CN113527678B - Polyimide foam composite material and preparation method and application thereof - Google Patents
Polyimide foam composite material and preparation method and application thereof Download PDFInfo
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- 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
- C08G73/1071—Wholly aromatic polyimides containing oxygen in the form of ether bonds in the main chain
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- 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
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
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- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C08K3/00—Use of inorganic substances as compounding ingredients
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- C08K3/041—Carbon nanotubes
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- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
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- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K9/00—Screening of apparatus or components against electric or magnetic fields
- H05K9/0073—Shielding materials
- H05K9/0081—Electromagnetic shielding materials, e.g. EMI, RFI shielding
- H05K9/0083—Electromagnetic shielding materials, e.g. EMI, RFI shielding comprising electro-conductive non-fibrous particles embedded in an electrically insulating supporting structure, e.g. powder, flakes, whiskers
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- C—CHEMISTRY; METALLURGY
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- 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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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2265—Oxides; Hydroxides of metals of iron
- C08K2003/2275—Ferroso-ferric oxide (Fe3O4)
Abstract
The invention discloses a polyimide foam composite material and a preparation method and application thereof. The method comprises the following steps: (1) Mixing carbon nanotube and Fe 3 O 4 And 4,4-diaminodiphenyl ether are added into the organic solvent and mixed to form uniform suspension; (2) Adding pyromellitic dianhydride into the suspension obtained in the step (1) for multiple times, and reacting for 3-5 hours to obtain a polyamic acid solution; (3) And coating the polyamic acid solution on a substrate, carrying out coagulation bath for 3-5 h, then carrying out gradient temperature rise under the condition of inert gas or nitrogen, and carrying out imidization to obtain the polyimide foam composite material. The compounding of the polymer foam material with high and low temperature resistance, flexibility and excellent tensile property and the conductive electromagnetic conductive material with high electromagnetic shielding property is realized by compounding the carbon nano tube, the carbonyl iron nano particle and the polymer foam. The invention has simple preparation process and certain industrialization possibility, and has certain value in the application of electromagnetic shielding materials.
Description
Technical Field
The invention belongs to the field of polymer composite materials, and particularly relates to a polyimide foam composite material, and a preparation method and application thereof.
Background
With the rapid development of modern high and new technologies such as internet +, cloud computing, big data, artificial intelligence, 5G and the like, various commercial and household electronic devices are continuously popularized, so that electronic devices used daily are easily interfered by external electromagnetic waves. Meanwhile, electromagnetic waves are emitted to the outside by ubiquitous electronic equipment, so that the living environment of people is secretly under the electromagnetic pollution cage. However, electronic devices are developed toward intellectualization, miniaturization, integration and light weight, and higher requirements are made on electromagnetic shielding materials. The traditional electromagnetic shielding material at present has the defects of high filling amount, poor filler dispersibility, mechanical property which can not reach the practical application strength and the like.
Since the discovery of carbon materials, they have been widely studied in the fields of electronic information, life science, environmental governance, aerospace, etc., and nanocarbon materials represented by three-dimensional carbon material fullerenes, two-dimensional material graphene, and one-dimensional material carbon nanotubes have surface effects, small-size effects, macroscopic quantum tunneling effects, and quantum confinement effects different from those of macroscopic materials, so that they have high strength, low density, excellent electrical and thermal conductivity, etc., and thus they are often used as materials for preparing materials having properties of light, electricity, magnetism, heat, mechanics, machinery, etc. However, in these composite materials, the nano-filler is difficult to form a good conductive path, and the filler has a single performance, so that in order to enhance the conductive performance and further enhance the electromagnetic shielding effect, only a large amount of electrically lossy materials and less magnetically lossy materials can be added, thereby affecting the mechanical properties and the narrow frequency bandwidth of the composite materials.
Constructing an effective conductive network and a filler that increases magnetic losses is an effective way to address the excessive use of composite fillers and to broaden the frequency band. Each carbon atom on the carbon nanotube adopts sp 2 And hybridizing and combining the carbon-carbon delta bonds with each other to form a honeycomb structure consisting of hexagons as a framework of the carbon nano tube. A pair of p electrons which do not participate in hybridization on each carbon atom form conjugated pi electron cloud which spans the whole carbon nano tube, so that the carbon nano tube has excellent conductivity.
At present, the practical application can be achieved only by the filling type electromagnetic shielding composite material with over-high filling load (generally more than 50 percent)The electromagnetic shielding standard results in poor mechanical performance and high cost of the electromagnetic shielding material. Besides, in order to enhance the bandwidth, nano-magnetic particles Fe with magnetic loss and high conductivity are introduced 3 O 4 . With the load of the conductive and magnetic conductive nano filler on the polymer foam, the foam material has excellent electromagnetic shielding performance and mechanical and thermal properties.
Therefore, the invention aims to prepare the composite material with high-efficiency shielding performance and excellent mechanical and thermal properties and expand the application of the composite material in the fields of polymer composite materials and electromagnetic shielding.
Disclosure of Invention
In order to overcome the defects and shortcomings of the existing electromagnetic shielding material such as high filler load, low performance and poor mechanical and thermal properties, the invention aims to provide a preparation method of a polyimide foam composite material.
The invention also aims to provide a polyimide foam composite material prepared by the method.
The invention further aims to provide application of the polyimide foam composite material in the field of electromagnetic shielding.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a polyimide foam composite material comprises the following steps:
(1) Mixing carbon nanotube and Fe 3 O 4 And 4,4-diaminodiphenyl ether are added into an organic solvent and mixed to form a uniform suspension;
(2) Under the stirring state, adding pyromellitic dianhydride into the suspension in the step (1) for multiple times, and reacting for 3-5 hours to obtain a polyamic acid solution;
(3) And coating the polyamic acid solution on a substrate, carrying out coagulation bath for 3-5 h, then carrying out gradient temperature rise under the condition of inert gas or nitrogen, and carrying out imidization to obtain the polyimide foam composite material.
Preferably, the carbon nanotubes obtained in step (1) are polyaniline-modified carbon nanotubes, wherein the mass ratio of polyaniline to carbon nanotubes is 1: (0.5 to 1.0), more preferably 1:0.8.
preferably, said Fe of step (1) 3 O 4 Fe modified for polydopamine 3 O 4 Wherein polydopamine is in combination with Fe 3 O 4 The mass ratio of (1): (3 to 6), more preferably 1:5.
preferably, the carbon nanotubes and Fe in the step (1) 3 O 4 And 4,4-diaminodiphenyl ether in a mass ratio of 1:1: (2 to 20), more preferably 1:1: (3 to 19), most preferably 1:1:3.14 to 6.3; the carbon nanotube and Fe 3 O 4 The mass ratio of the total mass to the organic solvent is 1:15 to 185, more preferably 1:18 to 179; most preferably.
Preferably, the organic solvent in step (1) is N, N-dimethylacetamide.
Preferably, the mixing mode in the step (1) is ultrasonic and mechanical stirring, and the ultrasonic time is 10-40 min.
Preferably, the molar ratio of 4,4-diaminodiphenyl ether in step (1) to pyromellitic anhydride in step (2) is 1:1 to 1.2, more preferably 1: (1.11-1.12).
Preferably, the rotation speed of the stirring in the step (2) is 200-600r/min, and the rotation speed of the pyromellitic anhydride is increased by 50-150r/min every time.
Preferably, the pyromellitic anhydride in the step (2) is added for 3 to 6 times, and the interval of each time is 5 to 15min.
And (3) gradually thickening the mixed solution in the reaction process of the step (2) to generate a climbing rod effect.
Preferably, the temperature of the reaction in step (2) is room temperature.
Preferably, the solid content of the polyamic acid solution in the step (3) is 10 to 15%.
Preferably, the coating method in the step (3) is a doctor blade method.
Preferably, the substrate in step (3) is a glass plate.
Preferably, the solvent of the coagulating bath in the step (3) is ethanol and water, and the volume ratio of ethanol to water is 1: (1-2), more preferably 1:1.5; the temperature was room temperature.
Preferably, the gradient temperature rise in the step (3) is that the temperature rises from room temperature to 80 ℃ in the first stage, then the temperature is kept at 80 ℃ for 30min, the temperature rises from 80 ℃ to 150 ℃ in the second stage, the temperature is kept at 150 ℃ for 30min, the temperature rises from 150 ℃ to 250 ℃ in the third stage, the temperature is kept at 250 ℃ for 30min, and the temperature rises from 250 ℃ to 375 ℃ in the fourth stage, and the temperature is kept at 375 ℃ for 30min.
The polyimide foam composite material prepared by the method.
The polyimide foam composite material is applied to the field of electromagnetic shielding.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) According to the polyimide composite foam material prepared by the method, the polyaniline-modified carbon nano tube is used as a conductive filler, the polydopamine-modified ferroferric oxide nano particles are used as a magnetic filler to form a continuous load on a polyimide foam framework, a three-dimensional continuous conductive and magnetic network is formed, the mechanical property of the foam polymer is enhanced by the carbon nano tube, and the maximization of the electromagnetic screen performance is ensured by the electric loss and the magnetic loss.
(2) The preparation method provided by the invention has the advantages of low cost, simple process, safety, no toxicity and the like, can be used for preparing the composite material with electromagnetic shielding performance and excellent mechanical performance, has high exploitable potential value, and provides an effective solution for the manufacture of the electromagnetic shielding material.
(3) The polymer has excellent mechanical property and flexibility, because the reflection of electromagnetic waves is increased by the porous foam structure, the electric loss of the electromagnetic waves is increased by loading three-dimensional continuous carbon nano tubes between the foam framework and the framework, and the magnetic loss of the electromagnetic waves is increased by the magnetic particles, so that the electromagnetic waves gradually consume energy in the composite material to form the absorption of the electromagnetic waves. The compounding of the polymer foam material with high and low temperature resistance, flexibility and excellent tensile property and the conductive magnetic material with high electromagnetic shielding property is realized by compounding the carbon nano tube, the carbonyl iron nano particle and the polymer foam.
Drawings
FIG. 1 is a scanning electron microscope photograph of the surface of the polyimide foam composite of example 1.
FIG. 2 is a scanning electron microscope image of a cross section of the polyimide foam composite of example 1 without liquid nitrogen freezing.
FIG. 3 is a scanning electron microscope cross-sectional view of the polyimide foam composite of example 1 frozen by liquid nitrogen.
FIG. 4 is a diagram showing the effect of flexibility of the polyimide foam composite obtained in example 1.
FIG. 5 is a thermogravimetric plot of the polyimide foam composite obtained in example 1.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Those who do not specify specific conditions in the examples of the present invention follow conventional conditions or conditions recommended by the manufacturer. The raw materials, reagents and the like which are not indicated for manufacturers are all conventional products which can be obtained by commercial purchase.
The coating methods described in the examples are all doctor blade methods.
Example 1
1.0g of carbon nanotubes was added to 50ml of an HCl solution (1.0 mol/L) containing ammonium persulfate at a concentration of 40.0 mg-ml in the HCl solution -1 Adding 0.8g of aniline, reacting at 0 ℃ for 6h at a stirring speed of 400r/min, washing with deionized water for multiple times, separating at a rotating speed of 8000r/min, and finally drying at 50 ℃ in vacuum to constant weight to obtain the polyaniline-modified carbon nanotube. 2.0g of magnetic Fe 3 O 4 Adding the nanoparticles into 50ml of Tris-HCl buffer solution containing dopamine, wherein the concentration of the dopamine in the Tris-HCl buffer solution is 8.0 mg-ml -1 The pH value of Tris-HCl buffer solution is 8.5, ultrasonic treatment is carried out for 20 minutes, the reaction is carried out for 8 hours at room temperature at the stirring speed of 600r/min, and the Fe modified by polydopamine is obtained after repeated deionized water washing, 6000r/min rotating speed separation and finally vacuum drying at 50 ℃ to constant weight 3 O 4 。
0.056g polyaniline-modified carbon nanotube and 0.056g polydopamine-modified F are weighede 3 O 4 And 1.06g of 4, 4-diaminodiphenyl ether are respectively dispersed in 5g, 5g and 10g of N, N-dimethylacetamide, and the mixture is poured into the same container for mechanical stirring after ultrasonic dispersion for 30min at the rotating speed of 200r/min to form uniform suspension. Adding 1.18g of pyromellitic dianhydride into the suspension for three times at intervals of 5 minutes, increasing the rotating speed by 80r/min for each addition, and reacting for 5 hours at room temperature to form polyamic acid with the solid content of 10%, wherein the filler (polyaniline-modified carbon nanotube and polydopamine-modified Fe) 3 O 4 ) The mass ratio to the polymer foam (4,4-diaminodiphenyl ether plus pyromellitic anhydride) is 5:100. after the polyamic acid solution with the solid content of 10% is coated on a clean glass plate, the plate is placed in a state that the volume ratio of ethanol to water is 2:3, standing for 3 hours at room temperature, finally placing the polyimide foam composite material in an atmosphere furnace, and performing gradient temperature rise under the protection of argon, wherein the gradient temperature rise is that the temperature rises from the room temperature to 80 ℃ in the first stage, then the temperature is kept for 30min at 80 ℃, the temperature rises from 80 ℃ to 150 ℃ in the second stage, the temperature is kept for 30min at 150 ℃, the temperature rises from 150 ℃ to 250 ℃ in the third stage, the temperature is kept for 30min at 250 ℃, the temperature rises from 250 ℃ to 375 ℃ in the fourth stage, and the temperature is kept for 30min at 375 ℃, so that the polyimide foam composite material is finally obtained. The aperture of the obtained composite material pore is 2-5 μm, the tensile strength is more than or equal to 26MPa, and the electromagnetic shielding effectiveness is more than or equal to 7dB.
Example 2
1.0g of carbon nanotubes was added to 50ml of an HCl solution (1.0 mol/L) containing ammonium persulfate at a concentration of 40.0 mg-ml in the HCl solution -1 Adding 0.8g of aniline, reacting at 0 ℃ for 6h at a stirring speed of 400r/min, washing with deionized water for multiple times, separating at a rotating speed of 8000r/min, and finally drying at 50 ℃ in vacuum to constant weight to obtain the polyaniline-modified carbon nanotube. 2.0g of magnetic Fe 3 O 4 Adding the nanoparticles into 50ml of Tris-HCl buffer solution containing dopamine, wherein the concentration of the dopamine in the Tris-HCl buffer solution is 8.0 mg-ml -1 The pH value of Tris-HCl buffer solution is 8.5, the reaction is carried out for 20 minutes by ultrasonic treatment at the stirring speed of 600r/min for 8 hours at room temperature, and the polydopamine modified Fe is obtained after repeated deionized water washing, 6000r/min rotating speed separation and final vacuum drying at 50 ℃ to constant weight 3 O 4 。
Weighing 0.168g polyaniline-modified carbon nanotube and 0.168g polydopamine-modified Fe 3 O 4 And 1.06g of 4, 4-diaminodiphenyl ether are respectively dispersed in 5g, 5g and 10g of N, N-dimethylacetamide, and the mixture is poured into the same container for mechanical stirring after ultrasonic dispersion for 30min at the rotating speed of 200r/min to form uniform suspension. Adding 1.18g of pyromellitic dianhydride into the suspension for three times at intervals of 5 minutes, increasing the rotating speed by 80r/min for each addition, and reacting for 5 hours at room temperature to form polyamic acid with the solid content of 10%, wherein the filler (polyaniline-modified carbon nanotube and polydopamine-modified Fe) 3 O 4 ) The mass ratio to the polymer foam (4,4-diaminodiphenyl ether plus pyromellitic anhydride) was 15:100. after the polyamic acid solution with the solid content of 10% is coated on a clean glass plate, the plate is placed in a state that the volume ratio of ethanol to water is 2:3, standing for 3 hours at room temperature, finally placing the polyimide foam composite material in an atmosphere furnace, and performing gradient temperature rise under the protection of argon, wherein the gradient temperature rise is from room temperature to 80 ℃ in the first stage, then keeping the temperature at 80 ℃ for 30min, from 80 ℃ to 150 ℃ in the second stage, from 150 ℃ to 150 ℃ for 30min, from 150 ℃ to 250 ℃ in the third stage, from 250 ℃ to 250 ℃ for 30min, from 250 ℃ to 375 ℃ in the fourth stage, and keeping the temperature at 375 ℃ for 30min, thus finally obtaining the polyimide foam composite material. The aperture of the obtained composite material pore is 4-7 μm, the tensile strength is more than or equal to 22MPa, and the electromagnetic shielding effectiveness is more than or equal to 21dB.
Example 3
1.0g of carbon nanotubes was added to 50ml of an HCl solution (1.0 mol/L) containing ammonium persulfate at a concentration of 40.0 mg-ml in the HCl solution -1 Adding 0.8g of aniline, reacting at 0 ℃ for 6h at a stirring speed of 400r/min, washing with deionized water for multiple times, separating at a rotating speed of 8000r/min, and finally drying at 50 ℃ in vacuum to constant weight to obtain the polyaniline-modified carbon nanotube. 2.0g of magnetic Fe 3 O 4 Adding the nanoparticles into 50ml of Tris-HCl buffer solution containing dopamine, wherein the concentration of the dopamine in the Tris-HCl buffer solution is 8.0 mg-ml -1 The pH value of the Tris-HCl buffer solution is 8.5, the mixture is subjected to ultrasonic treatment for 20 minutes, and the mixture reacts for 8 hours at room temperature at the stirring speed of 600r/min for a plurality of timesWashing with deionized water, separating at 6000r/min, and vacuum drying at 50 deg.C to constant weight to obtain polydopamine-modified Fe 3 O 4 。
Weighing 0.336g polyaniline-modified carbon nanotube and 0.336g polydopamine-modified Fe 3 O 4 And 1.06g of 4, 4-diaminodiphenyl ether are respectively dispersed in 5g, 5g and 10g of N, N-dimethylacetamide, and the mixture is poured into the same container for mechanical stirring after ultrasonic dispersion for 30min at the rotating speed of 200r/min to form uniform suspension. Adding 1.18g of pyromellitic dianhydride into the suspension for three times at intervals of 5 minutes, increasing the rotating speed by 80r/min for each addition, and reacting for 5 hours at room temperature to form polyamic acid with the solid content of 10%, wherein the filler (polyaniline-modified carbon nanotube and polydopamine-modified Fe) 3 O 4 ) The mass ratio to the polymer foam (4,4-the sum of diaminodiphenyl ether and pyromellitic anhydride) was 30:100. after the polyamic acid solution with the solid content of 10% is coated on a clean glass plate, the plate is placed in a state that the volume ratio of ethanol to water is 2:3, standing for 3 hours at room temperature, finally placing the polyimide foam composite material in an atmosphere furnace, and performing gradient temperature rise under the protection of argon, wherein the gradient temperature rise is that the temperature rises from the room temperature to 80 ℃ in the first stage, then the temperature is kept for 30min at 80 ℃, the temperature rises from 80 ℃ to 150 ℃ in the second stage, the temperature is kept for 30min at 150 ℃, the temperature rises from 150 ℃ to 250 ℃ in the third stage, the temperature is kept for 30min at 250 ℃, the temperature rises from 250 ℃ to 375 ℃ in the fourth stage, and the temperature is kept for 30min at 375 ℃, so that the polyimide foam composite material is finally obtained. The aperture of the obtained composite material pore is 4-8 μm, the tensile strength is more than or equal to 16MPa, and the electromagnetic shielding effectiveness is more than or equal to 43dB.
Example 4
1.0g of carbon nanotubes was added to 50ml of an HCl solution (1.0 mol/L) containing ammonium persulfate at a concentration of 40.0 mg-ml in the HCl solution -1 Adding 0.8g of aniline, reacting at 0 ℃ for 6h at a stirring speed of 400r/min, washing with deionized water for multiple times, separating at a rotating speed of 8000r/min, and finally drying at 50 ℃ in vacuum to constant weight to obtain the polyaniline-modified carbon nanotube. 2.0g of magnetic Fe 3 O 4 Adding the nanoparticles into 50ml of Tris-HCl buffer solution containing dopamine, wherein the concentration of the dopamine in the Tris-HCl buffer solution is 8.0mg·ml -1 The pH value of Tris-HCl buffer solution is 8.5, the reaction is carried out for 20 minutes by ultrasonic treatment at the stirring speed of 600r/min for 8 hours at room temperature, and the polydopamine modified Fe is obtained after repeated deionized water washing, 6000r/min rotating speed separation and final vacuum drying at 50 ℃ to constant weight 3 O 4 。
0.088g of polyaniline-modified carbon nanotube and 0.088g of polydopamine-modified Fe 3 O 4 1.66g of 4, 4-diaminodiphenyl ether is respectively dispersed in 5g, 5g and 10g of N, N-dimethylacetamide, and the mixture is poured into the same container for mechanical stirring after ultrasonic dispersion for 30min at the rotating speed of 300r/min to form uniform suspension. Adding 1.86g of pyromellitic dianhydride into the suspension for three times at intervals of 5 minutes, increasing the rotating speed by 100r/min every time of adding, and reacting for 5 hours at room temperature to form polyamic acid with the solid content of 15%, wherein the filler (polyaniline-modified carbon nanotube and polydopamine-modified Fe) 3 O 4 ) The mass ratio to the polymer foam (4,4-diaminodiphenyl ether plus pyromellitic anhydride) is 5:100. after the polyamic acid solution with the solid content of 15% is coated on a clean glass plate, the plate is placed in a state that the volume ratio of ethanol to water is 2:3, standing for 3 hours at room temperature, finally placing the polyimide foam composite material in an atmosphere furnace, and performing gradient temperature rise under the protection of argon, wherein the gradient temperature rise is from room temperature to 80 ℃ in the first stage, then keeping the temperature at 80 ℃ for 30min, from 80 ℃ to 150 ℃ in the second stage, from 150 ℃ to 150 ℃ for 30min, from 150 ℃ to 250 ℃ in the third stage, from 250 ℃ to 250 ℃ for 30min, from 250 ℃ to 375 ℃ in the fourth stage, and keeping the temperature at 375 ℃ for 30min, thus finally obtaining the polyimide foam composite material. The aperture of the obtained composite material pore is 3-6 μm, the tensile strength is more than or equal to 23MPa, and the electromagnetic shielding effectiveness is more than or equal to 9dB.
Example 5
1.0g of carbon nanotubes was added to 50ml of an HCl solution (1.0 mol/L) containing ammonium persulfate at a concentration of 40.0 mg-ml in the HCl solution -1 Adding 0.8g of aniline, reacting at 0 ℃ for 6h at a stirring speed of 400r/min, washing with deionized water for multiple times, separating at a rotating speed of 8000r/min, and finally drying at 50 ℃ in vacuum to constant weight to obtain the polyaniline-modified carbon nanotube. 2.0g of magnetic Fe 3 O 4 Adding the nanoparticles into 50ml of Tris-HCl buffer solution containing dopamine, wherein the concentration of the dopamine in the Tris-HCl buffer solution is 8.0 mg-ml -1 The pH value of Tris-HCl buffer solution is 8.5, the reaction is carried out for 20 minutes by ultrasonic treatment at the stirring speed of 600r/min for 8 hours at room temperature, and the polydopamine modified Fe is obtained after repeated deionized water washing, 6000r/min rotating speed separation and final vacuum drying at 50 ℃ to constant weight 3 O 4 。
0.264g of polyaniline-modified carbon nanotube and 0.264g of polydopamine-modified Fe 3 O 4 1.66g of 4, 4-diaminodiphenyl ether is respectively dispersed in 5g, 5g and 10g of N, N-dimethylacetamide, and the mixture is poured into the same container for mechanical stirring after ultrasonic dispersion for 30min at the rotating speed of 300r/min to form uniform suspension. Adding 1.86g of pyromellitic dianhydride into the suspension for three times at intervals of 5 minutes, increasing the rotating speed by 100r/min every time of adding, and reacting for 5 hours at room temperature to form polyamic acid with the solid content of 15%, wherein the filler (polyaniline-modified carbon nanotube and polydopamine-modified Fe) 3 O 4 ) With polymer foam (4,4-diaminodiphenyl ether) and the sum of pyromellitic anhydride) in a mass ratio of 15:100. after the polyamic acid solution with the solid content of 15% is coated on a clean glass plate, the plate is placed in a state that the volume ratio of ethanol to water is 2:3, standing for 3 hours at room temperature, finally placing the polyimide foam composite material in an atmosphere furnace, and performing gradient temperature rise under the protection of argon, wherein the gradient temperature rise is that the temperature rises from the room temperature to 80 ℃ in the first stage, then the temperature is kept for 30min at 80 ℃, the temperature rises from 80 ℃ to 150 ℃ in the second stage, the temperature is kept for 30min at 150 ℃, the temperature rises from 150 ℃ to 250 ℃ in the third stage, the temperature is kept for 30min at 250 ℃, the temperature rises from 250 ℃ to 375 ℃ in the fourth stage, and the temperature is kept for 30min at 375 ℃, so that the polyimide foam composite material is finally obtained. The aperture of the obtained composite material pore is 2-4 μm, the tensile strength is more than or equal to 19MPa, and the electromagnetic shielding effectiveness is more than or equal to 23dB.
Example 6
1.0g of carbon nanotubes was added to 50ml of an HCl solution (1.0 mol/L) containing ammonium persulfate at a concentration of 40.0 mg-ml in the HCl solution -1 Adding 0.8g aniline, reacting at 0 deg.C for 6h at a stirring speed of 400r/min, washing with deionized water for several times, and rotating at 8000r/minAnd (4) separating, and finally drying at 50 ℃ in vacuum to constant weight to obtain the polyaniline-modified carbon nanotube. 2.0g of magnetic Fe 3 O 4 Adding the nanoparticles into 50ml of Tris-HCl buffer solution containing dopamine, wherein the concentration of the dopamine in the Tris-HCl buffer solution is 8.0 mg-ml -1 The pH value of Tris-HCl buffer solution is 8.5, the reaction is carried out for 20 minutes by ultrasonic treatment at the stirring speed of 600r/min for 8 hours at room temperature, and the polydopamine modified Fe is obtained after repeated deionized water washing, 6000r/min rotating speed separation and final vacuum drying at 50 ℃ to constant weight 3 O 4 。
0.528g of polyaniline-modified carbon nano-tube and 0.528g of polydopamine-modified Fe 3 O 4 1.66g of 4, 4-diaminodiphenyl ether is respectively dispersed in 5g, 5g and 10g of N, N-dimethylacetamide, and the mixture is poured into the same container for mechanical stirring after ultrasonic dispersion for 30min at the rotating speed of 300r/min to form uniform suspension. Adding 1.86g of pyromellitic dianhydride into the suspension for three times at intervals of 5 minutes, increasing the rotating speed by 100r/min every time of adding, and reacting for 5 hours at room temperature to form polyamic acid with the solid content of 15%, wherein the filler (polyaniline-modified carbon nanotube and polydopamine-modified Fe) 3 O 4 ) The mass ratio to the polymer foam (4,4-the sum of diaminodiphenyl ether and pyromellitic anhydride) was 30:100. after the polyamic acid solution with the solid content of 15% is coated on a clean glass plate, the clean glass plate is placed in a state that the volume ratio of ethanol to water is 2:3, standing for 3 hours at room temperature, finally placing the polyimide foam composite material in an atmosphere furnace, and performing gradient temperature rise under the protection of argon, wherein the gradient temperature rise is that the temperature rises from the room temperature to 80 ℃ in the first stage, then the temperature is kept for 30min at 80 ℃, the temperature rises from 80 ℃ to 150 ℃ in the second stage, the temperature is kept for 30min at 150 ℃, the temperature rises from 150 ℃ to 250 ℃ in the third stage, the temperature is kept for 30min at 250 ℃, the temperature rises from 250 ℃ to 375 ℃ in the fourth stage, and the temperature is kept for 30min at 375 ℃, so that the polyimide foam composite material is finally obtained. The aperture of the obtained composite material pore is 3-5 μm, the tensile strength is more than or equal to 15MPa, and the electromagnetic shielding effectiveness is more than or equal to 44dB.
Comparative example 1
The volume ratio of ethanol to water of the coagulation bath in example 6 was 2:3 is changed to 0: and 3, the other conditions are completely the same as those in the embodiment 6, and the polyimide foam composite material is finally obtained, has no obvious porous structure, and has the electromagnetic shielding efficiency of less than or equal to 13dB which is far lower than the performance of the embodiment 6.
Comparative example 2
0.528g of carbon nanotubes which are not modified by polyaniline and 0.528g of Fe which is not modified by polydopamine 3 O 4 1.66g of 4, 4-diaminodiphenyl ether is respectively dispersed in 5g, 5g and 10g of N, N-dimethylacetamide, and the mixture is poured into the same container for mechanical stirring after ultrasonic dispersion for 30min at the rotating speed of 300r/min to form uniform suspension. Adding 1.86g of pyromellitic dianhydride into the suspension for three times at intervals of 5 minutes, increasing the rotating speed by 100r/min for each addition, and reacting for 5 hours at room temperature to form polyamic acid with the solid content of 15%, wherein the filler (the carbon nano tube and the Fe) is filled in the polyamic acid 3 O 4 ) The mass ratio to the polymer foam (4,4-the sum of diaminodiphenyl ether and pyromellitic anhydride) was 30:100. after the polyamic acid solution with the solid content of 15% is coated on a clean glass plate, the plate is placed in a state that the volume ratio of ethanol to water is 2:3, standing for 3 hours at room temperature, finally placing the polyimide foam composite material in an atmosphere furnace, and performing gradient temperature rise under the protection of argon, wherein the gradient temperature rise is that the temperature rises from the room temperature to 80 ℃ in the first stage, then the temperature is kept for 30min at 80 ℃, the temperature rises from 80 ℃ to 150 ℃ in the second stage, the temperature is kept for 30min at 150 ℃, the temperature rises from 150 ℃ to 250 ℃ in the third stage, the temperature is kept for 30min at 250 ℃, the temperature rises from 250 ℃ to 375 ℃ in the fourth stage, and the temperature is kept for 30min at 375 ℃, so that the polyimide foam composite material is finally obtained. The aperture of the obtained composite material pore is 4-8 μm, the tensile strength is less than or equal to 6MPa, and the electromagnetic shielding efficiency is less than or equal to 15dB. The unmodified filler agglomerated resulting in a significantly lower performance than example 6 under comparable conditions.
TABLE 1 Properties and electromagnetic shielding effectiveness of polyimide foam composites obtained in examples 1 to 6
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (9)
1. The preparation method of the polyimide foam composite material is characterized by comprising the following steps:
(1) Mixing carbon nanotube and Fe 3 O 4 And 4,4-diaminodiphenyl ether are added into the organic solvent and mixed to form uniform suspension;
(2) Adding pyromellitic dianhydride into the suspension in the step (1) for multiple times under a stirring state, and reacting for 3 to 5 hours to obtain a polyamic acid solution;
(3) Coating a polyamic acid solution on a substrate, carrying out coagulation bath for 3-5h, then carrying out gradient temperature rise under the condition of inert gas or nitrogen, and carrying out imidization to obtain a polyimide foam composite material;
the carbon nano tube in the step (1) is a polyaniline-modified carbon nano tube, wherein the mass ratio of polyaniline to the carbon nano tube is 1: (0.5 to 1.0); said Fe 3 O 4 Fe modified for polydopamine 3 O 4 Wherein polydopamine is in combination with Fe 3 O 4 The mass ratio of (1): (3~6);
and (3) the solvent of the coagulating bath is ethanol and water, and the volume ratio of the ethanol to the water is 1: (1~2).
2. The method for preparing polyimide foam composite material according to claim 1, wherein the carbon nanotubes and Fe in step (1) 3 O 4 And 4,4-diaminodiphenyl ether in a mass ratio of 1:1: (2 to 20); the molar ratio of 4,4-diaminodiphenyl ether in the step (1) to pyromellitic anhydride in the step (2) is 1:1 to 1.2.
3. The method for preparing polyimide foam composite material according to claim 1 or 2, wherein the rotation speed of the stirring in the step (2) is 200-600r/min, and the rotation speed is increased by 50-150r/min every time pyromellitic anhydride is added; the pyromellitic anhydride is added in 3~6 times at intervals of 5 to 15min.
4. The method for preparing the polyimide foam composite material as claimed in claim 1 or 2, wherein the solid content of the polyamic acid solution in the step (3) is 10 to 15%.
5. The method for preparing a polyimide foam composite material according to claim 1 or 2, wherein the temperature in the step (3) is room temperature; the gradient temperature rise is that the temperature is raised from room temperature to 80 ℃ in the first stage, then the temperature is maintained at 80 ℃ for 30min, the temperature is raised from 80 ℃ to 150 ℃ in the second stage, the temperature is maintained at 150 ℃ for 30min, the temperature is raised from 150 ℃ to 250 ℃ in the third stage, the temperature is maintained at 250 ℃ for 30min, and the temperature is raised from 250 ℃ to 375 ℃ in the fourth stage, and the temperature is maintained at 375 ℃ for 30min.
6. The method for preparing polyimide foam composite material according to claim 1 or 2, wherein the carbon nanotubes and Fe in the step (1) 3 O 4 The mass ratio of the total mass to the organic solvent is 1:15 to 185 percent; the mixing mode comprises ultrasonic and mechanical stirring, and the ultrasonic time is 10 to 40min; the reaction temperature in the step (2) is room temperature.
7. The method for preparing a polyimide foam composite material according to claim 1 or 2, wherein the organic solvent in the step (1) is N, N-dimethylacetamide; the coating method in the step (3) is a doctor blade method; the substrate is a glass plate.
8. A polyimide foam composite made by the method of any one of claims 1~7.
9. Use of a polyimide foam composite according to claim 8 in the field of electromagnetic shielding.
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