京市射线应用研究中心 | Polyimide foam and method of producing the same |
| CN103254565A (en) * | 2013-06-04 | 2013-08-21 | 上海海事大学 | Preparation method of toughened modified phenolic foams |
| CN105085916A (en) * | 2015-09-25 | 2015-11-25 | 青岛海洋新材料科技有限公司 | Low-density polyimide foam and production process thereof |
| 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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