CN108774490B - Preparation method of microwave multi-band response multiple mesoporous structure wave absorber - Google Patents
Preparation method of microwave multi-band response multiple mesoporous structure wave absorber Download PDFInfo
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- 238000000576 coating method Methods 0.000 claims abstract description 32
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- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 15
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- 229940076136 ferrous iodide Drugs 0.000 claims description 11
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 claims description 11
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Abstract
The invention relates to the technical field of wave-absorbing composite materials, in particular to a method for preparing a wave absorber with a multi-mesoporous structure and a microwave multi-band response function, which comprises the steps of firstly preparing a multi-walled carbon nanotube/manganese dioxide compound, then preparing a wave absorber with a multi-walled carbon nanotube/mesoporous polyaniline micro-mesoporous structure by using the compound, and finally coating the wave absorber on a polyurethane foam carrier to form a wave absorber; the wave absorber has corresponding performance of multiple frequency bands.
Description
Technical Field
The invention relates to the technical field of wave-absorbing composite materials, in particular to a preparation method of a microwave multi-band response multiple mesoporous structure wave absorber.
Background
At present, the electronic information and communication industry develops rapidly, China has fully advanced the 4G era, the spanning from 2G to 4G only takes less than 10 years, and the electromagnetic wave as an important carrier of information transmission greatly promotes the development of each industry. However, the exponential growth of electronic and electrical equipment brings people into an environment full of electromagnetic wave radiation while facilitating life, and the electromagnetic wave seriously threatens the health of people, information safety, aviation safety and normal work of electronic and electrical equipment and systems, and becomes the fourth most pollution source following air pollution, water pollution and noise pollution.
For the existing electromagnetic wave radiation, a proper wave-absorbing material is needed for shielding, but the existing shielding material has a narrow frequency band and cannot effectively shield electromagnetic waves in various frequency band ranges, so that the shielding effect for the existing complex electromagnetic wave environment is poor, and the actual requirement cannot be met. Therefore, in order to meet the electromagnetic wave shielding requirements for the increasingly living environment of electromagnetic wave radiation, a high-performance, multi-band response absorber is needed for shielding a source of disturbance or securing protected equipment from interference. Meanwhile, the method can be used for improving the current situation of shortage of good wave-absorbing materials at present and getting rid of the current dilemma.
Disclosure of Invention
The invention aims to solve the problems and provides a preparation method of a microwave multi-band response multiple mesoporous structure wave absorber.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a microwave multi-band response multiple mesoporous structure wave absorber comprises the following steps:
(1) mixing 0.05-0.2g of multi-walled carbon nanotube and 0.5-1.5g of potassium permanganate, fully grinding to obtain a mixture, dispersing the mixture in 50-200mL of water, stirring for 5-20 minutes, adding a strong acid solution, continuously stirring for 1-3 hours, transferring the mixture into an oil bath, stirring for reaction for 1-3 hours, centrifugally washing a product after the reaction is finished, and fully drying to obtain a multi-walled carbon nanotube/manganese dioxide compound;
(2) taking 100mg of the compound, and stirring the compound in 50-200mL of water at low temperature for 0.5-2 hours to obtain a dispersion liquid; adding 0.1-0.5mL of aniline monomer and doping acid into the dispersion liquid to enable the acidic condition of the system to be 1mol/L, polymerizing for 6-24 hours at low temperature, and then centrifuging and washing to obtain the multiwalled carbon nanotube/mesoporous polyaniline micro-mesoporous structure wave absorber;
centrifugally washing with deionized water for at least 3 times until the washing liquid is clear and transparent and does not appear green; drying in a forced air drying oven at 60 ℃ for not less than 24 hours to obtain the wave absorbing agent;
the wave absorbing agent is a multi-walled carbon nanotube/polyaniline coating type wave absorbing agent;
(3) preparing the wave absorbing agent and ethanol solution into mixed solution with the content of 5-10 mg/mL, then soaking the cleaned, pretreated and dried polyurethane foam into the mixed solution, repeatedly soaking and extruding for many times, taking out the polyurethane foam absorbing the saturated mixed solution, and drying to obtain the porous structure type wave absorbing system.
Furthermore, after the multi-wall carbon nano tube and the potassium permanganate are fully ground, the particle size of the potassium permanganate is smaller than 100nm, wherein the part with the particle size smaller than 50nm accounts for more than or equal to 50%, and the part with the particle size larger than 80nm accounts for less than or equal to 10%.
Further, the pH after the strong acid is added in the step (1) is 1.5-2.5.
Further, the low temperature condition in the step (2) is-5 ℃ to 4 ℃.
Further, the oil bath condition is 50-62 ℃.
Further, the molar concentration of the doping acid after the doping acid is added in the step (2) is 1 mol/L.
Further, the mass ratio of the multi-walled carbon nanotube to the potassium permanganate is 1: (5-10) and adding ferrous iodide 2-3 times of the mass of the multi-wall carbon nano-tube.
Further, the doping acid is hydrochloric acid, perchloric acid, camphorsulfonic acid or benzenesulfonic acid.
Further, in the step (3), water and a coating auxiliary agent are added into the mixed solution of the wave absorbing agent and the ethanol solution, the mass ratio of the water to the ethanol is 1 (5-8), the content of the coating auxiliary agent in the mixed solution is 10-15mg/ml, and the coating auxiliary agent comprises the following components in parts by weight: 1-2 parts of urea, 3-4 parts of glyoxal, 8-10 parts of cyclohexanone and 0.5-1 part of EDTA.
Further, the thickness of the polyurethane foam in the step (3) is 10-100 mm.
According to the invention, a multiwall carbon nanotube/polyaniline coating type wave absorbing agent with microscopic mesopores is prepared by carrying out structural modification on the multiwall carbon nanotube, and the wave absorbing agent with the microscopic mesopores is coated on the surface of polyurethane foam with a macroscopic mesopore structure by a coating process, so that the conductive polyurethane foam wave absorbing material with a multiple mesopore structure is prepared. The novel wave-absorbing material can meet the requirements on the characteristics of strength, width, lightness, thinness and the like of the novel wave-absorbing material, and can also meet the requirements on flexibility and adjustable thickness and simultaneously realize the multi-band strong absorption characteristic of electromagnetic waves.
The following key points also exist during the whole preparation process: 1. the preparation performance of the obtained multi-wall carbon nano tube/manganese dioxide compound; 2, forming a wave absorbing agent mesoporous structure; 3 coating the wave absorber in polyurethane foam;
regarding the first point, the invention adopts potassium permanganate as a manganese source to prepare the multi-walled carbon nanotube/manganese dioxide compound, and multiple experiments of the inventor find that a certain amount of ferrous iodide is added into a reaction system, so that the compound time can be shortened, and the generation rate of the compound can be improved, which is very important and can improve the most basic conditions for improving the whole subsequent wave-absorbing system; because ferrous iodide is dissolved in water, after the reaction in the step (1) is finished, the product is centrifugally washed, and if necessary, cold water is used for washing, so that the ferrous iodide doped in the composite is favorably removed, and the purity of the composite is improved. In this step, comparison with a comparative experiment shows that the conversion rate of the product can be increased by 20-35% after the ferrous iodide is added, which has a great influence on the subsequent process.
Regarding the second point, the formation of the mesoporous structure of the wave absorber directly affects the performance of the wave absorber and finally has a crucial influence on the performance of the wave absorbing system, so the formation of the mesoporous structure of the wave absorber must meet the actual requirements as much as possible. The inventor finds through experiments that in the reaction process of the step (1), the direct factor of the formation of mesopores is the addition of a strong acid solution, in the process, a strong acid is added to create an acidic environment, the pH value of the acidic environment is enabled to be 1.5-2.5, and a mesoporous structure can be formed under the acidic condition; however, through the experiments of the inventors, although the mesoporous structure can be formed under the acidic condition, that is, the key point of forming the mesoporous structure is to control the acidic condition, the uniformity of the simultaneously formed mesoporous structure is poor, and the yield is low, at this time, the added ferrous iodide can adjust the uniformity of the mesoporous structure, and simultaneously the yield of the mesoporous structure is improved.
With respect to the third point, it is the coating of the wave absorber in the polyurethane foam; in order to ensure the performance of the finally prepared wave absorber, the coating effect of the wave absorber in the polyurethane foam is very critical, and only by coating the wave absorber on the polyurethane foam in a sufficient amount, a foundation can be provided for the wave absorbing performance of the wave absorber; it must therefore be ensured that the wave absorber can be applied to the polyurethane foam in a sufficient amount and has a certain durability after application.
The inventors found through experiments that the coating effect on the polyurethane foam can be improved by adding a certain amount of the coating auxiliary agent in the process of dip-coating the polyurethane foam in the mixed solution of the wave absorbing agent and the ethanol solution, and the wave absorbing agent does not easily fall off after coating. The performance of the wave absorber can be ensured only if the wave absorber has sufficient durability on the surface of the polyurethane foam. The coating auxiliary agent is urea, glyoxal, cyclohexanone and EDTA, and the substances are added into the mixed solution to accelerate the coating of the wave absorbing agent on the polyurethane foam,
compared with the prior art, the invention has the beneficial effects that:
according to the invention, a multiple mesoporous structure type wave absorbing system with microwave multi-band response is constructed through the structural design of the coating type wave absorbing agent, the wave absorbing system has the characteristics of both the coating type wave absorbing material and the structure type wave absorbing material, the wave absorbing parameter can be adjusted by adjusting the thickness of the wave absorbing system, and the defects of electromagnetic disorder, poor conductivity and non-uniform conductivity of the shielding material in the rubber-based flexible wave absorbing material are overcome.
The prepared wave-absorbing material (namely a wave absorber) has the dielectric loss characteristics of a carbon-series wave-absorbing material and a conductive polymer, also has the interface polarization characteristic, realizes a multiple loss mechanism of electromagnetic waves, and has excellent wave-absorbing performance. The wave absorbing darkroom can be applied to the fields of intelligent wearing, wave absorbing darkroom design and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a wave absorber of the present invention;
FIG. 2 is a diagram showing the results of the corresponding test of the microwave multiband of the absorber of the present invention.
Detailed Description
The technical solution of the present invention is further described below by means of specific examples.
The raw materials used in the examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art, unless otherwise specified.
Example 1:
a preparation method of a microwave multi-band response multiple mesoporous structure wave absorber comprises the following steps:
(1) mixing 0.05g of multi-walled carbon nanotube and 1.5g of potassium permanganate, fully grinding to obtain a mixture, dispersing the mixture in 200mL of water, stirring for 5-6 minutes, adding 0.5mL of strong acid solution, continuously stirring for 1 hour, (regarding the addition of the strong acid, the pH after the addition is 2-2.5 is optimal), transferring the mixture into an oil bath, stirring and reacting for 1-3 hours, centrifugally washing a product after the reaction is finished, and fully drying to obtain a multi-walled carbon nanotube/manganese dioxide compound; the oil bath condition is 50-62 ℃; after the multi-wall carbon nano tube and the potassium permanganate are fully ground, the particle size of the potassium permanganate is smaller than 100nm, wherein the part with the particle size smaller than 50nm accounts for more than or equal to 50%, and the part with the particle size larger than 80nm accounts for less than or equal to 10%;
(2) taking 100mg of the compound, and stirring the compound in 200mL of water at low temperature for 0.5 to 2 hours to obtain a dispersion liquid; adding 0.1mL of aniline monomer and doping acid into the dispersion liquid to enable the acidic condition of the system to be 1mol/L, polymerizing for 24 hours at low temperature, and centrifuging and washing to obtain the multiwalled carbon nanotube/mesoporous polyaniline micro-mesoporous structure wave absorber; the low temperature is-5 ℃ to 4 ℃; the doping acid is hydrochloric acid, perchloric acid, camphorsulfonic acid or benzenesulfonic acid;
(3) preparing the wave absorbing agent and an ethanol solution into a mixed solution with the content of 5mg/mL, then soaking the cleaned, pretreated and dried polyurethane foam into the mixed solution, repeatedly soaking and extruding for many times, taking out the polyurethane foam absorbing the saturated mixed solution, and drying to obtain the porous structure type wave absorbing system.
Example 2:
a preparation method of a microwave multi-band response multiple mesoporous structure wave absorber comprises the following steps:
(1) mixing 0.2g of multi-walled carbon nanotube and 1.5g of potassium permanganate, fully grinding to obtain a mixture, dispersing the mixture in 200mL of water, stirring for 15-20 minutes, adding a strong acid solution, continuously stirring for 3 hours, (regarding the addition of the strong acid, the pH after the addition is 2-2.5 is optimal), transferring the mixture into an oil bath, stirring and reacting for 1-3 hours, centrifugally washing a product after the reaction is finished, and fully drying to obtain a multi-walled carbon nanotube/manganese dioxide compound; the oil bath condition is 50-62 ℃; after the multi-wall carbon nano tube and the potassium permanganate are fully ground, the particle size of the potassium permanganate is smaller than 100nm, wherein the part with the particle size smaller than 50nm accounts for more than or equal to 50%, and the part with the particle size larger than 80nm accounts for less than or equal to 10%;
(2) taking 100mg of the compound, and stirring the compound in 150 mL of water at low temperature for 2 hours to obtain a dispersion liquid; adding 0.5mL of aniline monomer and doping acid into the dispersion liquid to enable the acidic condition of the system to be 1mol/L, polymerizing for 24 hours at low temperature, and centrifuging and washing to obtain the multiwalled carbon nanotube/mesoporous polyaniline micro-mesoporous structure wave absorber; the low temperature is-5 ℃ to 4 ℃; the doping acid is hydrochloric acid, perchloric acid, camphorsulfonic acid or benzenesulfonic acid;
(3) preparing the wave absorbing agent and ethanol solution into mixed solution with the content of 10mg/mL, then soaking the cleaned, pretreated and dried polyurethane foam into the mixed solution, repeatedly soaking and extruding for many times, taking out the polyurethane foam absorbing the saturated mixed solution, and drying to obtain the porous structure type wave absorbing system.
Example 3:
a preparation method of a microwave multi-band response multiple mesoporous structure wave absorber comprises the following steps:
(1) mixing 0.05g of multi-walled carbon nanotube and 0.5g of potassium permanganate, fully grinding to obtain a mixture, dispersing the mixture in 100mL of water, stirring for 5-20 minutes, adding 1mL of strong acid solution, continuously stirring for 1-3 hours, (regarding the addition of the strong acid, the pH after the addition is 2-2.5 is optimal), transferring the mixture into an oil bath, stirring and reacting for 1-3 hours, centrifugally washing a product after the reaction is finished, and fully drying to obtain a multi-walled carbon nanotube/manganese dioxide compound; the oil bath condition is 50-62 ℃; after the multi-wall carbon nano tube and the potassium permanganate are fully ground, the particle size of the potassium permanganate is smaller than 100nm, wherein the part with the particle size smaller than 50nm accounts for more than or equal to 50%, and the part with the particle size larger than 80nm accounts for less than or equal to 10%;
(2) taking 100mg of the compound, and stirring the compound in 50 mL of water at low temperature for 0.5 to 2 hours to obtain a dispersion liquid; adding 0.1mL of aniline monomer and doping acid into the dispersion liquid to enable the acidic condition of the system to be 1mol/L, polymerizing for 6-24 hours at low temperature, and centrifuging and washing to obtain the multiwalled carbon nanotube/mesoporous polyaniline micro-mesoporous structure wave absorber; the low temperature is-5 ℃ to 4 ℃; the doping acid is hydrochloric acid, perchloric acid, camphorsulfonic acid or benzenesulfonic acid;
(3) preparing the wave absorbing agent and ethanol solution into mixed solution with the content of 10mg/mL, then soaking the cleaned, pretreated and dried polyurethane foam into the mixed solution, repeatedly soaking and extruding for many times, taking out the polyurethane foam absorbing the saturated mixed solution, and drying to obtain the porous structure type wave absorbing system.
Example 4:
a preparation method of a microwave multi-band response multiple mesoporous structure wave absorber comprises the following steps:
(1) mixing 0.1g of multi-walled carbon nanotube and 1.5g of potassium permanganate, fully grinding to obtain a mixture, dispersing the mixture in 100mL of water, stirring for 10 minutes, adding a strong acid solution, continuously stirring for 1-3 hours, (regarding the addition of the strong acid, the pH after the addition is 2-2.5 is optimal), transferring the mixture into an oil bath, stirring and reacting for 1-3 hours, centrifugally washing a product after the reaction is finished, and fully drying to obtain a multi-walled carbon nanotube/manganese dioxide compound; the oil bath condition is 50-62 ℃; after the multi-wall carbon nano tube and the potassium permanganate are fully ground, the particle size of the potassium permanganate is smaller than 100nm, wherein the part with the particle size smaller than 50nm accounts for more than or equal to 50%, and the part with the particle size larger than 80nm accounts for less than or equal to 10%;
(2) taking 100mg of the compound, and stirring the compound in 50 mL of water at low temperature for 0.5 to 2 hours to obtain a dispersion liquid; adding 0.3mL of aniline monomer and doping acid into the dispersion liquid to enable the acidic condition of the system to be 1mol/L, polymerizing for 6-24 hours at low temperature, and centrifuging and washing to obtain the multiwalled carbon nanotube/mesoporous polyaniline micro-mesoporous structure wave absorber; the low temperature is-5 ℃ to 4 ℃; the doping acid is hydrochloric acid, perchloric acid, camphorsulfonic acid or benzenesulfonic acid;
(3) preparing the wave absorbing agent and an ethanol solution into a mixed solution with the content of 8 mg/mL, then soaking the cleaned, pretreated and dried polyurethane foam into the mixed solution, repeatedly soaking and extruding for many times, taking out the polyurethane foam absorbing the saturated mixed solution, and drying to obtain the porous structure type wave absorbing system.
Example 5:
a preparation method of a microwave multi-band response multiple mesoporous structure wave absorber comprises the following steps:
(1) mixing 0.2g of multi-walled carbon nanotube and 0.5g of potassium permanganate, fully grinding to obtain a mixture, dispersing the mixture in 100mL of water, stirring for 5-20 minutes, adding a strong acid solution, continuously stirring for 1-3 hours, (regarding the addition of the strong acid, the pH after the addition is 2-2.5 is optimal), transferring the mixture into an oil bath, stirring and reacting for 1-3 hours, centrifugally washing a product after the reaction is finished, and fully drying to obtain a multi-walled carbon nanotube/manganese dioxide compound; the oil bath condition is 50-62 ℃; after the multi-wall carbon nano tube and the potassium permanganate are fully ground, the particle size of the potassium permanganate is smaller than 100nm, wherein the part with the particle size smaller than 50nm accounts for more than or equal to 50%, and the part with the particle size larger than 80nm accounts for less than or equal to 10%;
(2) taking 100mg of the compound, and stirring the compound in 50-200mL of water at low temperature for 0.5-2 hours to obtain a dispersion liquid; adding 0.1-0.5mL of aniline monomer and doping acid into the dispersion liquid to enable the acidic condition of the system to be 1mol/L, polymerizing for 6-24 hours at low temperature, and then centrifuging and washing to obtain the multiwalled carbon nanotube/mesoporous polyaniline micro-mesoporous structure wave absorber; the low temperature is-5 ℃ to 4 ℃; the doping acid is hydrochloric acid, perchloric acid, camphorsulfonic acid or benzenesulfonic acid;
(3) preparing the wave absorbing agent and ethanol solution into mixed solution with the content of 5-10 mg/mL, then soaking the cleaned, pretreated and dried polyurethane foam into the mixed solution, repeatedly soaking and extruding for many times, taking out the polyurethane foam absorbing the saturated mixed solution, and drying to obtain the porous structure type wave absorbing system.
Example 6
On the basis of the above embodiments, the multi-walled carbon nanotube/manganese dioxide composite of step (1); the preparation is improved, the multi-walled carbon nanotube and the potassium permanganate are mixed, simultaneously, ferrous iodide with the quality 3 times that of the multi-walled carbon nanotube is added, and simultaneously, the mass ratio of the multi-walled carbon nanotube to the potassium permanganate is ensured to be 1: 5.
example 7
On the basis of the above embodiments, the multi-walled carbon nanotube/manganese dioxide composite of step (1); the preparation is improved, the multi-walled carbon nanotube and the potassium permanganate are mixed, simultaneously, ferrous iodide with the quality 2 times that of the multi-walled carbon nanotube is added, and simultaneously, the mass ratio of the multi-walled carbon nanotube to the potassium permanganate is ensured to be 1: 10.
example 8
On the basis of the above embodiments, the following improvements are made, in the step (3), water and a coating auxiliary agent are further added to the mixed solution of the wave absorbing agent and the ethanol solution, the mass ratio of the water to the ethanol is 1:8, the content of the coating auxiliary agent in the mixed solution is 15mg/ml, and the coating auxiliary agent is composed of the following components in parts by weight: 1 part of urea, 4 parts of glyoxal, 8 parts of cyclohexanone and 1 parts of EDTA.
Example 9
On the basis of the above embodiments, the following improvements are made, in the step (3), water and a coating auxiliary agent are further added to the mixed solution of the wave absorbing agent and the ethanol solution, the mass ratio of the water to the ethanol is 1:5, the content of the coating auxiliary agent in the mixed solution is 10mg/ml, and the coating auxiliary agent is composed of the following components in parts by weight: 2 parts of urea, 3 parts of glyoxal, 10 parts of cyclohexanone and 0.5 part of EDTA.
Finally, the obtained composite is a flexible polyurethane foam/multi-walled carbon nanotube/mesoporous polyaniline multiple mesoporous structure wave absorbing system constructed by the polyurethane foam/multi-walled carbon nanotube/mesoporous polyaniline multiple mesoporous structure composite.
The wave absorbers prepared in examples 1 to 5 were formed to have thicknesses of 50 mm, 60 mm, 70 mm, 80 mm and 90mm, respectively. The corresponding test result of the microwave multiband of each wave absorber is shown in figure 2; as can be seen from the figure, the wave absorber prepared by the invention has good multi-band wave absorbing performance. The wave absorbing effect in each frequency band can be seen visually from the figure.
Therefore, the wave absorption system of the invention can improve the existing defects to a certain extent and solve the existing problems to a certain extent.
Examples 6 and 7 are modifications to step (1). By comparing the results of examples 6 and 7 with the data of examples 1 to 6, it was found that the yield of the product was improved by 20 to 35% by adding ferrous iodide in step (1). Meanwhile, after ferrous iodide is added, the generated multi-walled carbon nanotube/manganese dioxide compound has a relatively uniform mesoporous structure, and the quality stability of the product can be ensured.
Examples 8 and 9 are improvements in the quality of the absorber produced. Coating by way of examples 8 and 9 found more uniform coating than examples 1-5, and the reflection attenuation could be increased by 10-15% as shown in the reflection loss test data;
meanwhile, after the results of examples 8 and 9 and examples 1 and 5 are compared by adopting an artificial aging test, the wave absorbing performance of examples 8 and 9 caused by poor coating is only reduced by 3-5% after the artificial aging is carried out for 200 hours, but the wave absorbing performance of examples 1-5 is reduced by 10-15%. Thus, it can be shown that the use of the coating assistant improves the coating effect of the wave absorber and prolongs the service life of the wave absorber.
Claims (4)
1. A preparation method of a microwave multi-band response multiple mesoporous structure wave absorber is characterized by comprising the following steps:
(1) mixing 0.05-0.2g of multi-walled carbon nanotube and 0.5-1.5g of potassium permanganate, fully grinding to obtain a mixture, dispersing the mixture in 50-200mL of water, stirring for 5-20 minutes, adding a strong acid solution, continuously stirring for 1-3 hours, centrifugally washing a product after the reaction is finished, and fully drying to obtain a multi-walled carbon nanotube/manganese dioxide compound; the pH value after the strong acid is added is 1.5-2.5; the oil bath condition is 50-62 ℃;
(2) taking 100mg of the compound, and stirring the compound in 50-200mL of water at low temperature for 0.5-2 hours to obtain a dispersion liquid; adding 0.1-0.5mL of aniline monomer and doping acid into the dispersion liquid to enable the system to be in an acidic condition, polymerizing for 6-24 hours at a low temperature, and centrifuging and washing to obtain the multiwalled carbon nanotube/mesoporous polyaniline micro-mesoporous structure wave absorber; the low temperature is-5 ℃ to 4 ℃,
(3) preparing a mixed solution with the content of 5-10 mg/mL by using the wave absorbing agent and an ethanol solution, then soaking the cleaned, pretreated and dried polyurethane foam into the mixed solution, repeatedly soaking and extruding for many times, taking out the polyurethane foam absorbing the saturated mixed solution, and drying to obtain a porous structure type wave absorbing system;
the mass ratio of the multi-walled carbon nanotube to the potassium permanganate is 1: (5-10), and adding ferrous iodide 2-3 times of the mass of the multi-wall carbon nano-tubes;
and (3) adding water and a coating auxiliary agent into the mixed solution of the wave absorbing agent and the ethanol solution in the step (3), wherein the mass ratio of the water to the ethanol is 1 (5-8), the content of the coating auxiliary agent in the mixed solution is 10-15mg/ml, and the coating auxiliary agent comprises the following components in parts by weight: 1-2 parts of urea, 3-4 parts of glyoxal, 8-10 parts of cyclohexanone and 0.5-1 part of EDTA.
2. The method of claim 1, wherein the multi-walled carbon nanotubes and potassium permanganate are fully ground to obtain potassium permanganate with a particle size of less than 100nm, wherein the part with a particle size of less than 50nm accounts for 50% or more, and the part with a particle size of more than 80nm accounts for 10% or less.
3. The method according to claim 1, wherein the doping acid is added in step (2) at a molar concentration of 1 mol/L.
4. The method of claim 1, wherein the doping acid is hydrochloric acid, perchloric acid, camphorsulfonic acid or benzenesulfonic acid.
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