CN116731383A - Preparation method of broadband high-temperature-resistant structural polyimide composite wave-absorbing foam - Google Patents
Preparation method of broadband high-temperature-resistant structural polyimide composite wave-absorbing foam Download PDFInfo
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- 239000004642 Polyimide Substances 0.000 title claims abstract description 71
- 239000006260 foam Substances 0.000 title claims abstract description 71
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- 239000002131 composite material Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims description 8
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000006096 absorbing agent Substances 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 26
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- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims abstract description 13
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- 239000006229 carbon black Substances 0.000 claims description 18
- 239000002041 carbon nanotube Substances 0.000 claims description 17
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- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 8
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 238000001723 curing Methods 0.000 claims description 6
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- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 claims description 5
- 239000004088 foaming agent Substances 0.000 claims description 5
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- VLDPXPPHXDGHEW-UHFFFAOYSA-N 1-chloro-2-dichlorophosphoryloxybenzene Chemical compound ClC1=CC=CC=C1OP(Cl)(Cl)=O VLDPXPPHXDGHEW-UHFFFAOYSA-N 0.000 claims description 4
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical compound C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 claims description 4
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- RGSFGYAAUTVSQA-UHFFFAOYSA-N pentamethylene Natural products C1CCCC1 RGSFGYAAUTVSQA-UHFFFAOYSA-N 0.000 claims description 4
- 229920002545 silicone oil Polymers 0.000 claims description 4
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N heptamethylene Natural products C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 claims description 3
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- ISKQADXMHQSTHK-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CN)C=C1 ISKQADXMHQSTHK-UHFFFAOYSA-N 0.000 claims description 2
- UKLDJPRMSDWDSL-UHFFFAOYSA-L [dibutyl(dodecanoyloxy)stannyl] dodecanoate Chemical compound CCCCCCCCCCCC(=O)O[Sn](CCCC)(CCCC)OC(=O)CCCCCCCCCCC UKLDJPRMSDWDSL-UHFFFAOYSA-L 0.000 claims description 2
- 125000001511 cyclopentyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- 239000012975 dibutyltin dilaurate Substances 0.000 claims description 2
- 238000005576 amination reaction Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
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- 239000011358 absorbing material Substances 0.000 description 16
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- 229920007790 polymethacrylimide foam Polymers 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
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- 125000003118 aryl group Chemical group 0.000 description 2
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- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- 229920005830 Polyurethane Foam Polymers 0.000 description 1
- 239000004964 aerogel Substances 0.000 description 1
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Classifications
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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
- C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
- C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
- C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
- C08J9/141—Hydrocarbons
-
- 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
-
- 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
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
-
- 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
- C08J9/0066—Use of inorganic compounding ingredients
- C08J9/0071—Nanosized fillers, i.e. having at least one dimension below 100 nanometers
-
- 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
- C08J2203/00—Foams characterized by the expanding agent
- C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
-
- 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
A method for preparing broadband high-temperature resistant structural polyimide composite wave-absorbing foam includes preparing polyimide dianhydride monomer/wave-absorbing agent/auxiliary agent emulsion, adding polyisocyanate/wave-absorbing agent emulsion for in-situ polymerization, stirring, foaming and aminating by high Wen Xianya. The three-dimensional porous structure not only endows the material with good impedance matching characteristics, but also is beneficial to multiple reflection and scattering of incident microwaves. The carbon nano material is partially embedded into the polymer skeleton in the in-situ polymerization process, so that the mechanical property of the material is further enhanced, and meanwhile, the carbon nano material can be used as a wave absorber to greatly reduce electromagnetic waves entering the foam by utilizing mechanisms such as polarization loss, leakage conductance and the like. The prepared polyimide composite wave-absorbing foam not only has excellent wave-absorbing performance, and the effective absorption bandwidth reaches 15GHz under the single-layer thickness, but also has excellent mechanical properties, and is expected to meet the requirements of the aerospace and national defense fields on polymer foam materials with the characteristics of bearing and wave absorption.
Description
Technical Field
The invention relates to the field of polyimide foam composite wave-absorbing materials, in particular to a preparation method of broadband high-temperature-resistant structural polyimide composite wave-absorbing foam.
Background
The porous polymer foam has the characteristics of light weight, excellent mechanical property and high processing flexibility, and the porous structure can effectively improve the impedance matching characteristic of the material and promote the microwave absorption performance by enhancing the multiple reflection and scattering of the incident electromagnetic wave, so that the porous polymer foam has wide application prospect in the microwave absorption field.
In fact, foams based on polyurethane, polymethacrylimide (PMI) and the like have been applied in various electromagnetic compatibility fields, such as the fields of aircrafts, missiles, ships, aerospace and the like. Although the processing technology of the materials is stable and reliable, the instability and flammable molecular structure of the polymer matrix directly lead to poor heat resistance and fire resistance, and influence the use safety of the materials. For example, polyurethane foams generally have long-term service temperatures below 120 ℃ and the combustion process releases large amounts of toxic cyanide; the highest use temperature of the PMI foam is 180-240 ℃, but the PMI foam has combustibility, and a certain flame retardant is required to be added to meet the fire-proof requirement, so that the heat resistance and the mechanical property of the foam are affected to a certain extent. Compared with PMI foam, the aromatic polyimide foam contains little or no fatty chain, so that the aromatic polyimide foam has more excellent thermal stability, can resist the temperature of minus 250-300 ℃ for a long time and can resist the high temperature of 400-500 ℃ for a short time. In addition, the polyimide foam has the advantages of excellent mechanical property, self-flame retardance, strong radiation resistance, super fatigue resistance and the like, can be used for a long time under extreme conditions of super high temperature, super low temperature, high salt fog, strong noise, strong corrosion, strong radiation and the like, and is widely applied to the fields of aerospace, aviation, microelectronics and the like. Because polyimide has low dielectric constant and good wave permeability, an additional wave absorber is generally required to be added to form an effective conductive network to realize broadband microwave absorption. The carbon material (nano carbon black, carbon nano tube, graphene and the like) has high dielectric loss, low density, high conductivity and excellent thermal and chemical stability, and can lose electromagnetic waves through electric conduction loss and polarization relaxation, so that the carbon material is a good candidate material for preparing the light microwave absorbing material. The carbon material is used as a wave absorber to be added into the polyimide foam material, so that the structure/invisible integrated functional composite material with light weight, high temperature stability, high mechanical strength and strong microwave response is expected to be produced.
Currently, laboratory acquisition of polyimide/carbon composite foams is mainly based on several methods: precursor powder foaming, phase inversion, freeze drying, impregnation, and the like. The precursor powder foaming method generally adds a wave absorber into polyimide foam precursor solid powder, uniformly mixes the powder by physical or mechanical means, and then foams the powder again, so that the problems of uneven materials, poor product stability and the like are easily generated. Phase inversion is a process in which a polymer solution undergoes mass transfer exchange between a solvent and a non-solvent in the surrounding environment by a certain physical method, and further phase separation occurs to be converted into a solid phase. The pore structure of the product can be controlled in the phase change process, but the wave absorber is easy to subside, and is usually used for preparing film products. The freeze-drying method generally comprises the steps of uniformly mixing a water-soluble PAA dispersion liquid and a wave absorber dispersion liquid, and obtaining the aerogel structure of the three-dimensional network through freeze-drying and subsequent heat treatment processes. The method mainly obtains a soft open-cell foam structure, and cannot prepare a structural wave-absorbing composite material with load-bearing characteristics. The impregnation method is to impregnate a polyimide foam having a certain shape into a uniform dispersion containing a wave absorber, and remove a solvent by subsequent drying to obtain a composite wave-absorbing foam, but the method is only suitable for a foam template having a high open cell content, and the load and dispersion uniformity of the absorber are difficult to improve.
Therefore, there is an urgent need to develop a reliable method for preparing the rigid polyimide wave-absorbing foam to meet the application requirements of the rigid polyimide foam in the fields of aerospace and the like. In general, domestic research on polyimide foam composite wave-absorbing materials is still in the beginning stage. In addition, the microwave frequency band mainly focused by the reported researches is the X-band, and the preparation of the polyimide foam wave-absorbing composite material for realizing strong absorption in the full frequency band of 2-18 GHz is still a significant challenging subject.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a preparation method of broadband high-temperature-resistant structural polyimide composite wave-absorbing foam, which not only can ensure that materials obtain good mechanical properties and broadband wave-absorbing effects, but also has the advantages of simple and convenient operation, low production cost and potential application prospect.
In order to achieve the above purpose, the invention adopts the following technical scheme:
the broadband high-temperature-resistant structural polyimide composite wave-absorbing foam comprises the following raw materials in parts by weight: 100 parts of polyimide dianhydride monomer, 80-90 parts of polyisocyanate, 200-250 parts of solvent, 1.5-2.5 parts of catalyst, 2.5-4.5 parts of silicone oil, 10-15 parts of foaming agent and 0.5-20 parts of wave absorber.
A preparation method of broadband high-temperature-resistant structural polyimide composite wave-absorbing foam comprises the following steps:
1) Polyimide dianhydride monomer is dissolved in polar solvent at a certain temperature to obtain polyimide dianhydride monomer solution;
2) Adding a proper amount of catalyst, silicone oil and foaming agent into the polyimide dianhydride monomer solution obtained in the step 1), stirring to uniformly mix, then adding a wave absorbing agent accounting for 0.5-20wt% of the polyimide dianhydride monomer, and fully stirring to form uniform slurry serving as a component A;
3) Adding a wave absorber accounting for 0.5-20wt% of the weight of the polyisocyanate and the polyisocyanate into a proper amount of polar solvent to uniformly disperse the wave absorber in emulsion to be used as a component B;
4) Adding the component B into the component A in batches, continuously stirring until the system product has obvious lines, pouring the polymerization product into an open stainless steel mold, heating in an oven for foaming and curing to obtain a foam precursor;
5) And 5) aminating the foam precursor obtained in the step 4) by high Wen Xianya to obtain the polyimide composite wave-absorbing foam.
The wave absorber is one or more of carbon black nano particles, graphene and carbon nano tubes. Preferably, the wave absorber comprises carbon black nano particles, graphene and carbon nanotubes, wherein the mass ratio of the carbon black nano particles to the graphene to the carbon nanotubes is 1 (0.05-0.2) (0.1-0.6).
The polyimide dianhydride monomer is one or more of pyromellitic dianhydride (PMDA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and 4,4' -oxydiphthalic anhydride (ODPA).
The polar solvent is one or more of N, N-Dimethylformamide (DMF), N, N-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP).
The polyisocyanate is one or more of Toluene Diisocyanate (TDI), diphenylmethane-4, 4' -diisocyanate (MDI) and polymethylene polyphenyl polyisocyanate (PAPI).
The catalyst is at least one selected from dibutyl tin diacetate, dibutyl tin dilaurate, triethanolamine, triethylamine and triethylene diamine.
The foaming agent is cyclopentane.
Preferably, the polyimide dianhydride monomer is 3,3', 4' -benzophenone tetracarboxylic dianhydride, the polar solvent is N, N-dimethylformamide, the catalyst is triethylene diamine, and the isocyanate is polymethylene polyphenyl polyisocyanate.
In the step 3), the foaming temperature is 50-70 ℃ and the curing time is 12-15 h.
In step 4), the imidization conditions are: 120 ℃/1 to 2 hours, 150 ℃/1 to 2 hours, 180 ℃/0.5 to 1.5 hours, 220 ℃/0.5 to 1 hour, 350 ℃/0.5 to 1 hour
Compared with the prior art, the technical scheme of the invention has the beneficial effects that:
1. the slurry phase polymerization-foaming integrated method provided by the invention can effectively avoid the defects of sedimentation, non-uniformity, unstable performance and the like of wave-absorbing agents existing in other methods, and is hopeful to realize strong absorption of broadband microwaves in a smaller thickness.
2. The broadband high-temperature-resistant structural polyimide composite wave-absorbing foam provided by the invention has the advantages that the three-dimensional porous structure can enable the composite material to have a proper impedance matching value, so that microwaves can enter the material as much as possible under the condition of almost no reflection, and in addition, the multiple internal reflection and propagation caused by the three-dimensional porous structure are beneficial to dissipation of microwave energy; the carbon nanomaterial has excellent dielectric properties and can consume energy of incident microwaves through polarization, multiple scattering and leakage conductance among particles. The three-dimensional crosslinked conductive network formed by adding a certain content of carbon nano material into the polyimide foam system as a wave absorber can obviously enhance the conduction loss, and meanwhile, various interfaces formed between the carbon nano material and polyimide can enhance the dielectric loss, so that the wave absorbing performance of the polyimide foam material is greatly improved.
3. The one-step in-situ polymerization method provided by the invention can embed the conductive nano particles into the polymer skeleton, thereby improving the overall conductivity of the material, enhancing the wave absorbing performance of the material and improving the mechanical property of the material.
4. The polyimide foam composite wave-absorbing material obtained by the invention can resist high temperature of more than 500 ℃, and is particularly suitable for wave-absorbing material products resistant to high temperature; under the single-layer matching thickness, the effective absorption bandwidth (RL < -10 dB) can cover the frequency band of 3-18 GHz;
5. the polyimide foam composite wave-absorbing material obtained by the invention has excellent mechanical property, and the compression deformation of the polyimide foam composite wave-absorbing material is 10 percent, and the compression strength of the polyimide foam composite wave-absorbing material reaches 0.63MPa.
6. The nano carbon black particles used in the invention have low price and wide sources, can greatly reduce the production cost of the polyimide foam composite wave-absorbing material, and have good economic benefit and certain production application prospect.
Drawings
Fig. 1 is an SEM image of the polyimide foam composite wave-absorbing material obtained in example 1.
Fig. 2 is a thermal weight loss curve of the polyimide foam composite wave-absorbing material obtained in example 1.
Fig. 3 is a test result of the wave absorbing performance of the polyimide foam composite wave absorbing material obtained in example 1.
Fig. 4 is a graph showing the mechanical properties of the polyimide foam composite wave-absorbing material obtained in example 1.
Detailed Description
In order to make the technical problems, technical schemes and beneficial effects to be solved more clear and obvious, the invention is further described in detail below with reference to the accompanying drawings and embodiments.
All the raw materials of the present invention are not particularly limited in their sources, and may be purchased on the market or prepared according to conventional methods well known to those skilled in the art.
Example 1
60g of 3,3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) was dissolved in 75g of N, N-dimethylformamide at 110℃in an oil bath, and then 1.2g of catalyst, 2.0g of silicone oil and 7g of cyclopentane were added thereto, followed by stirring to obtain an orange transparent solution. Then adding 3g of nano carbon black accounting for 5wt% of the BTDA mass, 1.8g of carbon nano tube accounting for 3wt% of the BTDA mass and 0.6g of graphene accounting for 1wt% of the BTDA mass into the mixture as a wave absorbing agent, and continuously stirring the mixture for a period of time to form uniform slurry which is recorded as a component A;
50g of polymethylene polyphenyl polyisocyanate (PAPI) is added into 40g of N, N-dimethylformamide, then 2.5g of nano carbon black accounting for 5wt% of the mass of the PAPI, 1.5g of carbon nano tube accounting for 3wt% of the mass of the PAPI and 0.5g of graphene accounting for 1wt% of the mass of the PAPI are added into the mixture as a wave absorber, and the mixture is continuously and uniformly stirred to obtain a component B;
and (3) adding the component B into the component A in batches under the room temperature condition, carrying out in-situ polymerization with mechanical stirring, pouring the polymerized product into an open stainless steel mold preheated to 60 ℃ in advance after obvious lines (3 h) appear on the product, and then placing the stainless steel mold filled with the polymerized product into an oven at 60 ℃ for foaming and curing. After curing for 12-15 h, taking out the product to obtain a foam precursor, and then respectively heating at 120 ℃,150 ℃,180 ℃,220 ℃ and 350 ℃ for 2h, 1.5h, 1h and 1h to carry out thermal imidization to finally obtain the polyimide composite wave-absorbing foam.
Example 2
The other steps of this example are the same as in example 1, except that the wave absorber in components A and B is 1wt% of nano carbon black.
Example 3
The other steps of this example are the same as in example 1, except that the wave absorber in components A and B is 3wt% of nano carbon black.
Example 4
The other steps of this example are the same as in example 1, except that the wave absorber in components A and B is 5wt% of nano carbon black.
Example 5
The other steps of this example are the same as in example 1, except that the wave absorber in components A and B is 7wt% of nano carbon black.
Example 6
The other steps of this example are the same as in example 1, except that the wave absorber in components A and B is 10wt% of nano carbon black.
Example 7
The other steps of this example are the same as in example 1, except that the wave-absorbing agent in components A and B is 1wt% of carbon nanotubes.
Example 8
The other steps of this example are the same as in example 1, except that the wave-absorbing agent in components A and B is 3wt% of carbon nanotubes.
Example 9
The other steps of this example are the same as in example 1, except that the wave-absorbing agent in components A and B is 5wt% of carbon nanotubes.
Example 10
The other steps of this example are the same as in example 1, except that the wave-absorbing agent in components A and B is 7wt% carbon nanotubes.
Example 11
The other steps of this example are the same as example 1, except that the wave absorber in components a and B is 0.5wt% graphene.
Example 12
The other steps of this example are the same as example 1, except that the wave absorber in components a and B is 1wt% graphene.
Example 13
The other steps of this example are the same as example 1, except that the wave absorber in components a and B is 1.5wt% graphene.
Example 14
The other steps of this example are the same as example 1, except that the wave absorber in components a and B is 2wt% graphene.
Example 15
The other steps of this example are the same as example 1, except that the wave-absorbing agent in components a and B is 7wt% of nano carbon black, 1wt% of carbon nanotube and 0.5wt% of graphene.
The prepared polyimide composite wave-absorbing foam (180 mm multiplied by 30 mm) is directly used for testing by an arch method, so that the wave-absorbing performance of the material at 2-18 GHz is obtained, and the test results are shown in Table 1.
TABLE 1
From the results shown in table 1, by constructing a multi-scale multi-layer composite system with coupling and synergistic effects of 0-dimensional nano carbon black, 1-dimensional carbon nano tube, 2-dimensional graphene and 3-dimensional foam structure, the wave-absorbing frequency bandwidth can be effectively widened, the re-stacking of graphene sheets and the winding aggregation of carbon nano tubes can be prevented, the effects of strong interface polarization and three-dimensional crosslinked conductive network of the carbon nano material hybrid system can be exerted to the greatest extent, the polarization loss and the conduction loss of the composite materials are enhanced, and the attenuation capability of the composite materials on incident electromagnetic waves is improved. The polyimide foam composite material obtained when the addition amounts of the nano carbon black, the carbon nano tube and the graphene are respectively 5wt%, 3wt% and 1wt% of the total mass of the monomer shows excellent wave absorbing performance.
Fig. 1 is an SEM image of the polyimide composite wave-absorbing foam prepared according to example 1.
Fig. 2 is a thermal weight loss curve of the polyimide composite wave-absorbing foam prepared according to example 1, and the temperature at the time of weight loss of 5% is 514.7 ℃, and the mass retention rate at 800 ℃ can reach 68%, which shows that the wave-absorbing foam has good high-temperature stability.
FIG. 3 is a test result of the wave absorbing performance of the polyimide composite wave absorbing foam prepared in an enlarged scale according to example 1, and the effective absorption band bandwidth (RL < -10 dB) of the wave absorbing foam is 15GHz, which almost covers the full frequency range of 2-18 GHz.
Fig. 4 is a mechanical property diagram of the polyimide foam composite wave-absorbing material prepared according to example 1, and the compression set of the polyimide foam composite wave-absorbing material is 10% and the compression strength reaches 0.63MPa, which shows that the wave-absorbing foam has good mechanical property and bearing property.
According to the invention, the carbon nanomaterial and the polyimide monomer are organically combined, the integrated polyimide foam wave-absorbing composite material is obtained through slurry phase polymerization and one-step foaming, and isocyanate is selected as one of the monomers to participate in polymerization reaction so as to enhance the mechanical property of the polyimide foam material. The one-step in-situ polymerization method has simple process and high efficiency, can effectively avoid the problems of sedimentation, uneven dispersion and the like of the wave absorbing agent, and is suitable for large-scale production; the porous structure cooperates with the dielectric loss capability of the carbon nanomaterial to effectively improve the impedance matching performance of the composite wave-absorbing foam, and is expected to be applied to the actual production of microwave absorbing materials.
The preparation method and the beneficial effects of the broadband high-temperature-resistant structural polyimide composite wave-absorbing foam provided by the invention are further described in detail in the above specific embodiments, and it should be pointed out that modifications, substitutions, improvements and the like of the specific embodiments are required to be within the protection scope of the invention on the basis of not deviating from the design ideas and principles of the invention.
Claims (10)
1. The preparation method of the broadband high-temperature-resistant structural polyimide composite wave-absorbing foam is characterized by comprising the following steps of:
1) Adding a catalyst, silicone oil, a foaming agent and a wave absorber into a polyimide dianhydride monomer solution to serve as a component A, wherein the added wave absorber accounts for 0.5-20% of the mass of the polyimide dianhydride monomer;
2) Adding polyisocyanate and a wave absorber into a polar solvent to serve as a component B, wherein the added wave absorber accounts for 0.5% -20% of the mass of the polyisocyanate;
3) Adding the component B into the component A in batches, continuously stirring until the system product has obvious lines, pouring the polymerization product into a mold, and then heating, foaming and curing to obtain a foam precursor;
4) Subjecting the foam precursor obtained in the step 3) to high Wen Xianya amination to obtain polyimide composite wave-absorbing foam;
in the step 1) and the step 2), the wave absorber is one or more of carbon black nano particles, graphene and carbon nano tubes.
2. The method for preparing the broadband high-temperature-resistant structural polyimide composite wave-absorbing foam according to claim 1, which is characterized in that: the wave absorber comprises carbon black nano particles, graphene and carbon nanotubes, wherein the mass ratio of the carbon black nano particles to the graphene to the carbon nanotubes is 1 (0.05-0.2) to 0.1-0.6.
3. The method for preparing the broadband high-temperature-resistant structural polyimide composite wave-absorbing foam according to claim 1, which is characterized in that: the polyimide dianhydride monomer is one or more of pyromellitic dianhydride (PMDA), 3', 4' -Benzophenone Tetracarboxylic Dianhydride (BTDA) and 4,4' -oxydiphthalic anhydride (ODPA).
4. The method for preparing the broadband high-temperature-resistant structural polyimide composite wave-absorbing foam according to claim 1, which is characterized in that: in the step 1), the solvent of the polyimide dianhydride monomer solution is a polar solvent; the polar solvent is one or more of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc) and N-methylpyrrolidone (NMP).
5. The method for preparing the broadband high-temperature-resistant structural polyimide composite wave-absorbing foam according to claim 1, which is characterized in that: the polar solvent is N, N-dimethylformamide.
6. The method for preparing the broadband high-temperature-resistant structural polyimide composite wave-absorbing foam according to claim 1, which is characterized in that: the catalyst is at least one selected from dibutyl tin diacetate, dibutyl tin dilaurate, triethanolamine, triethylamine and triethylene diamine; the foaming agent is cyclopentane.
7. The method for preparing the broadband high-temperature-resistant structural polyimide composite wave-absorbing foam according to claim 1, which is characterized in that: the polyisocyanate is one or more of Toluene Diisocyanate (TDI), diphenylmethane-4, 4' -diisocyanate (MDI) and polymethylene polyphenyl polyisocyanate (PAPI).
8. The method for preparing the broadband high-temperature-resistant structural polyimide composite wave-absorbing foam according to claim 1, which is characterized in that: the polyimide dianhydride monomer is 3,3', 4' -benzophenone tetracarboxylic dianhydride, the catalyst is triethylene diamine, and the polyisocyanate is polymethylene polyphenyl polyisocyanate.
9. The method for preparing the broadband high-temperature-resistant structural polyimide composite wave-absorbing foam according to claim 1, which is characterized in that: in the step 3), the foaming temperature is 50-70 ℃ and the curing time is 12-15 h.
10. The method for preparing the broadband high-temperature-resistant structural polyimide composite wave-absorbing foam according to claim 1, which is characterized in that: in step 4), the imidization conditions are: 120 ℃/1-2 h,150 ℃/1-2 h,180 ℃/0.5-1.5 h,220 ℃/0.5-1 h,350 ℃/0.5-1 h.
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