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 sp2And 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 spanning the whole carbon nanotube mutually, so that the carbon nanotube has excellent conductivity, and in addition, the carbon nanotube has extremely high length-diameter ratio, thereby being beneficial to constructing an effective conductive network.
At present, the filling type electromagnetic shielding composite material can reach the electromagnetic shielding standard of practical application only by too high loading (generally more than 50 percent), and the mechanical property of the electromagnetic shielding material is poor and the cost is too high. Besides, in order to enhance the bandwidth, nano-magnetic particles Fe with magnetic loss and high conductivity are introduced3O4. 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 Fe3O4Adding 4, 4-diaminodiphenyl ether into an organic solvent, and mixing to form a uniform suspension;
(2) adding pyromellitic dianhydride into the suspension obtained in the step (1) for multiple times under a stirring state, and reacting for 3-5 hours to obtain a polyamic acid solution;
(3) and coating a 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)3O4Fe modified for polydopamine3O4Wherein polydopamine is in combination with Fe3O4The mass ratio of (1): (3-6), more preferably 1: 5.
preferably, the carbon nanotubes and Fe in the step (1)3O4And 4, 4-diaminodiphenyl ether in a mass ratio of 1: 1: (2-20), more preferably 1: 1: (3-19), most preferably 1: 1: 3.14 to 6.3; the carbon nanotube and Fe3O4The 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 the 4, 4-diaminodiphenyl ether in the step (1) to the pyromellitic anhydride in the 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 dianhydride in the step (2) is added for 3-6 times at intervals of 5-15 min.
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 10-15%.
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 30 min.
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 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.
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 (1.0mol/L) containing ammonium persulfate at a concentration of 40.0 mg-ml in the HCl solution-1Adding 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 Fe3O4Adding 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-1The 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 weight3O4。
0.056g of polyaniline-modified carbon nanotube and 0.056g of polydopamine-modified Fe are weighed3O4And 1.06g of 4, 4-diaminodiphenyl ether are respectively dispersed in 5g of N-dimethylacetamide, 5g of N-dimethylacetamide and 10g N of N-dimethylacetamide, and the mixture is poured into the same container for ultrasonic dispersion for 30min and mechanically stirred 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)3O4) The mass ratio of the polymer foam to the polymer foam (the sum of 4, 4-diaminodiphenyl ether and pyromellitic dianhydride) 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 7 dB.
Example 2
Will be 1.0g carbon nanotubes were added to 50ml of an HCl solution (1.0mol/L) containing ammonium persulfate at a concentration of 40.0 mg-ml in the HCl solution-1Adding 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 Fe3O4Adding 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-1The 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 weight3O4。
Weighing 0.168g polyaniline-modified carbon nanotube and 0.168g polydopamine-modified Fe3O4And 1.06g of 4, 4-diaminodiphenyl ether are respectively dispersed in 5g of N-dimethylacetamide, 5g of N-dimethylacetamide and 10g N of N-dimethylacetamide, and the mixture is poured into the same container for ultrasonic dispersion for 30min and mechanically stirred 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)3O4) The mass ratio of the polyurethane foam to the polymer foam (the sum of 4, 4-diaminodiphenyl ether and pyromellitic anhydride) is 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 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 pore diameter of the obtained composite material is 4-7 mu m, and the tensile strength is not less than22MPa, and the electromagnetic shielding effectiveness is more than or equal to 21 dB.
Example 3
1.0g of carbon nanotubes was added to 50ml of an HCl solution (1.0mol/L) containing ammonium persulfate at a concentration of 40.0 mg-ml in the HCl solution-1Adding 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 Fe3O4Adding 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-1The 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 weight3O4。
Weighing 0.336g polyaniline-modified carbon nanotube and 0.336g polydopamine-modified Fe3O4And 1.06g of 4, 4-diaminodiphenyl ether are respectively dispersed in 5g of N-dimethylacetamide, 5g of N-dimethylacetamide and 10g N of N-dimethylacetamide, and the mixture is poured into the same container for ultrasonic dispersion for 30min and mechanically stirred 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)3O4) The mass ratio of the polyurethane foam to the polymer foam (the sum of 4, 4-diaminodiphenyl ether and pyromellitic anhydride) is 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 at room temperature for 3h, finally placing in an atmosphere furnace, and performing gradient heating under the protection of argon, wherein the gradient heating is performed in a first stage of heating from room temperature to 80 ℃, then keeping at 80 ℃ for 30min, in a second stage of heating from 80 ℃ to 150 ℃, keeping at 150 ℃ for 30min, in a third stage of heating from 150 ℃ to 250 ℃, keeping at 250 ℃ for 30min, and in a fourth stage of heating from 250 ℃ to 375 ℃, and 375 DEG CKeeping for 30min to finally obtain the polyimide foam composite material. 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 43 dB.
Example 4
1.0g of carbon nanotubes was added to 50ml of an HCl solution (1.0mol/L) containing ammonium persulfate at a concentration of 40.0 mg-ml in the HCl solution-1Adding 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 Fe3O4Adding 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-1The 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 weight3O4。
0.088g of polyaniline-modified carbon nanotube and 0.088g of polydopamine-modified Fe3O41.66g of 4, 4-diaminodiphenyl ether are respectively dispersed in 5g of N-dimethylacetamide, 5g of N-dimethylacetamide and 10g N, and the mixture is poured into the same container for mechanical stirring after ultrasonic dispersion for 30min, and the rotating speed is 300r/min, so that uniform suspension is formed. 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)3O4) The mass ratio of the polymer foam to the polymer foam (the sum of 4, 4-diaminodiphenyl ether and pyromellitic dianhydride) 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 mixture 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 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,keeping the temperature at 150 ℃ for 30min, heating the temperature from 150 ℃ to 250 ℃ in the third stage, keeping the temperature at 250 ℃ for 30min, heating the temperature from 250 ℃ to 375 ℃ in the fourth stage, and keeping the temperature at 375 ℃ for 30min to finally obtain 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 9 dB.
Example 5
1.0g of carbon nanotubes was added to 50ml of an HCl solution (1.0mol/L) containing ammonium persulfate at a concentration of 40.0 mg-ml in the HCl solution-1Adding 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 Fe3O4Adding 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-1The 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 weight3O4。
0.264g polyaniline-modified carbon nano tube and 0.264g polydopamine-modified Fe3O41.66g of 4, 4-diaminodiphenyl ether are respectively dispersed in 5g of N-dimethylacetamide, 5g of N-dimethylacetamide and 10g N, and the mixture is poured into the same container for mechanical stirring after ultrasonic dispersion for 30min, and the rotating speed is 300r/min, so that uniform suspension is formed. 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)3O4) The mass ratio of the polyurethane foam to the polymer foam (the sum of 4, 4-diaminodiphenyl ether and pyromellitic anhydride) is 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 in a coagulating bath, finally placing the solution in an atmosphere furnace, and carrying out gradient temperature rise under the protection of argonAnd 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, the temperature is raised from 250 ℃ to 375 ℃ in the fourth stage, and the temperature is maintained at 375 ℃ for 30min, 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 23 dB.
Example 6
1.0g of carbon nanotubes was added to 50ml of an HCl solution (1.0mol/L) containing ammonium persulfate at a concentration of 40.0 mg-ml in the HCl solution-1Adding 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 Fe3O4Adding 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-1The 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 weight3O4。
0.528g of polyaniline-modified carbon nano-tube and 0.528g of polydopamine-modified Fe3O41.66g of 4, 4-diaminodiphenyl ether are respectively dispersed in 5g of N-dimethylacetamide, 5g of N-dimethylacetamide and 10g N, and the mixture is poured into the same container for mechanical stirring after ultrasonic dispersion for 30min, and the rotating speed is 300r/min, so that uniform suspension is formed. 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)3O4) The mass ratio of the polyurethane foam to the polymer foam (the sum of 4, 4-diaminodiphenyl ether and pyromellitic anhydride) is 30: 100. coating the polyamic acid solution with the solid content of 15 percent on a clean glass plate, and then placing the plate in ethanol and waterIs 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 44 dB.
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 polydopamine3O41.66g of 4, 4-diaminodiphenyl ether are respectively dispersed in 5g of N-dimethylacetamide, 5g of N-dimethylacetamide and 10g N, and the mixture is poured into the same container for mechanical stirring after ultrasonic dispersion for 30min, and the rotating speed is 300r/min, so that uniform suspension is formed. 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 acid3O4) The mass ratio of the polyurethane foam to the polymer foam (the sum of 4, 4-diaminodiphenyl ether and pyromellitic anhydride) is 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 at room temperature for 3h, finally placing 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 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, the temperature rises from 250 ℃ to 375 ℃ in the fourth stage, and the temperature is kept at 375 ℃ for 30miAnd n, finally obtaining the polyimide foam composite material. 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 15 dB. The unmodified filler agglomerated resulting in a significantly lower performance than example 6 under comparable conditions.
TABLE 1 Properties and electromagnetic shielding effectiveness of the polyimide foam composites obtained in examples 1-6
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 changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.