CN111471342A - Manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating and preparation method thereof - Google Patents
Manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of wave-absorbing materials, and discloses a manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating, which comprises the following formula raw materials and components: the manganese-zinc ferrite loads carbon nano tubes, aniline, ammonium persulfate and p-toluenesulfonic acid. According to the manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating, manganese-zinc ferrite nanofibers have good nanometer appearance and enter the tube wall of an aminated carbon nanotube to form a manganese-zinc ferrite loaded carbon nanotube material, aniline and the aminated carbon nanotube are subjected to in-situ polymerization, so that the carbon nanotube and polyaniline are subjected to covalent bond form copolymer, the dispersibility and compatibility of the carbon nanotube and the manganese-zinc ferrite in polyaniline are improved, and the polyaniline coating has excellent interface impedance matching performance and wave-absorbing performance under the combined action of manganese-zinc ferrite magnetic loss, carbon nanotube dielectric loss and polyaniline polarization relaxation effect.
Description
Technical Field
The invention relates to the technical field of wave-absorbing materials, in particular to a manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating and a preparation method thereof.
Background
Electromagnetic waves are shocking particle waves which are derived and emitted in space by an in-phase and mutually vertical electric field and a magnetic field, the shocking particle waves are electromagnetic fields which are transmitted in a wave form, along with the rapid development of electronic information technology, broadcasting and radio frequency technology, the normal life of people is influenced by electromagnetic radiation, the mechanism that the electromagnetic radiation harms human bodies mainly comprises heat effect, non-heat effect, accumulation effect and the like, the immune system, the reproductive system, the cardiovascular system and the like of the human bodies are influenced by the electromagnetic radiation after being received for a long time, the health of the human bodies is seriously influenced, meanwhile, the normal work of electronic equipment such as airplane navigation, medical treatment and the like is influenced, and therefore, a novel efficient wave absorbing material needs to be developed to solve.
The manganese-zinc ferrite is a soft magnetic ferrite wave-absorbing material, has good magnetic loss performance, high initial permeability and high impedance, but the single ferrite material has poor impedance matching performance, so that better wave-absorbing performance is difficult to obtain, the polyaniline is simple to prepare, low in density, light in material and good in dielectric property, and has wide research in electromagnetic shielding and wave-absorbing materials, inorganic materials such as the manganese-zinc ferrite can be compounded with the polyaniline to obtain an organic-inorganic hybrid material, so that the impedance matching performance and the wave-absorbing performance of the material are enhanced, but the manganese-zinc ferrite, the carbon nano tube and the polyaniline have poor compatibility, are easy to aggregate and agglomerate in the polyaniline, and can seriously affect the mechanical property of the polyaniline.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating and a preparation method thereof.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating comprises the following formula raw materials in parts by weight: 3-17 parts of manganese-zinc ferrite loaded carbon nano tube, 28-32 parts of aniline, 52-60 parts of ammonium persulfate and 3-5 parts of p-toluenesulfonic acid.
Preferably, the preparation method of the manganese-zinc ferrite loaded carbon nanotube comprises the following steps:
(1) adding distilled water and a carboxylated carbon nanotube into a reaction bottle, adding thionyl chloride as an acyl chlorination reagent after uniform ultrasonic dispersion, placing the reaction bottle into an oil bath kettle, heating to 80-90 ℃ under the nitrogen atmosphere, stirring at a constant speed for reaction for 30-40h, drying the solution in vacuum to remove the solvent, washing a solid product with distilled water and ethanol, fully drying to obtain the acyl chlorinated carbon nanotube, adding distilled water and the acyl chlorinated carbon nanotube into the reaction bottle, after uniform ultrasonic dispersion, adding p-phenylenediamine, placing the reaction bottle into the oil bath kettle, heating to 80-90 ℃ under the nitrogen atmosphere, stirring at a constant speed for reaction for 15-20h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and preparing the p-phenylenediamine covalent modified aminated carbon nanotube.
(2) Adding N, N-dimethylformamide solvent and polyvinylpyrrolidone into a reaction bottle, stirring for 10-15h, adding FeCl3、MnCl2And ZnCl2Continuously stirring for 10-15h to form electrospinning liquid, injecting the electrospinning liquid into a micro injector to perform an electrostatic spinning process, wherein the voltage is 18-20Kv, the flow rate is 0.5-1ml/h, the distance between the micro injector and a receiver is 15-18cm, preparing to obtain a nanofiber precursor, placing the nanofiber precursor in a muffle furnace, heating at the rate of 5-10 ℃/min, and calcining at 650-680 ℃ for 3-5h to obtain the manganese-zinc ferrite nanofiber.
(3) Adding distilled water, aminated carbon nano-tubes and manganese zinc ferrite nano-fibers into a reaction bottle, placing the solution into an automatic reaction kettle after uniform ultrasonic dispersion, heating to 120 ℃ and 150 ℃, stirring at constant speed for adsorption for 20-30h, filtering the solution to remove the solvent, and drying the solid product to obtain the manganese zinc ferrite loaded carbon nano-tubes.
Preferably, the oil bath pot is including the pot body, the last swing joint of the pot body has the oil bath pot cover, the left side and the intake pipe fixed connection of the pot body, intake pipe swing joint has the admission valve, the right side fixedly connected with outlet duct of the pot body, outlet duct and outlet valve swing joint, the inside fixedly connected with heating ring of the pot body, the below fixedly connected with safety cover of the pot body, the inside of safety cover is provided with the circulator, circulator and bearing fixed connection, bearing swing joint has the rotary rod, the top fixedly connected with base of rotary rod, the last fixed surface of base is connected with the guide rail, guide rail and pulley swing joint, the top and the protection shield fixed connection of pulley, the top of base is provided.
Preferably, the mass ratio of the carboxylated carbon nanotubes to the thionyl chloride is 6-8:1, and the mass ratio of the acyl chlorinated carbon nanotubes to the p-phenylenediamine is 1: 5-10.
Preferably, the FeCl3、MnCl2And ZnCl2The mass ratio of the substances is 4:0.2-0.4: 0.6-0.8.
Preferably, the mass ratio of the aminated carbon nanotube to the manganese-zinc ferrite nanofiber is 10-15: 1.
Preferably, the preparation method of the manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating comprises the following steps:
(1) adding distilled water, 3-17 parts of manganese-zinc ferrite loaded carbon nano-tubes and 28-32 parts of aniline into a reaction bottle, uniformly stirring, placing the mixture into a low-temperature reactor, adding 52-60 parts of ammonium persulfate and 3-5 parts of p-toluenesulfonic acid at 0-5 ℃, uniformly stirring and reacting for 8-12h, centrifugally washing the solution to remove the solvent, dissolving the solid product, pouring the dissolved solid product into a film forming mold, and naturally casting to form a film to prepare the manganese-zinc ferrite-carbon nano-tube grafted polyaniline wave-absorbing coating.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating is characterized in that thionyl chloride reacts with carboxyl of a carboxylated carbon nanotube to generate an acyl chlorinated carbon nanotube, acyl chloride groups react with amino of p-diphenylamine to generate an aminated carbon nanotube, and a manganese-zinc ferrite nanofiber is prepared by an electrostatic spinning method and has good nano-morphology, through a high-pressure hydrothermal method, manganese-zinc ferrite nanofibers enter the tube wall of a carbon nanotube to form a manganese-zinc ferrite loaded carbon nanotube material, ammonium persulfate is used as an initiator, p-toluenesulfonic acid is used as a catalyst, aniline and aminated carbon nanotubes are used for in-situ polymerization, so that the carbon nanotube and polyaniline are subjected to covalent bond form copolymer, the dispersibility and compatibility of the carbon nanotube and the manganese-zinc ferrite in the polyaniline are greatly improved, and the influence of the carbon nanotube and the manganese-zinc ferrite which are not uniformly dispersed on the mechanical performance of a polyaniline film coating is avoided.
The manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating has high magnetic conductivity and magnetic loss performance, a small amount of carbon nanotubes with excellent conductivity generate a low percolation threshold in polyaniline to generate a polarization effect so as to form dielectric loss, the polyaniline has good conductivity, a polymer molecular chain contains polarization carriers and dual-polarization carriers to generate a strong polarization relaxation effect, and under the combined action of the magnetic loss effect of the manganese-zinc ferrite, the dielectric loss effect of the carbon nanotubes and the polarization relaxation effect of the polyaniline, the polyaniline composite coating material has excellent interface impedance matching performance, incident electromagnetic waves can completely enter the coating and are attenuated and consumed by the magnetic loss and the dielectric loss, so that the polyaniline coating has excellent wave-absorbing performance.
Drawings
FIG. 1 is a schematic front view of an oil bath pan body;
FIG. 2 is an enlarged schematic view of the protection plate;
fig. 3 is a schematic view of the protection plate adjustment.
1. A pan body; 2. oil bath pan covers; 3. an air inlet pipe; 4. an intake valve; 5. an air outlet pipe; 6. an air outlet valve; 7. heating a ring; 8. a protective cover; 9. a rotator; 10. a bearing; 11. rotating the rod; 12. a base; 13. a guide rail; 14. a pulley; 15. protection plate, 16 reaction bottle.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating comprises the following formula raw materials in parts by weight: 3-17 parts of manganese-zinc ferrite loaded carbon nano tube, 28-32 parts of aniline, 52-60 parts of ammonium persulfate and 3-5 parts of p-toluenesulfonic acid.
The preparation method of the manganese-zinc ferrite loaded carbon nanotube comprises the following steps:
(1) adding distilled water and carboxylated carbon nanotubes into a reaction bottle, adding an acyl chloride reagent thionyl chloride after ultrasonic dispersion is uniform, the mass ratio of the distilled water to the carboxylated carbon nanotubes is 6-8:1, placing the reaction bottle into an oil bath pan, wherein the oil bath pan comprises a pan body, an oil bath pan cover is movably connected on the pan body, the left side of the pan body is fixedly connected with an air inlet pipe, the air inlet pipe is movably connected with an air inlet valve, the right side of the pan body is fixedly connected with an air outlet pipe, the air outlet pipe is movably connected with an air outlet valve, a heating ring is fixedly connected inside the pan body, a protective cover is fixedly connected below the pan body, a rotator is arranged inside the protective cover, the rotator is fixedly connected with a bearing, the bearing is movably connected with a rotary rod, a base is fixedly connected above the rotary rod, a guide rail is fixedly connected on the upper surface of, heating to 80-90 ℃ under nitrogen atmosphere, stirring at constant speed for reaction for 30-40h, vacuum drying the solution to remove the solvent, washing the solid product with distilled water and ethanol, fully drying to obtain the acyl chlorinated carbon nanotube, adding distilled water and the acyl chlorinated carbon nanotube into a reaction bottle, ultrasonically dispersing uniformly, adding p-phenylenediamine with the mass ratio of 1:5-10, placing the reaction bottle in an oil bath, heating to 80-90 ℃ under nitrogen atmosphere, stirring at constant speed for reaction for 15-20h, vacuum drying the solution to remove the solvent, washing the solid product with distilled water and ethanol, and preparing the p-phenylenediamine covalent modified aminated carbon nanotube.
(2) Adding N, N-dimethylformamide solvent and polyvinylpyrrolidone into a reaction bottle, stirring for 10-15h, adding FeCl3、MnCl2And ZnCl2Continuously stirring the three substances for 10-15h to form an electrospinning solution, injecting the solution into a miniature injector for electrostatic spinning at a voltage of 18-20Kv and a flow rate of 0.5-1ml/h, wherein the distance between the miniature injector and a receiver is 15-18cm, preparing to obtain a nanofiber precursor, and placing the nanofiber precursor in the miniature injector and the receiverAnd calcining the mixture for 3 to 5 hours at 650-680 ℃ in a muffle furnace at the heating rate of 5 to 10 ℃/min to prepare the manganese-zinc ferrite nanofiber.
(3) Adding distilled water, an aminated carbon nano tube and manganese-zinc ferrite nano fibers into a reaction bottle in a mass ratio of 10-15:1, placing the solution into an automatic reaction kettle after uniform ultrasonic dispersion, heating to 120 ℃ plus materials, stirring at a constant speed for adsorption for 20-30h, filtering the solution to remove the solvent, and drying the solid product to obtain the manganese-zinc ferrite loaded carbon nano tube.
The preparation method of the manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating comprises the following steps:
(1) adding distilled water, 3-17 parts of manganese-zinc ferrite loaded carbon nano-tubes and 28-32 parts of aniline into a reaction bottle, uniformly stirring, placing the mixture into a low-temperature reactor, adding 52-60 parts of ammonium persulfate and 3-5 parts of p-toluenesulfonic acid at 0-5 ℃, uniformly stirring and reacting for 8-12h, centrifugally washing the solution to remove the solvent, dissolving the solid product, pouring the dissolved solid product into a film forming mold, and naturally casting to form a film to prepare the manganese-zinc ferrite-carbon nano-tube grafted polyaniline wave-absorbing coating.
Example 1
(1) Preparing a p-phenylenediamine covalently modified aminated carbon nanotube component 1: adding distilled water and carboxylated carbon nanotubes into a reaction bottle, adding an acyl chloride reagent thionyl chloride after ultrasonic dispersion is uniform, the mass ratio of the distilled water to the carboxylated carbon nanotubes is 6:1, placing the reaction bottle into an oil bath pan, wherein the oil bath pan comprises a pan body, an oil bath pan cover is movably connected on the pan body, the left side of the pan body is fixedly connected with an air inlet pipe, the air inlet pipe is movably connected with an air inlet valve, the right side of the pan body is fixedly connected with an air outlet pipe, the air outlet pipe is movably connected with an air outlet valve, the interior of the pan body is fixedly connected with a heating ring, a protective cover is fixedly connected below the pan body, a rotator is arranged inside the protective cover, the rotator is fixedly connected with a bearing, the bearing is movably connected with a rotating rod, a base is fixedly connected above the rotating rod, a guide rail is fixedly connected with the, heating to 80 ℃ in nitrogen atmosphere, stirring at constant speed for reaction for 30h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, fully drying to obtain an acyl chlorinated carbon nanotube, adding distilled water and the acyl chlorinated carbon nanotube into a reaction bottle, adding p-phenylenediamine after uniform ultrasonic dispersion, wherein the mass ratio of the two is 1:5, placing the reaction bottle in an oil bath pot, heating to 80 ℃ in nitrogen atmosphere, stirring at constant speed for reaction for 15h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and preparing the p-phenylenediamine covalence modified aminated carbon nanotube component 1.
(2) Preparing a manganese-zinc ferrite nanofiber component 1: adding N, N-dimethylformamide solvent and polyvinylpyrrolidone into a reaction bottle, stirring for 10h, adding FeCl3、MnCl2And ZnCl2Continuously stirring the three substances for 10 hours to form electrospinning solution, injecting the solution into a micro injector for electrostatic spinning process at the voltage of 18Kv and the flow rate of 0.5ml/h, wherein the distance between the micro injector and a receiver is 15cm, preparing to obtain a nanofiber precursor, placing the nanofiber precursor in a muffle furnace, heating at the rate of 5 ℃/min, and calcining at 650 ℃ for 3 hours to obtain the manganese-zinc ferrite nanofiber component 1.
(3) Preparing a manganese-zinc ferrite loaded carbon nanotube component 1: adding distilled water, an aminated carbon nanotube component 1 and a manganese-zinc ferrite nanofiber component 1 into a reaction bottle in a mass ratio of 10:1, placing the solution into an automatic reaction kettle after ultrasonic dispersion is uniform, heating to 120 ℃, stirring at a constant speed for adsorption for 20 hours, filtering the solution to remove the solvent, and drying a solid product to obtain the manganese-zinc ferrite loaded carbon nanotube component 1.
(4) Preparing a manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating material 1: adding distilled water and 17 parts of manganese-zinc ferrite loaded carbon nanotube component 1 and 28 parts of aniline into a reaction bottle, uniformly stirring, placing the mixture into a low-temperature reactor, adding 52 parts of ammonium persulfate and 3 parts of p-toluenesulfonic acid at 0 ℃, uniformly stirring and reacting for 8 hours, centrifugally washing the solution to remove the solvent, dissolving a solid product, pouring the dissolved solid product into a film forming mold, and naturally casting to form a film to prepare the manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating material 1.
Example 2
(1) Preparing a p-phenylenediamine covalently modified aminated carbon nanotube component 2: adding distilled water and carboxylated carbon nanotubes into a reaction bottle, adding an acyl chloride reagent thionyl chloride after ultrasonic dispersion is uniform, wherein the mass ratio of the distilled water to the carboxylated carbon nanotubes to the thionyl chloride is 8:1, placing the reaction bottle into an oil bath pan, the oil bath pan comprises a pan body, an oil bath pan cover is movably connected to the upper part of the pan body, the left side of the pan body is fixedly connected with an air inlet pipe, the air inlet pipe is movably connected with an air inlet valve, the right side of the pan body is fixedly connected with an air outlet pipe, the air outlet pipe is movably connected with an air outlet valve, the interior of the pan body is fixedly connected with a heating ring, a protective cover is fixedly connected to the lower part of the pan body, a rotator is arranged in the protective cover, the rotator is fixedly connected with a bearing, the bearing is movably connected with a rotating rod, a base is fixedly connected to, heating to 80 ℃ in nitrogen atmosphere, stirring at constant speed for reaction for 40h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, fully drying to obtain the acyl chlorinated carbon nanotube, adding distilled water and the acyl chlorinated carbon nanotube into a reaction bottle, adding p-phenylenediamine after uniform ultrasonic dispersion, wherein the mass ratio of the two is 1:10, placing the reaction bottle in an oil bath pot, heating to 80 ℃ in nitrogen atmosphere, stirring at constant speed for reaction for 20h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and preparing the p-phenylenediamine covalence modified aminated carbon nanotube component 2.
(2) Preparing a manganese-zinc ferrite nanofiber component 2: adding N, N-dimethylformamide solvent and polyvinylpyrrolidone into a reaction bottle, stirring for 10h, adding FeCl3、MnCl2And ZnCl2Continuously stirring the three substances for 15 hours to form electrospinning solution, injecting the solution into a micro injector to perform an electrostatic spinning process, wherein the voltage is 18Kv, the flow rate is 0.5ml/h, the distance between the micro injector and a receiver is 18cm, preparing to obtain a nanofiber precursor, placing the nanofiber precursor into a muffle furnace, heating at the rate of 5 ℃/min, and calcining at 650 ℃ for 5 hours to obtain the manganese-zinc ferrite sodiumRice fibre component 2.
(3) Preparing a manganese-zinc ferrite loaded carbon nanotube component 2: adding distilled water, an aminated carbon nanotube component 2 and a manganese-zinc ferrite nanofiber component 2 into a reaction bottle in a mass ratio of 10:1, placing the solution into an automatic reaction kettle after ultrasonic dispersion is uniform, heating to 150 ℃, stirring at a constant speed for adsorption for 30 hours, filtering the solution to remove the solvent, and drying a solid product to obtain the manganese-zinc ferrite loaded carbon nanotube component 2.
(4) Preparing a manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating material 2: adding distilled water and 13.5 parts of manganese-zinc ferrite loaded carbon nanotube component 2 and 29 parts of aniline into a reaction bottle, uniformly stirring, placing the mixture into a low-temperature reactor, adding 54 parts of ammonium persulfate and 3.5 parts of p-toluenesulfonic acid at 5 ℃, uniformly stirring and reacting for 8 hours, centrifugally washing the solution to remove the solvent, dissolving the solid product, pouring the dissolved solid product into a film forming mold, and naturally casting to form a film to prepare the manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating material 2.
Example 3
(1) Preparing a p-phenylenediamine covalently modified aminated carbon nanotube component 3: adding distilled water and carboxylated carbon nanotubes into a reaction bottle, adding an acyl chloride reagent thionyl chloride after ultrasonic dispersion is uniform, the mass ratio of the two is 7:1, placing the reaction bottle into an oil bath pan, wherein the oil bath pan comprises a pan body, an oil bath pan cover is movably connected on the pan body, the left side of the pan body is fixedly connected with an air inlet pipe, the air inlet pipe is movably connected with an air inlet valve, the right side of the pan body is fixedly connected with an air outlet pipe, the air outlet pipe is movably connected with an air outlet valve, the interior of the pan body is fixedly connected with a heating ring, a protective cover is fixedly connected below the pan body, a rotator is arranged inside the protective cover, the rotator is fixedly connected with a bearing, the bearing is movably connected with a rotating rod, a base is fixedly connected above the rotating rod, a guide rail is fixedly connected with the upper surface of the base and, heating to 85 ℃ in nitrogen atmosphere, stirring at constant speed for reaction for 35h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, fully drying to obtain an acyl chlorinated carbon nanotube, adding distilled water and the acyl chlorinated carbon nanotube into a reaction bottle, adding p-phenylenediamine after uniform ultrasonic dispersion, wherein the mass ratio of the two is 1:8, placing the reaction bottle in an oil bath pot, heating to 85 ℃ in nitrogen atmosphere, stirring at constant speed for reaction for 17h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and preparing the p-phenylenediamine covalence modified aminated carbon nanotube component 3.
(2) Preparing a manganese-zinc ferrite nanofiber component 3: adding N, N-dimethylformamide solvent and polyvinylpyrrolidone into a reaction bottle, stirring for 12h, adding FeCl3、MnCl2And ZnCl2Continuously stirring the three substances for 13 hours to form electrospinning solution, injecting the solution into a micro injector to perform an electrostatic spinning process, controlling the voltage to be 19Kv, the flow rate to be 0.8ml/h, controlling the distance between the micro injector and a receiver to be 16cm, preparing to obtain a nanofiber precursor, placing the nanofiber precursor in a muffle furnace, heating at the rate of 10 ℃/min, and calcining at 675 ℃ for 4 hours to obtain the manganese-zinc ferrite nanofiber component 3.
(3) Preparing a manganese-zinc ferrite loaded carbon nanotube component 3: adding distilled water, an aminated carbon nanotube component 3 and a manganese-zinc ferrite nanofiber component 3 into a reaction bottle in a mass ratio of 12:1, placing the solution into an automatic reaction kettle after uniform ultrasonic dispersion, heating to 135 ℃, stirring at a constant speed for adsorption for 20 hours, filtering the solution to remove the solvent, and drying the solid product to obtain the manganese-zinc ferrite loaded carbon nanotube component 3.
(4) Preparing a manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating material 3: adding distilled water and 10 parts of manganese-zinc ferrite loaded carbon nanotube component 3 and 30 parts of aniline into a reaction bottle, uniformly stirring, placing into a low-temperature reactor, adding 56 parts of ammonium persulfate and 4 parts of dissolved ammonium persulfate at the temperature of 2 ℃, pouring into a film forming mold, and naturally casting to form a film to prepare the manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating material 3.
Example 4
(1) Preparing a p-phenylenediamine covalently modified aminated carbon nanotube component 4: adding distilled water and carboxylated carbon nanotubes into a reaction bottle, adding an acyl chloride reagent thionyl chloride after ultrasonic dispersion is uniform, the mass ratio of the distilled water to the carboxylated carbon nanotubes is 6:1, placing the reaction bottle into an oil bath pan, wherein the oil bath pan comprises a pan body, an oil bath pan cover is movably connected on the pan body, the left side of the pan body is fixedly connected with an air inlet pipe, the air inlet pipe is movably connected with an air inlet valve, the right side of the pan body is fixedly connected with an air outlet pipe, the air outlet pipe is movably connected with an air outlet valve, the interior of the pan body is fixedly connected with a heating ring, a protective cover is fixedly connected below the pan body, a rotator is arranged inside the protective cover, the rotator is fixedly connected with a bearing, the bearing is movably connected with a rotating rod, a base is fixedly connected above the rotating rod, a guide rail is fixedly connected with the, heating to 80 ℃ in nitrogen atmosphere, stirring at constant speed for reaction for 40h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, fully drying to obtain the acyl chlorinated carbon nanotube, adding distilled water and the acyl chlorinated carbon nanotube into a reaction bottle, adding p-phenylenediamine after uniform ultrasonic dispersion, wherein the mass ratio of the two is 1:5, placing the reaction bottle in an oil bath pot, heating to 90 ℃ in nitrogen atmosphere, stirring at constant speed for reaction for 20h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and preparing the p-phenylenediamine covalence modified aminated carbon nanotube component 4.
(2) Preparing a manganese-zinc ferrite nanofiber component 4: adding N, N-dimethylformamide solvent and polyvinylpyrrolidone into a reaction bottle, stirring for 10h, adding FeCl3、MnCl2And ZnCl2And the mass ratio of the three substances is 4:0.4:0.6, continuously stirring for 15h to form electrospinning solution, injecting the solution into a micro injector for electrostatic spinning process, wherein the voltage is 18Kv, the flow rate is 1ml/h, the distance between the micro injector and a receiver is 15cm, preparing to obtain a nanofiber precursor, placing the nanofiber precursor into a muffle furnace, heating at the rate of 10 ℃/min, and calcining at 680 ℃ for 3h to obtain the manganese-zinc ferrite nanofiber component 4.
(3) Preparing a manganese-zinc ferrite loaded carbon nanotube component 4: adding distilled water, an aminated carbon nanotube component 4 and a manganese-zinc ferrite nanofiber component 4 into a reaction bottle in a mass ratio of 15:1, placing the solution into an automatic reaction kettle after ultrasonic dispersion is uniform, heating to 120 ℃, stirring at a constant speed for adsorption for 30 hours, filtering the solution to remove the solvent, and drying a solid product to obtain the manganese-zinc ferrite loaded carbon nanotube component 4.
(4) Preparing a manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating material 4: adding distilled water and 6.5 parts of manganese-zinc ferrite loaded carbon nanotube component 4 and 31 parts of aniline into a reaction bottle, uniformly stirring, placing the mixture into a low-temperature reactor, adding 58 parts of ammonium persulfate and 4.5 parts of p-toluenesulfonic acid at 5 ℃, uniformly stirring for reaction for 8 hours, centrifugally washing the solution to remove the solvent, dissolving a solid product, pouring the dissolved solid product into a film forming mold, and naturally casting to form a film to prepare the manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating material 4.
Example 5
(1) Preparing a p-phenylenediamine covalently modified aminated carbon nanotube component 5: adding distilled water and carboxylated carbon nanotubes into a reaction bottle, adding an acyl chloride reagent thionyl chloride after ultrasonic dispersion is uniform, wherein the mass ratio of the distilled water to the carboxylated carbon nanotubes to the thionyl chloride is 8:1, placing the reaction bottle into an oil bath pan, the oil bath pan comprises a pan body, an oil bath pan cover is movably connected to the upper part of the pan body, the left side of the pan body is fixedly connected with an air inlet pipe, the air inlet pipe is movably connected with an air inlet valve, the right side of the pan body is fixedly connected with an air outlet pipe, the air outlet pipe is movably connected with an air outlet valve, the interior of the pan body is fixedly connected with a heating ring, a protective cover is fixedly connected to the lower part of the pan body, a rotator is arranged in the protective cover, the rotator is fixedly connected with a bearing, the bearing is movably connected with a rotating rod, a base is fixedly connected to, heating to 90 ℃ under nitrogen atmosphere, stirring at constant speed for reaction for 40h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, fully drying to obtain the acyl chlorinated carbon nanotube, adding distilled water and the acyl chlorinated carbon nanotube into a reaction bottle, adding p-phenylenediamine after uniform ultrasonic dispersion, wherein the mass ratio of the two is 1:10, placing the reaction bottle in an oil bath pot, heating to 90 ℃ under nitrogen atmosphere, stirring at constant speed for reaction for 20h, drying the solution in vacuum to remove the solvent, washing the solid product with distilled water and ethanol, and preparing the p-phenylenediamine covalence modified aminated carbon nanotube component 5.
(2) Preparing a manganese-zinc ferrite nanofiber component 5: adding N, N-dimethylformamide solvent and polyvinylpyrrolidone into a reaction bottle, stirring for 15h, adding FeCl3、MnCl2And ZnCl2And the mass ratio of the three substances is 4:0.4:0.8, continuously stirring for 15h to form electrospinning solution, injecting the solution into a micro injector for electrostatic spinning process, wherein the voltage is 20Kv, the flow rate is 1ml/h, the distance between the micro injector and a receiver is 18cm, preparing to obtain a nanofiber precursor, placing the nanofiber precursor into a muffle furnace, heating at the rate of 10 ℃/min, and calcining at 680 ℃ for 5h to obtain the manganese-zinc ferrite nanofiber component 5.
(3) Preparing a manganese-zinc ferrite loaded carbon nanotube component 5: adding distilled water, an aminated carbon nanotube component 5 and a manganese-zinc ferrite nanofiber component 5 into a reaction bottle in a mass ratio of 15:1, placing the solution into an automatic reaction kettle after ultrasonic dispersion is uniform, heating to 150 ℃, stirring at a constant speed for adsorption for 30 hours, filtering the solution to remove the solvent, and drying a solid product to obtain the manganese-zinc ferrite loaded carbon nanotube component 5.
(4) Preparing a manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating material 5: adding distilled water and 3 parts of manganese-zinc ferrite loaded carbon nanotube component 5 and 32 parts of aniline into a reaction bottle, uniformly stirring, placing the mixture into a low-temperature reactor, adding 60 parts of ammonium persulfate and 5 parts of p-toluenesulfonic acid at 0 ℃, uniformly stirring and reacting for 12 hours, centrifugally washing the solution to remove the solvent, dissolving the solid product, pouring the dissolved solid product into a film forming mold, and naturally casting to form a film to prepare the manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating material 5.
The wave-absorbing performance of the manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating material in the embodiment 1-5 is tested by using an Agilent 8753ES vector network analyzer, and the test standard is GB/T34938-2017.
In summary, according to the manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating, thionyl chloride reacts with carboxyl of a carboxylated carbon nanotube to generate an acylchlorinated carbon nanotube, acyl chloride groups react with amino of p-diphenylamine to generate an aminated carbon nanotube, the manganese-zinc ferrite nanofiber is prepared by an electrostatic spinning method, the manganese-zinc ferrite nanofiber has good nanometer morphology, the manganese-zinc ferrite nanofiber enters the tube wall of the carbon nanotube by a high-pressure hydrothermal method to form a manganese-zinc ferrite loaded carbon nanotube material, ammonium persulfate is used as an initiator, p-toluenesulfonic acid is used as a catalyst, aniline and the aminated carbon nanotube are subjected to in-situ polymerization, the carbon nanotube and polyaniline are subjected to covalent bond type copolymer, the dispersibility and compatibility of the carbon nanotube and the manganese-zinc ferrite in polyaniline are greatly improved, and the influence of the carbon nanotube and the manganese-zinc ferrite which are not uniformly dispersed on the mechanical property of a polyaniline film coating is avoided.
The manganese-zinc ferrite has high magnetic conductivity and magnetic loss performance, a small amount of carbon nano tubes with excellent conductivity generate a low percolation threshold in polyaniline to generate a polarization effect so as to form dielectric loss, the polyaniline has good conductivity, and a polymer molecular chain has polarization carriers and dual-polarization carriers so as to generate a strong polarization relaxation effect.
Claims (7)
1. The manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating comprises the following formula raw materials and components in parts by weight, and is characterized in that: 3-17 parts of manganese-zinc ferrite loaded carbon nano tube, 28-32 parts of aniline, 52-60 parts of ammonium persulfate and 3-5 parts of p-toluenesulfonic acid.
2. The manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating as claimed in claim 1, wherein: the preparation method of the manganese-zinc ferrite loaded carbon nanotube comprises the following steps:
(1) adding distilled water and a carboxylated carbon nanotube into a reaction bottle, adding an acyl chloride reagent thionyl chloride after uniform ultrasonic dispersion, placing the reaction bottle into an oil bath pot, heating to 80-90 ℃ under the nitrogen atmosphere, reacting for 30-40h, removing the solvent from the solution, washing and drying to prepare an acyl chlorinated carbon nanotube, adding distilled water and the acyl chlorinated carbon nanotube into the reaction bottle, adding p-phenylenediamine after uniform ultrasonic dispersion, placing the reaction bottle into the oil bath pot, heating to 80-90 ℃ under the nitrogen atmosphere, reacting for 15-20h, removing the solvent from the solution, washing a solid product, and preparing the p-phenylenediamine covalence modified aminated carbon nanotube;
(2) adding polyvinylpyrrolidone into N, N-dimethylformamide solvent, stirring for 10-15h, adding FeCl3、MnCl2And ZnCl2Continuously stirring for 10-15h to form electrospinning liquid, injecting the electrospinning liquid into a micro injector to perform an electrostatic spinning process, wherein the voltage is 18-20Kv, the flow rate is 0.5-1ml/h, the distance between the micro injector and a receiver is 15-18cm, preparing to obtain a nanofiber precursor, placing the nanofiber precursor in a muffle furnace, heating at the rate of 5-10 ℃/min, and calcining at 650-680 ℃ for 3-5h to obtain the manganese-zinc ferrite nanofiber;
(3) adding aminated carbon nano tubes and manganese-zinc ferrite nano fibers into distilled water, placing the solution into an automatic reaction kettle after uniform ultrasonic dispersion, heating to the temperature of 120 ℃ and 150 ℃, stirring at constant speed for adsorption for 20-30h, filtering and drying the solution, and preparing the manganese-zinc ferrite loaded carbon nano tubes.
3. The manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating as claimed in claim 2, wherein: the oil bath pot is including the pot body, the last swing joint of the pot body has the oil bath pot cover, the left side and the intake pipe fixed connection of the pot body, intake pipe swing joint has the admission valve, the right side fixedly connected with outlet duct of the pot body, outlet duct and outlet valve swing joint, the inside fixedly connected with heating ring of the pot body, the below fixedly connected with safety cover of the pot body, the inside of safety cover is provided with the circulator, circulator and bearing fixed connection, bearing swing joint has the rotary rod, the top fixedly connected with base of rotary rod, the last fixed surface of base is connected with the guide rail, guide rail and pulley swing joint, the top and the protection shield fixed connection of pulley, the top of base is.
4. The manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating as claimed in claim 2, wherein: the mass ratio of the carboxylated carbon nano tube to the thionyl chloride is 6-8:1, and the mass ratio of the acyl chlorinated carbon nano tube to the p-phenylenediamine is 1: 5-10.
5. The manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating as claimed in claim 2, wherein: the FeCl3、MnCl2And ZnCl2The mass ratio of the substances is 4:0.2-0.4: 0.6-0.8.
6. The manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating as claimed in claim 2, wherein: the mass ratio of the aminated carbon nanotube to the manganese-zinc ferrite nanofiber is 10-15: 1.
7. The manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating as claimed in claim 1, wherein: the preparation method of the manganese-zinc ferrite-carbon nanotube grafted polyaniline wave-absorbing coating comprises the following steps:
(1) adding 3-17 parts of manganese-zinc ferrite loaded carbon nano-tubes and 28-32 parts of aniline into distilled water, stirring uniformly, adding 52-60 parts of ammonium persulfate and 3-5 parts of p-toluenesulfonic acid at 0-5 ℃, stirring at a constant speed for reacting for 8-12h, centrifuging and washing the solution, dissolving a solid product, pouring into a film forming mold, and naturally casting to form a film to prepare the manganese-zinc ferrite-carbon nano-tube grafted polyaniline wave-absorbing coating.
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