CN116199884A - High-performance high-temperature-resistant heat-insulation polyimide foam and application thereof - Google Patents
High-performance high-temperature-resistant heat-insulation polyimide foam and application thereof Download PDFInfo
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- CN116199884A CN116199884A CN202310141076.5A CN202310141076A CN116199884A CN 116199884 A CN116199884 A CN 116199884A CN 202310141076 A CN202310141076 A CN 202310141076A CN 116199884 A CN116199884 A CN 116199884A
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- 238000009413 insulation Methods 0.000 title abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 51
- 239000000843 powder Substances 0.000 claims abstract description 50
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- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 44
- 229920000728 polyester Polymers 0.000 claims abstract description 44
- 238000005187 foaming Methods 0.000 claims abstract description 32
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- CABPHMWTDYXRFV-UHFFFAOYSA-N 4-(4,4-diamino-2-methylcyclohexa-2,5-dien-1-ylidene)-3-methylcyclohexa-2,5-diene-1,1-diamine Chemical compound CC=1C(C=CC(C=1)(N)N)=C1C(=CC(N)(C=C1)N)C CABPHMWTDYXRFV-UHFFFAOYSA-N 0.000 claims description 2
- MQAHXEQUBNDFGI-UHFFFAOYSA-N 5-[4-[2-[4-[(1,3-dioxo-2-benzofuran-5-yl)oxy]phenyl]propan-2-yl]phenoxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC2=CC=C(C=C2)C(C)(C=2C=CC(OC=3C=C4C(=O)OC(=O)C4=CC=3)=CC=2)C)=C1 MQAHXEQUBNDFGI-UHFFFAOYSA-N 0.000 claims description 2
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- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 2
- 238000009835 boiling Methods 0.000 claims description 2
- 229910052731 fluorine Inorganic materials 0.000 claims description 2
- 239000011737 fluorine Substances 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 125000002183 isoquinolinyl group Chemical group C1(=NC=CC2=CC=CC=C12)* 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 238000011415 microwave curing Methods 0.000 claims description 2
- 125000006158 tetracarboxylic acid group Chemical group 0.000 claims description 2
- 239000011358 absorbing material Substances 0.000 claims 1
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- 238000010521 absorption reaction Methods 0.000 abstract description 4
- 238000004886 process control Methods 0.000 abstract 1
- 230000010261 cell growth Effects 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- IMNDHOCGZLYMRO-UHFFFAOYSA-N n,n-dimethylbenzamide Chemical compound CN(C)C(=O)C1=CC=CC=C1 IMNDHOCGZLYMRO-UHFFFAOYSA-N 0.000 description 18
- 230000006835 compression Effects 0.000 description 14
- 238000007906 compression Methods 0.000 description 14
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- YBRVSVVVWCFQMG-UHFFFAOYSA-N 4,4'-diaminodiphenylmethane Chemical compound C1=CC(N)=CC=C1CC1=CC=C(N)C=C1 YBRVSVVVWCFQMG-UHFFFAOYSA-N 0.000 description 1
- QYIMZXITLDTULQ-UHFFFAOYSA-N 4-(4-amino-2-methylphenyl)-3-methylaniline Chemical group CC1=CC(N)=CC=C1C1=CC=C(N)C=C1C QYIMZXITLDTULQ-UHFFFAOYSA-N 0.000 description 1
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- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
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- 125000005462 imide group Chemical group 0.000 description 1
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Images
Classifications
-
- 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
-
- 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
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
-
- 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 provides a high heat-resistant and radiation-resistant flexible polyimide foam with excellent heat insulation and mechanical properties and application thereof, and belongs to the technical field of advanced materials. The polyimide foam is obtained by foaming, curing and imidizing polyester ammonium salt precursor powder; the polyester ammonium salt precursor powder is obtained by directly copolymerizing dianhydride and two different diamines or by respectively reacting and then blending. The polyimide foam disclosed by the invention is light in weight, good in heat resistance, radiation resistance and heat insulation performance, excellent in flexibility and mechanical strength, capable of realizing anisotropic control of foam microstructure and performance through process control, and capable of being used as a high-temperature-resistant heat-proof material, a radiation-resistant material, a packaging material, a sound absorption material, a buffering and damping material and the like, and has wide application prospects in the fields of aerospace, nuclear power equipment, ship industry, medical appliances, new energy and the like.
Description
Technical Field
The invention belongs to the technical field of advanced materials, and particularly relates to high-performance high-temperature-resistant heat-insulation polyimide foam and application thereof.
Background
Polyimide is a heat-resistant polymer material with excellent comprehensive performance, and has good thermal performance, mechanical performance and chemical stability, and lower dielectric constant and thermal expansion coefficient. Meanwhile, the variety of dianhydride and diamine monomer structure types for preparing polyimide molecules ensures that polyimide molecules have multiple structure types, strong designability and wide application fields.
The polyimide foam is a foam plastic with polyimide resin as a matrix and a porous structure on the inner and outer layers. Polyimide foam not only has the characteristics of light weight, heat insulation, sound absorption and the like, but also has excellent heat resistance, radiation resistance, flame retardance and dimensional stability due to the excellent performance of polyimide, and is attracting more attention and importance of researchers, and has been widely applied to the fields of heat insulation and sound insulation materials of aircrafts and the like.
With the gradual development of the field equipment such as aerospace, nuclear power equipment, ship industry, medical equipment, new energy and the like towards high performance and high functionality, in order to meet the application requirements of the fields, a plurality of researches are currently focused on developing polyimide foam with higher thermal stability and mechanical property, but the polyimide foam tends to have high apparent density, mechanical elasticity and reduced heat insulation property; on the contrary, polyimide foam with light apparent density, good flexibility and heat insulation performance has poor performance of mechanical performance and thermal performance. For example, chinese patent CN101735457B discloses a method for producing a flexible polyimide foam, which is obtained by a free foaming method, and then is cured in a microwave oven and a high temperature oven, so that the prepared foam has low density, is soft and elastic, but has poor mechanical properties and thermal properties, and cannot meet the application in various fields. Ren et al succeeded in preparing a light isocyanate-based polyimide foam having a foam cell size of 518 to 791 μm and an open cell content of 6.85 to 58.46%, but having poor thermal performance (Ren, X.H.; sun, G.H.; wang, L.C.; chen, R.R.; wang, J.; han, S.H. facility Adjusting for Cells of Lightweight Isocyanate-based Polyimide Foam and Operable Combination between Different Distinctive Acoustic Foams for Higher performance.Chinese Journal of Polymer Science 2021,39 (2), 237-248).
Therefore, it has been a problem in the art to prepare polyimide foam having excellent mechanical properties, flexibility, high temperature resistance, radiation resistance and heat insulation properties. Patent application CN114213696a discloses a polyimide foam, which is prepared by combining microwave-assisted foaming and curing processes, has light weight, flexibility, high temperature resistance and excellent heat insulation performance, but the mechanical performance of the polyimide foam still needs to be further improved. How to improve the mechanical strength of polyimide foam while ensuring low apparent density, good flexibility, heat resistance and heat insulation performance is also needed to be explored more deeply. Meanwhile, the polyimide foam has important application in high-temperature heat insulation due to high heat resistance, but the heat conductivity of the polyimide foam is generally higher than 0.030W/m.K, for example, 3',4' -benzophenone tetracarboxylic dianhydride and 4,4' -diaminodiphenyl ether are used as raw materials in the literature (Jiangtian sweet. Preparation of polyimide foam and modification research of polyimide foam.2020), and the density is only 10kg/m by adopting a free foaming method 3 But the heat conductivity of the soft open-cell polyimide foam is higher than 0.035W/m.K, so that the preparation of the low-density high-heat-resistance polyimide foam with lower heat conductivity has important application value.
Therefore, through a simple and effective technology, the light and flexible polyimide foam material is provided, and particularly the light and flexible polyimide foam material has the advantages of light weight, high temperature resistance, radiation resistance, outstanding heat insulation performance, excellent flexibility and mechanical strength, and can realize anisotropic heat protection and infrared stealth, and has great significance, and has wide application prospects in various important fields such as aerospace, nuclear power equipment, ship industry, medical appliances, new energy sources and the like.
Disclosure of Invention
The invention aims to provide a polyimide foam material with low apparent density, good flexibility, excellent heat resistance, radiation resistance and heat insulation performance, higher compression strength and heat protection.
The invention provides polyimide foam, which is obtained by foaming, curing and imidizing polyester ammonium salt precursor powder;
the polyester ammonium salt precursor is obtained by reacting diacid diester with diamine A and diamine B;
or, the polyester ammonium salt precursor is obtained by blending the reaction product of diacid diester and diamine A and the reaction product of diacid diester and diamine B;
the diamine a and diamine B are different.
Further, the diacid diester is obtained by esterification of dianhydride; preferably, the esterification is by reaction with an alcohol.
Further, the dianhydride is 3,3',4' -diphenyl ether tetracarboxylic anhydride, 3',4' -benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 2, 3', one or more of 4' -biphenyltetracarboxylic dianhydride, 3',4' -biphenylsulfone tetracarboxylic dianhydride, bisphenol a dianhydride or hexafluorodianhydride;
preferably, the dianhydride is 3,3',4' -benzophenone tetracarboxylic dianhydride and the alcohol is methanol.
Further, the diamine A and the diamine B are respectively and independently selected from one of 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl methane, p-phenylenediamine, m-phenylenediamine, 3 '-diaminodiphenyl sulfone, 4' -diamino-2, 2 '-dimethylbenzidine and 2,2' -di (trifluoromethyl) diaminobenzidine;
preferably, the diamine a and the diamine B are each independently selected from: 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl methane, and 4,4 '-diamino-2, 2' -dimethylbenzidine.
Further, the mole fraction of the diacid diester, diamine A and diamine B is (1-3): 0.5-1.5; preferably 2:1:1.
Further, the particle size of the polyester ammonium salt precursor powder is less than 200 mu m.
Further, the polyester ammonium salt precursor powder is prepared according to the following method:
(1) The dianhydride and the alcohol are heated and reflux reacted for 2 to 6 hours in a low boiling point solvent under the protection of inert gas;
(2) Adding diamine, adding imidization accelerator and surfactant, and heating and refluxing for reaction for 1-3 hours; adding water, stirring and refluxing to obtain a polyester ammonium salt precursor solution;
(3) Removing solvent from the polyester ammonium salt precursor solution, grinding and sieving to obtain powder with the particle size smaller than 200 mu m;
wherein the diamine in the step (2) is a mixture of diamine A and diamine B to obtain polyester ammonium salt precursor powder; or, diamine in the step (2) is diamine A to prepare powder A, diamine in the step (2) is diamine B to prepare powder B, and the powder A, the powder B and the like are mixed by mass to obtain polyester ammonium salt precursor powder;
the imidization promoter is isoquinoline; the surfactant is silicone oil DC-193, DC-198, DC-200, nonionic fluorine surfactant
One or more of FS-3100, preferably silicone oil DC-193.
Further, the foaming is microwave foaming, and the imidization is thermal imidization.
Further, the microwave foaming is carried out for 3 to 7 minutes at 500 to 600W, and then 650 to 750W is carried out for 8 to 12 minutes;
the curing is 1000-1100W microwave curing for 8-12 min;
the thermal imidization is carried out for 1-3 hours at 250-300 ℃.
The invention also provides application of the polyimide foam in heat insulation materials, radiation-resistant materials, packaging materials, sound absorption materials and buffering and damping materials.
The invention has the beneficial effects that: the invention obtains the polyester ammonium salt precursor prepared from the dianhydride and two different diamines by using the mode of directly copolymerizing the two diamines with the dianhydride or respectively reacting with the dianhydride and then blending, and further foams, cures and imidizes the polyester ammonium salt precursor to prepare the polyimide foam, which has the advantages of light weight, good heat resistance, radiation resistance and heat insulation performance, excellent flexibility and mechanical strength, and can realize anisotropic thermal protection and infrared stealth, thus having wide application prospect in the fields of aerospace, nuclear power equipment, ship industry, medical appliances, new energy sources and the like.
It should be apparent that, in light of the foregoing, various modifications, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims.
The above-described aspects of the present invention will be described in further detail below with reference to specific embodiments in the form of examples. It should not be understood that the scope of the above subject matter of the present invention is limited to the following examples only. All techniques implemented based on the above description of the invention are within the scope of the invention.
Drawings
FIG. 1 is an SEM image of the optical, cell wall and bubble film of a high performance high temperature resistant thermal insulation polyimide foam (A) is an image of example 2; (B) is the image of example 5.
FIG. 2 is a thermal performance image of a high performance high temperature resistant thermal insulation polyimide foam (A) is a DSC graph; (B) is a DMA graph; (C) is a graph of thermal conductivity in the direction of cell growth; (D) is a graph of thermal conductivity in the direction perpendicular to the cell growth direction.
FIG. 3 is an anisotropic microstructure and mechanical properties image of a high performance high temperature resistant thermal insulation polyimide foam (A) is an SEM image of example 2 along the direction of cell growth; (B) SEM image of example 2 along the direction of vertical cell growth; (C) is a graph of compression performance in different directions for example 2; (D) SEM image of example 5 along the cell growth direction; (E) SEM image of example 5 along the vertical cell growth direction; (F) is a graph of the compression performance of example 5 in different directions.
Detailed Description
The raw materials and equipment used in the invention are all known products and are obtained by purchasing commercial products.
Example 1 preparation of polyimide foam of copolymerization System (BTDA/ODA-MDA System)
Into a three-necked flask, 96.66g of 3,3',4' -Benzophenone Tetracarboxylic Dianhydride (BTDA), 81.02mL of absolute methanol and 121.83mL of tetrahydrofuran were added, and the mixture was heated and refluxed under nitrogen protection at 65℃for 4 hours to obtain a clear and transparent solution of an aromatic diacid diester. Then, 30.03g of 4,4' -diaminodiphenyl ether (4, 4' -ODA) and 28.77g of 4,4' -diaminodiphenyl Methane (MDA) were added to the above clear and transparent solution, and 0.36mL of isoquinoline, 0.75mL of silicone oil DC-193 were added, and heated and refluxed at 70℃for 2 hours, cooled to room temperature, and then added with 4.95mL of deionized water, and refluxed with stirring for 1 hour, to obtain a polyester ammonium salt precursor solution. Drying, grinding and sieving the solution to obtain the polyester ammonium salt precursor powder smaller than 200 mu m, namely the polyester ammonium salt precursor copolymerization powder.
Adding a certain mass of polyester ammonium salt precursor powder into a mould, capping and sealing the mould, putting the mould into a microwave oven, starting the microwave oven, pre-foaming for 5min by using a low fire gear 560W, heating and foaming for 10min by using a medium fire gear 700W, curing for 10min by using a high fire gear 1050W, and then placing the mould into a high temperature oven with the temperature of 280 ℃ for imidization treatment for about 2h to obtain polyimide foam.
EXAMPLE 2 preparation of polyimide foam of copolymerization System (BTDA/ODA-DMBZ System)
96.66g BTDA,81.02mL absolute methanol, 121.83mL tetrahydrofuran, was added to a three-necked flask, and the mixture was heated and refluxed under nitrogen at 65℃for 4 hours to obtain a clear and transparent solution of the aromatic diacid diester. Then, 30.03g of 4,4' -ODA and 31.85g of 4,4' -diamino-2, 2' -Dimethylbiphenyl (DMBZ) were added to the above clear and transparent solution, and 0.38mL of isoquinoline, 0.77mL of silicone oil DC-193 were added, and heated and refluxed at 70℃for 2 hours, cooled to room temperature, then added with 4.98mL of deionized water, and stirred and refluxed for 1 hour to obtain a polyesterammonium salt precursor solution. Drying, grinding and sieving the solution to obtain the polyester ammonium salt precursor powder smaller than 200 mu m, namely the polyester ammonium salt precursor copolymerization powder.
Adding a certain mass of polyester ammonium salt precursor powder into a mould, capping and sealing the mould, putting the mould into a microwave oven, starting the microwave oven, pre-foaming for 5min by using a low fire gear 560W, heating and foaming for 10min by using a medium fire gear 700W, curing for 10min by using a high fire gear 1050W, and then placing the mould into a high temperature oven with the temperature of 280 ℃ for imidization treatment for about 2h to obtain polyimide foam.
EXAMPLE 3 preparation of polyimide foam of copolymerization System (BTDA/MDA-DMBZ System)
96.66g BTDA,81.02mL absolute methanol, 121.83mL tetrahydrofuran, was added to a three-necked flask, and the mixture was heated and refluxed under nitrogen at 65℃for 4 hours to obtain a clear and transparent solution of the aromatic diacid diester. Then, 28.77g of MDA and 31.85g of DMBZ were added to the above clear and transparent solution, and 0.38mL of isoquinoline and 0.77mL of silicone oil DC-193 were added thereto, and heated and refluxed at 70℃for 2 hours, cooled to room temperature, and then added with 4.98mL of deionized water, and stirred and refluxed for 1 hour, to obtain a precursor solution of a polyesterammonium salt. Drying, grinding and sieving the solution to obtain the polyester ammonium salt precursor powder smaller than 200 mu m, namely the polyester ammonium salt precursor copolymerization powder.
Adding a certain mass of polyester ammonium salt precursor powder into a mould, capping and sealing the mould, putting the mould into a microwave oven, starting the microwave oven, pre-foaming for 5min by using a low fire gear 560W, heating and foaming for 10min by using a medium fire gear 700W, curing for 10min by using a high fire gear 1050W, and then placing the mould into a high temperature oven with the temperature of 280 ℃ for imidization treatment for about 2h to obtain polyimide foam.
Example 4 preparation of polyimide foam of blend System (BTDA/ODA & BTDA/MDA System)
BTDA/ODA system: 96.66g BTDA,81.02mL absolute methanol, 121.83mL tetrahydrofuran, was added to a three-necked flask, and the mixture was heated and refluxed under nitrogen at 65℃for 4 hours to obtain a clear and transparent solution of the aromatic diacid diester. Then, 60.06g of 4,4' -ODA was added to the clear and transparent solution obtained, and 0.36mL of isoquinoline and 0.75mL of silicone oil DC-193 were added, and heated and refluxed at 70℃for 2 hours, cooled to room temperature, and then 4.95mL of deionized water was added, and stirred and refluxed for 1 hour, to obtain a polyester ammonium salt precursor solution. Drying, grinding and sieving the solution to obtain the polyester ammonium salt precursor powder smaller than 200 mu m.
BTDA/MDA system: 96.66g BTDA,81.02mL absolute methanol, 121.83mL tetrahydrofuran, was added to a three-necked flask, and the mixture was heated and refluxed under nitrogen at 65℃for 4 hours to obtain a clear and transparent solution of the aromatic diacid diester. Then, 59.48g of MDA was added to the clear and transparent solution obtained, and 0.36mL of isoquinoline and 0.75mL of silicone oil DC-193 were added, and heated and refluxed at 70℃for 2 hours, cooled to room temperature, and then 4.95mL of deionized water was added, and stirred and refluxed for 1 hour, to obtain a polyesterammonium salt precursor solution. Drying, grinding and sieving the solution to obtain the polyester ammonium salt precursor powder smaller than 200 mu m.
And mixing the prepared BTDA/ODA powder and the prepared BTDA/MDA powder in equal mass to prepare BTDA/ODA & BTDA/MDA blend powder, namely polyester ammonium salt precursor blend powder.
Adding a certain amount of polyester ammonium salt precursor powder into a mould, capping and sealing the mould, putting the mould into a microwave oven, starting the microwave oven, pre-foaming for 5min by using a low fire gear 560W, heating and foaming for 10min by using a medium fire gear 700W, curing for 10min by using a high fire gear 1050W, and then placing the mould into a high temperature oven with the temperature of 280 ℃ for imidization treatment for about 2h to obtain polyimide foam.
Example 5 preparation of polyimide foam of blend System (BTDA/ODA & BTDA/DMBZ System)
BTDA/ODA system: reference is made to the preparation of example 4.
BTDA/DMBZ system: 96.66g BTDA,81.02mL absolute methanol, 121.83mL tetrahydrofuran, was added to a three-necked flask, and the mixture was heated and refluxed under nitrogen at 65℃for 4 hours to obtain a clear and transparent solution of the aromatic diacid diester. Then, 63.69g of DMBZ was added to the clear and transparent solution obtained, and 0.38mL of isoquinoline and 0.78mL of silicone oil DC-193 were added thereto, and heated and refluxed at 70℃for 2 hours, cooled to room temperature, then 5.01mL of deionized water was added thereto, and refluxed with stirring for 1 hour, to obtain a precursor solution of a polyesterammonium salt. Drying, grinding and sieving the solution to obtain the polyester ammonium salt precursor powder smaller than 200 mu m.
And mixing the prepared BTDA/ODA and BTDA/DMBZ powder in equal mass to prepare BTDA/ODA & BTDA/DMBZ blend powder, namely polyester ammonium salt precursor blend powder.
Adding a certain amount of polyester ammonium salt precursor powder into a mould, capping and sealing the mould, putting the mould into a microwave oven, starting the microwave oven, pre-foaming for 5min by using a low fire gear 560W, heating and foaming for 10min by using a medium fire gear 700W, curing for 10min by using a high fire gear 1050W, and then placing the mould into a high temperature oven with the temperature of 280 ℃ for imidization treatment for about 2h to obtain polyimide foam.
Example 6 preparation of polyimide foam of blend System (BTDA/MDA & BTDA/DMBZ System)
BTDA/MDA system: reference is made to the preparation of example 4.
BTDA/DMBZ system: reference is made to the preparation of example 5.
And mixing the prepared BTDA/MDA and BTDA/DMBZ powder in equal mass to prepare BTDA/MDA & BTDA/DMBZ blend powder, namely polyester ammonium salt precursor blend powder.
Adding a certain amount of polyester ammonium salt precursor powder into a mould, capping and sealing the mould, putting the mould into a microwave oven, starting the microwave oven, pre-foaming for 5min by using a low fire gear 560W, heating and foaming for 10min by using a medium fire gear 700W, curing for 10min by using a high fire gear 1050W, and then placing the mould into a high temperature oven with the temperature of 280 ℃ for imidization treatment for about 2h to obtain polyimide foam.
Experimental example 1 optical and micro-morphology of polyimide foam of the present invention
1. Experimental method
The cell structure of the foam samples was characterized by scanning electron microscopy using the copolyfoam of examples 1-3 and the blended foam of examples 4-6. Prior to observation, the foam was cut into pieces, and the surface of each piece was sputtered with gold. And finally, measuring and analyzing the size of the cell pores by nano test software.
2. Experimental results
As shown in fig. 1, the microstructure of the foam exhibits a regular three-dimensional (3D) cellular morphology in the direction of cell growth, with uniform cell distribution. As shown in Table 1, the average pore diameters of examples 1-6 were 287, 270, 395, 248, 213 and 202 μm, respectively. The corresponding bubble wall and bubble film thickness are between 2-10 μm and 200-1000nm, respectively. The differences in the cell structure of the foam are mainly influenced by the combination of molecular structure, melt viscosity, volatile content and foaming temperature. The foam of the blend system has smaller, more uniform pore sizes and thicker bubble films, thereby helping to increase the mechanical flexibility of the foam material. The results show that all foams possess micro-nano multi-scale microstructures, which gives the foam material very excellent mechanical properties.
Experimental example 2 mechanical Properties and various physical Properties of polyimide foam of the invention
1. Experimental method
The apparent density of the foams was calculated according to GB/T6343-2009 using the copolyfoam of examples 1-3 and the blended foam of examples 4-6. According to GB/T10799-2008, the open cell content of the foam was evaluated using an automatic true densitometer. Foam samples (30X 15 mm) were evaluated using a universal mechanical tester 3 ) The compression ratio was 2mm/min.
2. Experimental results
The compressibility of the foam was studied to evaluate the correlation between mechanical flexibility and molecular structure and microstructure. As shown in Table 1, all foams exhibited light weight (25-30 kg/m 3 ) And full aperture ratio (99.99%). All foams possess excellent mechanical flexibility with a compression recovery of 96% to 98% at a maximum compression strain of 50%. All foams showed excellent mechanical strength, 10% compression strengthBetween 65 KPa and 103KPa, 50% compression strength is between 132 KPa and 191 KPa. Example 6 shows higher molecular chain stiffness, as well as smaller average pore size (202 μm) and thicker bubble film (918 nm), which is why it shows the highest compression performance (compression strength @10% 102.95KPa, compression strength @50% 190.75 KPa). In general, the blended foams possess better mechanical properties, mainly related to their more suitable micron-sized cells (200-250 μm) and thicker nanoscale bubble films. In summary, the polyimide foam prepared by the present invention exhibits excellent mechanical flexibility and high mechanical strength.
The physical properties of each foam of the present invention are shown in Table 1:
TABLE 1 physical Properties of the high-performance high-temperature resistant thermal insulation polyimide foam of the invention
Experimental example 3 thermal stability of polyimide foam of the present invention
1. Experimental method
The copolyfoam of examples 1-3 and the blended foam of examples 4-6 were heated from 35 ℃ to 800 ℃ at a rate of 10 ℃/min using a thermogravimetric analyzer to test the thermal stability of the fully imidized foam MAFs and the fully imidized foam PIFs.
2. Experimental results
As shown in Table 2, under nitrogen, the fully imidized MAF exhibited an initial thermal decomposition temperature (T 5％ ) And a weight residue at 800 ℃ (R 800 ) The decrease occurs with a slight weight loss peak at 200-300 ℃, mainly due to degradation of the polyester ammonium salt in the molecular chain. In contrast, fully imidized PIF exhibits good thermal stability, T 5％ Above 500 ℃, R 800 Higher than 55%. PIF copolymer system BTDA/ODA-MDA 、PIF BTDA/ODA-DMBZ And PIF BTDA/MDA-DMBZ T in nitrogen 5％ 527.9, 517.8 and 502.6℃R 800 55.1, 55.2 and 56.9%, respectively. PIF (PIF) blend system BTDA/ODA&BTDA/MDA 、PIF BTDA/ODA&BTDA/DMBZ And PIF BTDA/MDA&BTDA/DMBZ T in nitrogen 5％ 522.7, 510.3 and 505.2℃R 800 54.9, 56.1 and 57.1%, respectively. The small difference in thermal stability between the co-foam and the blended foam suggests that the thermal stability of polyimide foam is primarily affected by the molecular structure, rather than by the foaming and shaping process.
The above results prove that the polyimide foam prepared by the invention has good thermal stability.
TABLE 2 thermal stability of the high performance high temperature resistant thermal insulation polyimide foam of the invention
Experimental example 4 Heat resistance of polyimide foam of the invention
1. Experimental method
The copolyfoam of examples 1-3 and the blended foam of examples 4-6 were taken and differential scanning calorimetry measurements were performed using a DSC 3500Sirius instrument under nitrogen atmosphere while dynamic thermodynamic analysis was performed in compressed mode on a DMA Q800 analyzer.
2. Experimental results
As shown in fig. 2A, the glass transition temperatures (T g ) And molecular structure. T for DSC, foam g Has excellent heat resistance between 267-281 ℃. And the heat resistance of the foam increases with the rigidity of its molecular chain. However, due to T of the blended foam g Overlapping, the differences in molecular structure of the foam cannot be characterized by DSC. From the figure, the copolyfoam has a homogeneous structure, however, it cannot be judged whether the blended foam has a homogeneous structure by DSC.
As shown in fig. 2B, the PIF BTDA/ODA 、PIF BTDA/DMBZ 、PIF BTDA/ODA-DMBZ And PIF BTDA/ODA&BTDA/DMBZ T of (2) g 297.6, 348.2, 310.7 ℃, 294.4 and 348.1 ℃, respectively, the foam havingExcellent heat resistance. Through DMA analysis, the molecular structure of the precursor powder subjected to copolymerization is subjected to chemical crosslinking reaction in the synthesis process, and the foam finally presents a homogeneous structure; whereas two T are present for the two precursor powders blended g It can be seen that no chemical reaction occurs during foaming and the foam eventually assumes a phase-separated structure. DSC and DMA results indicate that all foams exhibit good heat resistance and are suitable for the high temperature resistant field.
The above results demonstrate that polyimide foams having excellent properties can be produced regardless of whether two different diamines are copolymerized together with a dianhydride or separately copolymerized with a dianhydride and then blended.
Experimental example 5 thermal insulation Property of polyimide foam of the invention
1. Experimental method
The thermal conductivity of the foams was evaluated using a thermal constant analyzer from the copolyfoam of examples 1 to 3 and the blended foam of examples 4 to 6. In order to qualitatively evaluate the insulating behavior of the foam, foam samples (15X 15 mm) placed on a pre-heating stage at 200℃were recorded using a thermal infrared imager 3 ) Is a change in the top surface temperature of (c).
2. Experimental results
Thermal conductivity in the direction of cell growth is shown in fig. 2C. All foams have a thermal conductivity between 0.031 and 0.033W/mK, exhibit a thermal conductivity close to that of air (0.026W/mK), and the polyimide foam of the present invention exhibits excellent heat insulating properties in the direction of cell growth. Meanwhile, the insulating properties of the foam were evaluated by in-situ monitoring of the surface temperature of the sample placed on a pre-heating stage at 200 ℃. The results showed that after 300s of the foam sample was placed on a 200℃platform, the surface temperature was between 40 and 65℃and the temperature increase was between 10 and 20 ℃. After further placing the foam sample on a preheating stage with a temperature fluctuation of 200 ℃ for 30 minutes, the top surface temperature of the foam sample is also about 60 ℃, and the excellent heat insulation performance of the polyimide foam of the invention is further shown. In conclusion, the polyimide foam has excellent heat insulation performance and can be used in the high-tech industrial sector.
Experimental example 6 radiation resistance of polyimide foam of the invention
1. Experimental method
The copolyfoam of example 1 and the blended foam of example 5 were used Co 60 as gamma radiation source (1.2 MeV) for testing the radiation resistance of foam sample, the average radiation metering rate is 13.40kGy/h, the effective radiation time is 750h, and the total radiation dose is 1.0X10% 4 kGy。
2. Experimental results
The radiation resistance of the polyimide foam of the present invention was evaluated by evaluating the changes in molecular structure, microstructure, thermal stability and mechanical properties of the polyimide foam before and after irradiation. The results show that the position and intensity of the infrared absorption peaks of the benzene ring and imide ring of the foam after irradiation do not significantly change, and only-CH in MDA 2 and-CH in DMBZ 3 The peak of (2) was attenuated after irradiation, while the peak of c=o in BTDA and C-O-C in ODA remained unchanged, indicating that the weak bond was broken during irradiation. After radiation treatment, the foam color turns yellow and deepens, and still shows a regular, micrometer/nanometer scale multi-scale pore structure, which is structurally stable, which is critical to maintaining mechanical properties. Table 3 shows PIF BTDA/ODA-MDA And PIF BTDA/ODA&BTDA/DMBZ The heat stability and mechanical property parameters before and after irradiation are calculated, and the heat stability retention rate of the foam after the irradiation treatment is 82.95 percent and 82.40 percent respectively. At the same time, PIF after radiation BTDA/ODA-MDA And PIF BTDA/ODA&BTDA/DMBZ The compressive strength retention of 10% and 50% in the vertical direction were 82.89%,80.06% and 81.36%,92.89%, respectively. Furthermore, the foam after the irradiation treatment still showed light weight (25-30 kg/m 3 ) And mechanical flexibility (94-95% compression recovery), which is related to the retention of the porous structure. Therefore, the polyimide foam of the invention has excellent radiation resistance and has great application potential in the nuclear industry.
TABLE 3 radiation resistance of the high performance high temperature resistant thermal insulation polyimide foam of the invention
Experimental example 7 Anisotropic Properties of polyimide foam of the invention
1. Experimental method
The copolyfoam of example 2 and the blended foam of example 5 were taken and the microstructure and mechanical properties of the cell growth direction and the perpendicular cell growth direction were measured, respectively. The foams of examples 1 to 6 were taken and compared for heat insulating properties in the cell growth direction and in the direction perpendicular to the cell growth direction using a thermal constant analyzer and a thermal infrared imager.
2. Experimental results
As shown in fig. 3, the microstructure in the cell growth direction (vertical direction) exhibited a regular porous nearly spherical morphology, while the microstructure in the vertical cell growth direction (horizontal direction) exhibited an aligned ellipsoidal stripe structure. The mechanism of this phenomenon is ascribed to the "bottom-up" foaming behavior of the precursor powder during rapid microwave foaming. Furthermore, the anisotropic microstructure of the foam results in significant anisotropic compression properties in both directions. The compressive strength in the cell growth direction is about 1.5 to 3 times that in the perpendicular cell growth direction, for example, the compressive strength @10% in the cell growth direction of example 5 is 99.09KPa, and the compressive strength @10% in the perpendicular cell growth direction is only 33.54KPa. Although the compressive strength of the foam in the vertical cell growth direction was low, it had a high mechanical flexibility in the vertical cell growth direction, for example, the compression recovery in example 5 in the vertical cell growth was 98.48%. As shown in FIG. 2D, the thermal conductivity in the vertical cell growth direction is 0.028 to 0.029W/mK, which is lower than that in the cell growth direction (0.031 to 0.033W/mK), showing particularly excellent heat insulating properties. After the foam samples in different directions are placed on a preheating platform with the temperature fluctuation of 200 ℃ for 30 minutes, the top surface temperature of the foam cells in the growth direction is about 60 ℃, and the top surface temperature of the foam cells in the vertical growth direction is about 55 ℃, further showing that the polyimide foam has excellent anisotropic heat insulation performance and can realize heat protection and infrared stealth. The ellipsoidal strip-shaped structure perpendicular to the growth direction of the cells effectively inhibits heat conduction, so that the heat insulation performance is enhanced, and the regular porous nearly spherical structure in the growth direction of the cells is easy to transfer heat, so that heat accumulation is reduced. In conclusion, compared with polyimide foam in the prior literature and patent, the high-performance high-temperature-resistant heat-insulation polyimide foam disclosed by the invention has lower heat conductivity, and meanwhile, the oriented porous foam has wide application prospects in the fields of heat protection and infrared stealth.
The polyimide foam has excellent anisotropic property and can further enrich application scenes.
In summary, the invention provides a method for preparing a polyester ammonium salt precursor from dianhydride and two different diamines by directly copolymerizing the two diamines with the dianhydride or respectively reacting with the dianhydride and then blending the two diamines, and further foaming, curing and imidizing the precursor to prepare polyimide foam, which has the advantages of light weight, good heat resistance, radiation resistance and heat insulation performance, excellent flexibility and mechanical strength, and can realize anisotropic thermal protection and infrared stealth, thus having wide application prospects in the fields of aerospace, nuclear power equipment, ship industry, medical appliances, new energy sources and the like.
Claims (10)
1. A polyimide foam is characterized in that the polyimide foam is obtained by foaming, curing and imidizing polyester ammonium salt precursor powder;
the polyester ammonium salt precursor is obtained by reacting diacid diester with diamine A and diamine B;
or, the polyester ammonium salt precursor is obtained by blending the reaction product of diacid diester and diamine A and the reaction product of diacid diester and diamine B;
the diamine a and diamine B are different.
2. The polyimide foam according to claim 1, wherein the diacid diester is obtained by esterification of dianhydride; preferably, the esterification is by reaction with an alcohol.
3. The polyimide foam of claim 2, wherein the dianhydride is 3,3',4' -diphenyl ether tetracarboxylic anhydride, 3',4' -benzophenone tetracarboxylic dianhydride, pyromellitic dianhydride, 2, 3', one or more of 4' -biphenyltetracarboxylic dianhydride, 3',4' -biphenylsulfone tetracarboxylic dianhydride, bisphenol a dianhydride or hexafluorodianhydride;
preferably, the dianhydride is 3,3',4' -benzophenone tetracarboxylic dianhydride and the alcohol is methanol.
4. The foam of claim 1, the diamine A and the diamine B are respectively and independently selected from one of 3,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl methane, p-phenylenediamine, m-phenylenediamine, 3 '-diaminodiphenyl sulfone, 4' -diamino-2, 2 '-dimethylbenzidine and 2,2' -di (trifluoromethyl) diaminobenzidine;
preferably, the diamine a and the diamine B are each independently selected from: 4,4 '-diaminodiphenyl ether, 4' -diaminodiphenyl methane, and 4,4 '-diamino-2, 2' -dimethylbenzidine.
5. The polyimide foam according to claim 1, wherein the mole fraction of the diacid diester, diamine A, and diamine B is (1-3): 0.5-1.5; preferably 2:1:1.
6. The polyimide foam according to any one of claims 1 to 5, characterized in that the polyester ammonium salt precursor powder has a particle size of less than 200 μm.
7. The polyimide foam according to claim 6, wherein the polyester ammonium salt precursor powder is prepared by the following method:
(1) The dianhydride and the alcohol are heated and reflux reacted for 2 to 6 hours in a low boiling point solvent under the protection of inert gas;
(2) Adding diamine, adding imidization accelerator and surfactant, and heating and refluxing for reaction for 1-3 hours; adding water, stirring and refluxing to obtain a polyester ammonium salt precursor solution;
(3) Removing solvent from the polyester ammonium salt precursor solution, grinding and sieving to obtain powder with the particle size smaller than 200 mu m;
wherein the diamine in the step (2) is a mixture of diamine A and diamine B to obtain polyester ammonium salt precursor powder; or, diamine in the step (2) is diamine A to prepare powder A, diamine in the step (2) is diamine B to prepare powder B, and the powder A, the powder B and the like are mixed by mass to obtain polyester ammonium salt precursor powder;
the imidization promoter is isoquinoline; the surfactant is silicone oil DC-193, DC-198, DC-200, nonionic fluorine surfactant
One or more of FS-3100, preferably silicone oil DC-193.
8. The polyimide foam of claim 1, wherein the foaming is microwave foaming and the imidization is thermal imidization.
9. The polyimide foam according to claim 8, wherein the microwave foaming is 500 to 600W foaming for 3 to 7min, and further 650 to 750W foaming for 8 to 12min;
the curing is 1000-1100W microwave curing for 8-12 min;
the thermal imidization is carried out for 1-3 hours at 250-300 ℃.
10. The polyimide foam according to any one of claims 1 to 9 has a wide application prospect in the fields of aerospace, nuclear power equipment, marine industry, medical equipment, new energy and the like as a heat insulating material, a radiation resistant material, a packaging material, a sound absorbing material, a buffering and damping material and the like.
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