CN111509401B - Wave-absorbing material of cobalt-doped zinc oxide-polymer-based carbon material and preparation method thereof - Google Patents
Wave-absorbing material of cobalt-doped zinc oxide-polymer-based carbon material 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 cobalt-doped zinc oxide-polymer-based carbon material wave-absorbing material, which comprises the following formula raw materials and components: the catalyst comprises cobalt-doped zinc oxide modified graphene, 9, 10-dibromoanthracene, p-diacetylene benzene, a catalyst and an accelerant. The cobalt-doped zinc oxide-polymer-based carbon material wave-absorbing material is characterized in that cobalt-doped zinc oxide hollow microspheres are favorable for improving the magnetic conductivity of zinc oxide and enhancing the electromagnetic loss performance of the zinc oxide on electromagnetic waves, high-conductivity graphene oxide can promote the material to perform resistance loss and electromagnetic loss on the electromagnetic waves, a porous super-crosslinked polymer is prepared through a coupling reaction and an in-situ polymerization method, the porous carbon material is coated with the cobalt-doped zinc oxide through high-temperature calcination, and the excellent impedance matching performance is achieved through the combination of magnetic loss, dielectric loss and resistance type loss, the electromagnetic waves are constantly reflected and consumed, and the cobalt-doped zinc oxide-polymer-based carbon material wave-absorbing material has excellent electromagnetic wave consumption performance and wave-absorbing performance.
Description
Technical Field
The invention relates to the technical field of wave-absorbing materials, in particular to a wave-absorbing material of a cobalt-doped zinc oxide-polymer-based carbon material and a preparation method thereof.
Background
The electromagnetic wave has electromagnetic radiation characteristics, such as radio wave, microwave, infrared ray, ultraviolet ray and the like, along with the development of modern science and technology, the influence of the electromagnetic wave radiation on the ecological environment is increasingly increased, the normal operation of electronic instruments such as an aircraft navigation system, a medical precision instrument, a mobile phone, a computer network and the like can be influenced, a human body can damage a central nervous system, an immune system, a visual system and the like of the human body through thermal effect, non-thermal effect and accumulation effect after contacting the electromagnetic wave for a long time, diseases such as immunity reduction, metabolism disorder, strength and hearing reduction and the like can be induced, the wave absorbing material can absorb and weaken the electromagnetic wave energy projected to the surface of the material and reduce the electromagnetic wave interference, and the wave absorbing material is required to have higher absorption rate on the electromagnetic wave in a wider frequency band in engineering application and simultaneously has light weight, temperature resistance and the like, Corrosion resistance and the like.
The existing wave-absorbing materials mainly comprise carbon-series wave-absorbing materials, such as graphene, carbon fibers, carbon nanotubes and the like, and can convert electromagnetic energy into heat energy through resistance-type loss to consume electromagnetic waves; iron-based wave-absorbing materials, such as ferrite, magnetic iron nano-materials and the like, can perform magnetic loss on electromagnetic waves through hysteresis loss, gyromagnetic eddy current, damping loss and magnetic after-effect; the porous carbon material has the advantages of high specific surface area, light weight, strong electromagnetic attenuation capability and the like, and is widely applied to wave-absorbing materials; the zinc oxide has the advantages of large dielectric constant, low density, light weight, low price and the like, is a wave-absorbing material with great potential, but the zinc oxide has low magnetic conductivity and poor dielectric loss capability and impedance matching performance, limits the application of the zinc oxide in the wave-absorbing material, and can combine the porous carbon material, the graphene and the zinc oxide to obtain the composite wave-absorbing material with high impedance matching performance combining the magnetic loss and the dielectric loss.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a wave-absorbing material of a cobalt-doped zinc oxide-polymer-based carbon material and a preparation method thereof, and solves the problems of low magnetic conductivity, poor dielectric loss capability and poor impedance matching performance of zinc oxide.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a cobalt-doped zinc oxide-polymer-based carbon material wave-absorbing material comprises the following formula raw materials in parts by weight: 40-52 parts of cobalt-doped zinc oxide modified graphene, 32-38 parts of 9, 10-dibromoanthracene, 14-18 parts of p-diethynylbenzene, 1.5-2.5 parts of catalyst and 0.5-1.5 parts of promoter.
Preferably, the catalyst is tetrakis (triphenylphosphine) palladium and the promoter is cuprous iodide.
Preferably, the preparation method of the cobalt-doped zinc oxide modified graphene comprises the following steps:
(1) adding concentrated sulfuric acid and polystyrene microspheres into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic instrument, performing ultrasonic dispersion treatment, heating to 40-60 ℃, performing magnetic stirring reaction at a constant speed for 4-8 hours, performing centrifugal separation on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare the sulfonated polystyrene microspheres.
(2) Adding ethanol solvent and sulfonated polystyrene microspheres into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic instrument, ultrasonically dispersing the mixture uniformly, and then adding ZnCl into the mixture2And CoCl2Heating to 50-80 ℃, magnetically stirring at a constant speed for reaction for 1-3h, adding NaOH to continue to react for 2-4h, centrifugally separating the solution to remove the solvent, washing the solid product by using distilled water and ethanol, placing the dried solid product in a muffle furnace, heating to 540-580 ℃ at the heating rate of 1-3 ℃/min, and calcining for 2-3h, wherein the calcined product is the cobalt-doped zinc oxide hollow microsphere.
(3) Adding distilled water, graphene oxide and cobalt-doped zinc oxide hollow microspheres into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic instrument, performing ultrasonic dispersion uniformly, centrifuging and washing the solution to remove the solvent, and fully drying to obtain the cobalt-doped zinc oxide modified graphene.
Preferably, the constant temperature ultrasonic instrument comprises an instrument shell, a sound insulation layer fixedly connected with the inside of the sound insulation layer, heating devices fixedly connected with the two sides of the inside of the heat insulation layer, an ultrasonic generator fixedly connected with the upside of the heat insulation layer, an ultrasonic probe fixedly connected with the lower part of the ultrasonic generator, a stirring device fixedly connected with the lower side of the instrument shell, a stirring device movably connected with a stirring shaft, a stirring fan blade fixedly connected with the surface of the stirring shaft, an iron-absorbing stone fixedly connected with the upper surface of the stirring fan blade, a stirring shaft movably connected with an adjuster, a telescopic rod movably connected with the upper part of the telescopic rod, a bearing fixedly connected with an objective table, a reaction bottle placed on the upper surface of the objective table, an adjusting rod movably connected with the upper part of the objective table, an adjusting rod movably connected with an adjusting valve, an adjusting rod movably connected with the adjusting valve, One end of the cross rod is fixedly connected with a baffle.
Preferably, the polystyrene microspheres and ZnCl2、CoCl2And NaOH in a mass ratio of 80-120:93-99:1-7: 120-140.
Preferably, the mass ratio of the graphene oxide to the cobalt-doped zinc oxide hollow microspheres is 1: 6-10.
Preferably, the preparation method of the wave-absorbing material of the cobalt-doped zinc oxide-polymer-based carbon material comprises the following steps:
(1) adding a mixed solvent of triethylamine and N, N-dimethylformamide into a reaction bottle, wherein the volume ratio of the mixed solvent to the cobalt-doped zinc oxide modified graphene is 1:1-1.5, adding 40-52 parts of cobalt-doped zinc oxide modified graphene, placing the graphene into a constant-temperature ultrasonic instrument, ultrasonically dispersing the graphene uniformly, adding 32-38 parts of 9, 10-dibromoanthracene and 14-18 parts of p-diacetylene benzene, stirring the graphene and the p-diacetylene for dissolving, adding 1.5-2.5 parts of catalyst tetrakis (triphenylphosphine) palladium and 0.5-1.5 parts of promoter cuprous iodide, heating the graphene and the p-dibromoanthracene to 75-95 ℃, stirring the graphene and the p-dibromoanthracene at a constant speed for reaction for 60-80 hours, placing the solution into an ice water bath, adding distilled water until a large amount of precipitate is separated out, filtering the solution to remove the solvent, washing a solid product by using the distilled water and diethyl ether, and fully drying the solid product to prepare the porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material.
(2) And (3) placing the porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material in an atmosphere resistance furnace, heating to 720-760 ℃ at the heating rate of 3-8 ℃/min, and carrying out heat preservation and calcination for 2-3h to obtain a calcined product, namely the wave-absorbing material of the cobalt-doped zinc oxide-polymer-based carbon material.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the wave-absorbing material of the cobalt-doped zinc oxide-polymer-based carbon material takes the sulfopolystyrene microsphere as a template, and Zn is added by the sulfogroup2+And Co2+The cobalt-doped zinc oxide hollow microspheres are uniformly adsorbed on the surfaces of polystyrene microspheres, and are prepared by a liquid phase deposition method and a high-temperature thermal cracking method, part of Zn lattices are replaced by Co doping, so that the magnetic conductivity of zinc oxide is improved, the electromagnetic loss performance of zinc oxide on electromagnetic waves is enhanced, and the zinc oxide hollow microspheres are loaded into graphene oxide with rich lamellar structures, and the high-conductivity graphene oxide can promote materials to perform resistance loss and electromagnetic loss on the electromagnetic waves.
The cobalt-doped zinc oxide-polymer-based carbon material wave-absorbing material is prepared by taking 9, 10-dibromoanthracene and 14-18 parts of p-diethynylbenzene as monomers through coupling reaction and in-situ polymerization, wherein the porous super-crosslinked polymer is coated with cobalt-doped zinc oxide, has rich pore channel structure and rigid structure containing benzene rings and anthracene condensed rings, maintains the pore channel structure not to collapse through thermal cracking calcination, and is prepared into the polymer-based porous carbon material coated with cobalt-doped zinc oxide, and the cobalt-doped zinc oxide has excellent impedance matching performance by combining magnetic loss, dielectric loss and resistance type loss, and has the advantages of promoting continuous reflection and consumption of electromagnetic waves, when a sample is 3mm in thickness and the absorption frequency band is 6.6-12.5GHz, the lowest reflectivity section can reach-10 to-32.1 dB, and when the absorption frequency is 9.9GHz, the lowest reflectivity can reach-32.1 dB, so that the wave absorbing material has excellent electromagnetic wave consumption capability and wave absorbing performance.
Drawings
FIG. 1 is a schematic front view of a constant temperature ultrasound apparatus;
FIG. 2 is an enlarged schematic view of the stage;
fig. 3 is a schematic view of stage adjustment.
1. An instrument housing; 2. a sound insulating layer; 3. a heat-insulating layer; 4. a heating device; 5. an ultrasonic generator; 6. an ultrasonic probe; 7. a stirring device; 8. a stirring shaft; 9. stirring fan blades; 10. a magnet; 11. a regulator; 12. a telescopic rod; 13. bearing, 14, object stage, 15, reaction bottle, 16, adjusting rod, 17, adjusting valve, 18, cross bar, 19 and baffle.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: a cobalt-doped zinc oxide-polymer-based carbon material wave-absorbing material comprises the following formula raw materials in parts by weight: 40-52 parts of cobalt-doped zinc oxide modified graphene, 32-38 parts of 9, 10-dibromoanthracene, 14-18 parts of p-diethynylbenzene, 1.5-2.5 parts of catalyst tetrakis (triphenylphosphine) palladium and 0.5-1.5 parts of accelerator cuprous iodide.
The preparation method of the cobalt-doped zinc oxide modified graphene comprises the following steps:
(1) adding concentrated sulfuric acid and polystyrene microspheres into a reaction bottle, placing the reaction bottle into a constant-temperature ultrasonic instrument for ultrasonic dispersion treatment, wherein the constant-temperature ultrasonic instrument comprises an instrument shell, a sound insulating layer is fixedly connected inside the instrument shell, the inner part of the sound insulating layer is fixedly connected with a heat insulating layer, heating devices are fixedly connected on two sides inside the heat insulating layer, an ultrasonic generator is fixedly connected on the upper side of the heat insulating layer, an ultrasonic probe is fixedly connected below the ultrasonic generator, a stirring device is fixedly connected on the lower side of the instrument shell, the stirring device is movably connected with a stirring shaft, the surface of the stirring shaft is fixedly connected with a stirring fan sheet, an iron-absorbing stone is fixedly connected on the upper surface of the stirring fan sheet, the stirring shaft is movably connected with an adjuster, the adjuster is movably connected with a telescopic rod, the upper part of the telescopic rod is movably connected with a bearing, the bearing is fixedly connected with an objective table, and the upper surface of the objective table is provided with the reaction bottle, an adjusting rod is movably connected above the objective table, the adjusting rod is movably connected with an adjusting valve, the adjusting valve is movably connected with a cross rod, one end of the cross rod is fixedly connected with a baffle, then the mixture is heated to 40-60 ℃, the mixture is stirred and reacted for 4-8 hours at a constant speed by magnetic force, the solution is centrifugally separated to remove the solvent, the solid product is washed by distilled water and ethanol, and the solid product is fully dried to prepare the sulfonated polystyrene microsphere.
(2) Adding ethanol solvent and sulfonated polystyrene microspheres into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic instrument, ultrasonically dispersing the mixture uniformly, and then adding ZnCl into the mixture2And CoCl2Heating to 50-80 deg.C, reacting for 1-3h under uniform magnetic stirring, adding NaOH, and reacting for 2-4h, wherein the polystyrene microsphere and ZnCl are present2、CoCl2And NaOH in a mass ratio of 80-120:93-99:1-7:120-140, centrifugally separating the solution to remove the solvent, washing the solid product by using distilled water and ethanol, placing the dried solid product in a muffle furnace, heating the dried solid product to 540-580 ℃ at a heating rate of 1-3 ℃/min, and calcining for 2-3h to obtain the cobalt-doped zinc oxide hollow microsphere.
(3) Adding distilled water, graphene oxide and cobalt-doped zinc oxide hollow microspheres into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic instrument with the mass ratio of 1:6-10, performing ultrasonic dispersion uniformly, centrifuging and washing the solution to remove the solvent, and fully drying to obtain the cobalt-doped zinc oxide modified graphene.
The preparation method of the wave-absorbing material of the cobalt-doped zinc oxide-polymer-based carbon material comprises the following steps:
(1) adding a mixed solvent of triethylamine and N, N-dimethylformamide into a reaction bottle, wherein the volume ratio of the mixed solvent to the cobalt-doped zinc oxide modified graphene is 1:1-1.5, adding 40-52 parts of cobalt-doped zinc oxide modified graphene, placing the graphene into a constant-temperature ultrasonic instrument, ultrasonically dispersing the graphene uniformly, adding 32-38 parts of 9, 10-dibromoanthracene and 14-18 parts of p-diacetylene benzene, stirring the graphene and the p-diacetylene for dissolving, adding 1.5-2.5 parts of catalyst tetrakis (triphenylphosphine) palladium and 0.5-1.5 parts of promoter cuprous iodide, heating the graphene and the p-dibromoanthracene to 75-95 ℃, stirring the graphene and the p-dibromoanthracene at a constant speed for reaction for 60-80 hours, placing the solution into an ice water bath, adding distilled water until a large amount of precipitate is separated out, filtering the solution to remove the solvent, washing a solid product by using the distilled water and diethyl ether, and fully drying the solid product to prepare the porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material.
(2) And (3) placing the porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material in an atmosphere resistance furnace, heating to 720-760 ℃ at the heating rate of 3-8 ℃/min, and carrying out heat preservation and calcination for 2-3h to obtain a calcined product, namely the wave-absorbing material of the cobalt-doped zinc oxide-polymer-based carbon material.
Example 1
(1) Preparation of a sulfopolystyrene microsphere component 1: adding concentrated sulfuric acid and polystyrene microspheres into a reaction bottle, arranging the reaction bottle in a constant-temperature ultrasonic instrument, performing ultrasonic dispersion treatment, wherein the constant-temperature ultrasonic instrument comprises an instrument shell, a sound insulation layer fixedly connected inside the instrument shell, the inside of the sound insulation layer is fixedly connected with a heat insulation layer, heating devices are fixedly connected on two sides inside the heat insulation layer, an ultrasonic generator is fixedly connected on the upper side of the heat insulation layer, an ultrasonic probe is fixedly connected below the ultrasonic generator, a stirring device is fixedly connected on the lower side of the instrument shell, a stirring shaft is movably connected with the stirring shaft, a stirring fan sheet is fixedly connected on the surface of the stirring shaft, an iron-absorbing stone is fixedly connected on the upper surface of the stirring fan sheet, the stirring shaft is movably connected with an adjuster, a telescopic rod is movably connected above the telescopic rod, a bearing is movably connected with an objective table, a reaction bottle is arranged on the upper surface of the objective table, an adjusting rod is movably connected above the objective table, an adjusting rod is movably connected with the upper surface of the objective table, Adjusting a regulating valve movably connected with the regulating rod, a cross rod movably connected with the regulating valve, and a baffle fixedly connected with one end of the cross rod, heating to 40 ℃, carrying out uniform magnetic stirring reaction for 4 hours, carrying out centrifugal separation on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to obtain the sulfonated polystyrene microsphere component 1.
(2) Preparing a cobalt-doped zinc oxide hollow microsphere component 1: adding ethanol solvent and the sulfopolystyrene microsphere component 1 into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic instrument, performing ultrasonic dispersion uniformly, and then adding ZnCl2And CoCl2Heating to 50 deg.C, magnetically stirring at uniform speed for 1 hr, adding NaOH, and reacting for 2 hr, wherein the polystyrene microsphere and ZnCl are added2、CoCl2And NaOH in a mass ratio of 80:99:1:120, centrifugally separating the solution to remove the solvent, washing the solid product by using distilled water and ethanol, placing the dried solid product in a muffle furnace, heating at a rate of 1 ℃/min to 540 ℃ for calcining for 2h, wherein the calcined product is the cobalt-doped zinc oxide hollow microsphere component 1.
(3) Preparing cobalt-doped zinc oxide modified graphene 1: adding distilled water, graphene oxide and the cobalt-doped zinc oxide hollow microsphere component 1 into a reaction bottle, wherein the mass ratio of the distilled water to the graphene oxide to the cobalt-doped zinc oxide hollow microsphere component 1 is 1:6, placing the reaction bottle into a constant-temperature ultrasonic instrument, performing ultrasonic dispersion uniformly, centrifuging and washing the solution to remove the solvent, and fully drying to obtain the cobalt-doped zinc oxide modified graphene 1.
(4) Preparing a porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 1: adding a mixed solvent of triethylamine and N, N-dimethylformamide into a reaction bottle, wherein the volume ratio of the mixed solvent to the mixed solvent is 1:1, adding 52 parts of cobalt-doped zinc oxide modified graphene component 1, placing the graphene component 1 into a constant-temperature ultrasonic instrument, adding 32 parts of 9, 10-dibromoanthracene and 14 parts of p-diethynylbenzene after uniform ultrasonic dispersion, stirring and dissolving, adding 1.5 parts of catalyst tetrakis (triphenylphosphine) palladium and 0.5 part of promoter cuprous iodide, heating to 75-95 ℃, uniformly stirring and reacting for 60-80h, placing the solution into an ice water bath, adding distilled water until a large amount of precipitate is separated out, filtering the solution to remove the solvent, washing a solid product with distilled water and diethyl ether, and fully drying to obtain the porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 1.
(5) Preparing a wave-absorbing material 1 of a cobalt-doped zinc oxide-polymer-based carbon material: and (3) placing the porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 1 in an atmosphere resistance furnace, heating to 720 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation and calcination for 2h to obtain a calcined product, namely the cobalt-doped zinc oxide-polymer-based carbon material wave-absorbing material 1.
Example 2
(1) Preparation of a sulfopolystyrene microsphere component 2: adding concentrated sulfuric acid and polystyrene microspheres into a reaction bottle, arranging the reaction bottle in a constant-temperature ultrasonic instrument, performing ultrasonic dispersion treatment, wherein the constant-temperature ultrasonic instrument comprises an instrument shell, a sound insulation layer fixedly connected inside the instrument shell, the inside of the sound insulation layer is fixedly connected with a heat insulation layer, heating devices are fixedly connected on two sides inside the heat insulation layer, an ultrasonic generator is fixedly connected on the upper side of the heat insulation layer, an ultrasonic probe is fixedly connected below the ultrasonic generator, a stirring device is fixedly connected on the lower side of the instrument shell, a stirring shaft is movably connected with the stirring shaft, a stirring fan sheet is fixedly connected on the surface of the stirring shaft, an iron-absorbing stone is fixedly connected on the upper surface of the stirring fan sheet, the stirring shaft is movably connected with an adjuster, a telescopic rod is movably connected above the telescopic rod, a bearing is movably connected with an objective table, a reaction bottle is arranged on the upper surface of the objective table, an adjusting rod is movably connected above the objective table, an adjusting rod is movably connected with the upper surface of the objective table, Adjusting a regulating valve movably connected with the regulating rod, a cross rod movably connected with the regulating valve, and a baffle fixedly connected with one end of the cross rod, heating to 40 ℃, carrying out uniform magnetic stirring reaction for 8 hours, carrying out centrifugal separation on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to obtain the sulfonated polystyrene microsphere component 2.
(2) Preparing a cobalt-doped zinc oxide hollow microsphere component 2: adding ethanol solvent and sulfopolystyrene microsphere component 2 into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic instrument, performing ultrasonic dispersion uniformly, and then adding ZnCl2And CoCl2Heating to 80 ℃, magnetically stirring at a constant speed for reaction for 1 hour, adding NaOH, and continuously reacting for 2 hours, wherein the polystyrene microspheres and ZnCl2、CoCl2And NaOH in a mass ratio of 120:98:2:120, centrifuging the solution to remove the solvent,washing the solid product by using distilled water and ethanol, putting the dried solid product into a muffle furnace, heating the dried solid product to 540 ℃ at the heating rate of 3 ℃/min, and calcining the dried solid product for 3 hours to obtain a cobalt-doped zinc oxide hollow microsphere component 2.
(3) Preparing cobalt-doped zinc oxide modified graphene 2: adding distilled water, graphene oxide and a cobalt-doped zinc oxide hollow microsphere component 2 into a reaction bottle, wherein the mass ratio of the distilled water to the graphene oxide to the cobalt-doped zinc oxide hollow microsphere component 2 is 1:6, placing the reaction bottle in a constant-temperature ultrasonic instrument, performing ultrasonic dispersion uniformly, centrifuging and washing the solution to remove the solvent, and fully drying to obtain the cobalt-doped zinc oxide modified graphene 2.
(4) Preparing a porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 2: adding a mixed solvent of triethylamine and N, N-dimethylformamide into a reaction bottle, wherein the volume ratio of the mixed solvent to the mixed solvent is 1:1.5, adding 49 parts of cobalt-doped zinc oxide modified graphene component 2, placing the mixture into a constant-temperature ultrasonic instrument, adding 33.5 parts of 9, 10-dibromoanthracene and 15 parts of p-diethynylbenzene after uniform ultrasonic dispersion, stirring and dissolving, adding 1.8 parts of catalyst tetrakis (triphenylphosphine) palladium and 0.7 part of promoter cuprous iodide, heating to 75-95 ℃, stirring at a constant speed for reaction for 60-80h, placing the solution into an ice water bath, adding distilled water until a large amount of precipitate is separated out, filtering the solution to remove the solvent, washing a solid product by using distilled water and diethyl ether, and fully drying to prepare the porous hypercrosslinked polymer coated cobalt-doped zinc oxide composite material 2.
(5) Preparing a wave-absorbing material 2 of the cobalt-doped zinc oxide-polymer-based carbon material: and (3) placing the porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 2 in an atmosphere resistance furnace, heating to 760 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation and calcination for 3h to obtain a calcination product, namely the cobalt-doped zinc oxide-polymer-based carbon material wave-absorbing material 2.
Example 3
(1) Preparation of a sulfopolystyrene microsphere component 3: adding concentrated sulfuric acid and polystyrene microspheres into a reaction bottle, arranging the reaction bottle in a constant-temperature ultrasonic instrument, performing ultrasonic dispersion treatment, wherein the constant-temperature ultrasonic instrument comprises an instrument shell, a sound insulation layer fixedly connected inside the instrument shell, the inside of the sound insulation layer is fixedly connected with a heat insulation layer, heating devices are fixedly connected on two sides inside the heat insulation layer, an ultrasonic generator is fixedly connected on the upper side of the heat insulation layer, an ultrasonic probe is fixedly connected below the ultrasonic generator, a stirring device is fixedly connected on the lower side of the instrument shell, a stirring shaft is movably connected with the stirring shaft, a stirring fan sheet is fixedly connected on the surface of the stirring shaft, an iron-absorbing stone is fixedly connected on the upper surface of the stirring fan sheet, the stirring shaft is movably connected with an adjuster, a telescopic rod is movably connected above the telescopic rod, a bearing is movably connected with an objective table, a reaction bottle is arranged on the upper surface of the objective table, an adjusting rod is movably connected above the objective table, an adjusting rod is movably connected with the upper surface of the objective table, Adjusting a regulating valve movably connected with the regulating rod, a cross rod movably connected with the regulating valve, and a baffle fixedly connected with one end of the cross rod, heating to 50 ℃, carrying out uniform magnetic stirring reaction for 6h, carrying out centrifugal separation on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to obtain the sulfonated polystyrene microsphere component 3.
(2) Preparing a cobalt-doped zinc oxide hollow microsphere component 3: adding ethanol solvent and sulfopolystyrene microsphere component 3 into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic instrument, performing ultrasonic dispersion uniformly, and then adding ZnCl2And CoCl2Heating to 65 ℃, magnetically stirring at a constant speed for reaction for 2 hours, adding NaOH, and continuously reacting for 3 hours, wherein the polystyrene microspheres and ZnCl2、CoCl2And NaOH, wherein the mass ratio of the solution to the NaOH is 100:96:4:130, the solution is centrifugally separated to remove the solvent, distilled water and ethanol are used for washing a solid product, the dried solid product is placed in a muffle furnace, the heating rate is 2 ℃/min, the temperature is increased to 560 ℃ and the calcination is carried out for 2.5h, and the calcination product is the cobalt-doped zinc oxide hollow microsphere component 3.
(3) Preparing cobalt-doped zinc oxide modified graphene 3: adding distilled water, graphene oxide and a cobalt-doped zinc oxide hollow microsphere component 3 into a reaction bottle, wherein the mass ratio of the distilled water to the graphene oxide to the cobalt-doped zinc oxide hollow microsphere component 3 is 1:6-10, placing the reaction bottle into a constant-temperature ultrasonic instrument, performing ultrasonic dispersion uniformly, centrifuging and washing the solution to remove the solvent, and fully drying to obtain the cobalt-doped zinc oxide modified graphene 3.
(4) Preparing a porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 3: adding a mixed solvent of triethylamine and N, N-dimethylformamide into a reaction bottle, wherein the volume ratio of the mixed solvent to the mixed solvent is 1:1.2, adding 46 parts of cobalt-doped zinc oxide modified graphene component 3, placing the mixture into a constant-temperature ultrasonic instrument, adding 35 parts of 9, 10-dibromoanthracene and 16 parts of p-diacetylene benzene after uniform ultrasonic dispersion, stirring and dissolving, adding 2 parts of catalyst palladium tetrakis (triphenylphosphine) and 1 part of accelerator cuprous iodide, heating to 85 ℃, uniformly stirring and reacting for 70 hours, placing the solution into an ice water bath, adding distilled water until a large amount of precipitate is separated out, filtering the solution to remove the solvent, washing a solid product with distilled water and diethyl ether, and fully drying to prepare the porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 3.
(5) Preparing a wave-absorbing material 3 of the cobalt-doped zinc oxide-polymer-based carbon material: and (3) placing the porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 3 in an atmosphere resistance furnace, heating to 740 ℃ at the heating rate of 5 ℃/min, and carrying out heat preservation and calcination for 2-3h to obtain a calcination product, namely the wave-absorbing material 3 of the cobalt-doped zinc oxide-polymer-based carbon material.
Example 4
(1) Preparation of a sulfopolystyrene microsphere component 4: adding concentrated sulfuric acid and polystyrene microspheres into a reaction bottle, arranging the reaction bottle in a constant-temperature ultrasonic instrument, performing ultrasonic dispersion treatment, wherein the constant-temperature ultrasonic instrument comprises an instrument shell, a sound insulation layer fixedly connected inside the instrument shell, the inside of the sound insulation layer is fixedly connected with a heat insulation layer, heating devices are fixedly connected on two sides inside the heat insulation layer, an ultrasonic generator is fixedly connected on the upper side of the heat insulation layer, an ultrasonic probe is fixedly connected below the ultrasonic generator, a stirring device is fixedly connected on the lower side of the instrument shell, a stirring shaft is movably connected with the stirring shaft, a stirring fan sheet is fixedly connected on the surface of the stirring shaft, an iron-absorbing stone is fixedly connected on the upper surface of the stirring fan sheet, the stirring shaft is movably connected with an adjuster, a telescopic rod is movably connected above the telescopic rod, a bearing is movably connected with an objective table, a reaction bottle is arranged on the upper surface of the objective table, an adjusting rod is movably connected above the objective table, an adjusting rod is movably connected with the upper surface of the objective table, Adjusting rods are movably connected with adjusting valves, the adjusting valves are movably connected with cross rods, one ends of the cross rods are fixedly connected with baffle plates, then heating is carried out to 60 ℃, magnetic stirring reaction is carried out at a constant speed for 4-8h, solution is centrifugally separated to remove solvents, distilled water and ethanol are used for washing solid products, and full drying is carried out, so that the sulfonated polystyrene microsphere component 4 is prepared.
(2) Preparing a cobalt-doped zinc oxide hollow microsphere component 4: adding ethanol solvent and sulfopolystyrene microsphere component 4 into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic instrument, performing ultrasonic dispersion uniformly, and then adding ZnCl2And CoCl2Heating to 80 ℃, magnetically stirring at a constant speed for reaction for 1 hour, adding NaOH, and continuously reacting for 2 hours, wherein the polystyrene microspheres and ZnCl2、CoCl2And NaOH in a mass ratio of 120:94:6:120, centrifugally separating the solution to remove the solvent, washing the solid product by using distilled water and ethanol, placing the dried solid product in a muffle furnace, heating at a heating rate of 3 ℃/min to 580 ℃ for calcining for 3h, wherein the calcined product is the cobalt-doped zinc oxide hollow microsphere component 4.
(3) Preparing cobalt-doped zinc oxide modified graphene 4: adding distilled water, graphene oxide and a cobalt-doped zinc oxide hollow microsphere component 4 into a reaction bottle, wherein the mass ratio of the distilled water to the graphene oxide to the cobalt-doped zinc oxide hollow microsphere component 4 is 1:6, placing the reaction bottle into a constant-temperature ultrasonic instrument, performing ultrasonic dispersion uniformly, centrifuging and washing the solution to remove the solvent, and fully drying to obtain the cobalt-doped zinc oxide modified graphene 4.
(4) Preparing a porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 4: adding a mixed solvent of triethylamine and N, N-dimethylformamide into a reaction bottle, wherein the volume ratio of the mixed solvent to the mixed solvent is 1:1.5, adding 43 parts of cobalt-doped zinc oxide modified graphene component 4, placing the mixture into a constant-temperature ultrasonic instrument, adding 36.5 parts of 9, 10-dibromoanthracene and 17 parts of p-diethynylbenzene after uniform ultrasonic dispersion, stirring and dissolving, adding 2.2 parts of catalyst tetrakis (triphenylphosphine) palladium and 1.3 parts of promoter cuprous iodide, heating to 95 ℃, uniformly stirring and reacting for 60 hours, placing the solution into an ice water bath, adding distilled water until a large amount of precipitate is separated out, filtering the solution to remove the solvent, washing a solid product by using distilled water and diethyl ether, and fully drying to prepare the porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 4.
(5) Preparing a wave-absorbing material of a cobalt-doped zinc oxide-polymer-based carbon material 4: and (3) placing the porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 4 in an atmosphere resistance furnace, heating to 720 ℃ at the heating rate of 8 ℃/min, and carrying out heat preservation and calcination for 3h to obtain a calcined product, namely the cobalt-doped zinc oxide-polymer-based carbon material wave-absorbing material 4.
Example 5
(1) Preparation of a sulfopolystyrene microsphere component 5: adding concentrated sulfuric acid and polystyrene microspheres into a reaction bottle, arranging the reaction bottle in a constant-temperature ultrasonic instrument, performing ultrasonic dispersion treatment, wherein the constant-temperature ultrasonic instrument comprises an instrument shell, a sound insulation layer fixedly connected inside the instrument shell, the inside of the sound insulation layer is fixedly connected with a heat insulation layer, heating devices are fixedly connected on two sides inside the heat insulation layer, an ultrasonic generator is fixedly connected on the upper side of the heat insulation layer, an ultrasonic probe is fixedly connected below the ultrasonic generator, a stirring device is fixedly connected on the lower side of the instrument shell, a stirring shaft is movably connected with the stirring shaft, a stirring fan sheet is fixedly connected on the surface of the stirring shaft, an iron-absorbing stone is fixedly connected on the upper surface of the stirring fan sheet, the stirring shaft is movably connected with an adjuster, a telescopic rod is movably connected above the telescopic rod, a bearing is movably connected with an objective table, a reaction, Adjusting rods are movably connected with adjusting valves, the adjusting valves are movably connected with cross rods, one ends of the cross rods are fixedly connected with baffle plates, then heating is carried out to 60 ℃, magnetic stirring reaction is carried out at a constant speed for 4-8h, solution is centrifugally separated to remove solvents, distilled water and ethanol are used for washing solid products, and full drying is carried out, so as to obtain the sulfonated polystyrene microsphere component 5.
(2) Preparing a cobalt-doped zinc oxide hollow microsphere component 5: adding ethanol solvent and sulfopolystyrene microsphere component 5 into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic instrument, performing ultrasonic dispersion uniformly, and then adding ZnCl2And CoCl2Heating to 80 ℃, magnetically stirring at a constant speed for reaction for 3 hours, adding NaOH, and continuously reacting for 4 hours, wherein the polystyrene microspheres and ZnCl2、CoCl2And NaOH in a mass ratio of 120:93:7:140, centrifugally separating the solution to remove the solvent, washing the solid product by using distilled water and ethanol, placing the dried solid product in a muffle furnace, heating at a heating rate of 3 ℃/min to 580 ℃ for calcining for 3h, wherein the calcined product is the cobalt-doped zinc oxide hollow microsphere component 5.
(3) Preparing cobalt-doped zinc oxide modified graphene 5: adding distilled water, graphene oxide and a cobalt-doped zinc oxide hollow microsphere component 5 into a reaction bottle, wherein the mass ratio of the distilled water to the graphene oxide to the cobalt-doped zinc oxide hollow microsphere component 5 is 1:10, placing the reaction bottle into a constant-temperature ultrasonic instrument, performing ultrasonic dispersion uniformly, centrifuging and washing the solution to remove the solvent, and fully drying to obtain the cobalt-doped zinc oxide modified graphene 5.
(4) Preparing a porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 5: adding a mixed solvent of triethylamine and N, N-dimethylformamide into a reaction bottle, wherein the volume ratio of the mixed solvent to the mixed solvent is 1:1.5, adding 40 parts of cobalt-doped zinc oxide modified graphene component 5, placing the graphene component in a constant-temperature ultrasonic instrument, adding 38 parts of 9, 10-dibromoanthracene and 14-18 parts of p-diethynylbenzene after uniform ultrasonic dispersion, stirring and dissolving, adding 2.5 parts of catalyst tetrakis (triphenylphosphine) palladium and 1.5 parts of promoter cuprous iodide, heating to 95 ℃, uniformly stirring and reacting for 60-80h, placing the solution in an ice water bath, adding distilled water until a large amount of precipitate is separated out, filtering the solution to remove the solvent, washing a solid product by using distilled water and diethyl ether, and fully drying to obtain the porous hypercrosslinked polymer coated cobalt-doped zinc oxide composite material 5.
(5) Preparing a wave-absorbing material 5 of the cobalt-doped zinc oxide-polymer-based carbon material: and (3) placing the porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 5 in an atmosphere resistance furnace, heating to 760 ℃ at the heating rate of 8 ℃/min, and carrying out heat preservation and calcination for 3h to obtain a calcination product, namely the cobalt-doped zinc oxide-polymer-based carbon material wave-absorbing material 5.
The materials of examples 1-5 were pressed into sheet materials with a thickness of 3mm, and the wave-absorbing properties of the materials of examples 1-5 in the frequency range of 2-18GHz were tested using an HP722ES vector network analyzer.
In summary, the wave-absorbing material of the cobalt-doped zinc oxide-polymer-based carbon material takes the sulfonated polystyrene microspheres as a template, the sulfo groups uniformly adsorb Zn2+ and Co2+ onto the surfaces of the polystyrene microspheres, and the cobalt-doped zinc oxide hollow microspheres are prepared by a liquid phase deposition method and a high-temperature thermal cracking method, Co doping replaces part of Zn lattices, so that the magnetic conductivity of zinc oxide is improved, the electromagnetic loss performance of the zinc oxide on electromagnetic waves is enhanced, and the cobalt-doped zinc oxide hollow microspheres are loaded into graphene oxide with rich lamellar structures, so that the high-conductivity graphene oxide can promote the resistance loss and the electromagnetic loss of the material on the electromagnetic waves.
The preparation method comprises the steps of taking 9, 10-dibromoanthracene and 14-18 parts of p-diacetylene benzene as monomers, preparing a porous super-crosslinked polymer coated with cobalt-doped zinc oxide through a coupling reaction and an in-situ polymerization method, wherein the porous super-crosslinked polymer has a rich pore channel structure and a rigid structure containing a benzene ring and an anthracene condensed ring, maintaining the pore channel structure not to collapse through thermal cracking and calcination, preparing a polymer-based porous carbon material coated with the cobalt-doped zinc oxide, achieving excellent impedance matching performance through the combination of magnetic loss, dielectric loss and resistance loss, promoting the continuous reflection and consumption of electromagnetic waves by the rich pore structure of the porous carbon material and the hollow structure of the cobalt-doped zinc oxide, and when a sample is 3mm in thickness and an absorption frequency band is 6.6-12.5GHz, the lowest reflection rate can reach-10 dB to-32.1 dB, and when the absorption frequency is 9.9GHz, the lowest reflectivity can reach-32.1 dB, and the wave absorbing material has excellent electromagnetic wave consumption capacity and wave absorbing performance.
Claims (1)
1. The wave-absorbing material of the cobalt-doped zinc oxide-polymer-based carbon material comprises the following formula raw materials and components in parts by weight, and is characterized in that: 40-52 parts of cobalt-doped zinc oxide modified graphene, 32-38 parts of 9, 10-dibromoanthracene, 14-18 parts of p-diethynylbenzene, 1.5-2.5 parts of a catalyst and 0.5-1.5 parts of an accelerator;
the preparation method of the wave-absorbing material of the cobalt-doped zinc oxide-polymer-based carbon material comprises the following steps:
(1) preparation of a sulfopolystyrene microsphere component 1: adding concentrated sulfuric acid and polystyrene microspheres into a reaction bottle, arranging the reaction bottle in a constant-temperature ultrasonic instrument, performing ultrasonic dispersion treatment, wherein the constant-temperature ultrasonic instrument comprises an instrument shell, a sound insulation layer fixedly connected inside the instrument shell, the inside of the sound insulation layer is fixedly connected with a heat insulation layer, heating devices are fixedly connected on two sides inside the heat insulation layer, an ultrasonic generator is fixedly connected on the upper side of the heat insulation layer, an ultrasonic probe is fixedly connected below the ultrasonic generator, a stirring device is fixedly connected on the lower side of the instrument shell, a stirring shaft is movably connected with the stirring shaft, a stirring fan sheet is fixedly connected on the surface of the stirring shaft, an iron-absorbing stone is fixedly connected on the upper surface of the stirring fan sheet, the stirring shaft is movably connected with an adjuster, a telescopic rod is movably connected above the telescopic rod, a bearing is movably connected with an objective table, a reaction bottle is arranged on the upper surface of the objective table, an adjusting rod is movably connected above the objective table, an adjusting rod is movably connected with the upper surface of the objective table, Adjusting a regulating valve movably connected with a regulating rod, a cross rod movably connected with the regulating valve, and a baffle fixedly connected with one end of the cross rod, heating to 40 ℃, carrying out uniform magnetic stirring reaction for 4 hours, carrying out centrifugal separation on the solution to remove the solvent, washing the solid product by using distilled water and ethanol, and fully drying to prepare a sulfopolystyrene microsphere component 1;
(2) preparing a cobalt-doped zinc oxide hollow microsphere component 1: adding an ethanol solvent and a sulfonated polystyrene microsphere component 1 into a reaction bottle, placing the reaction bottle in a constant-temperature ultrasonic instrument, adding ZnCl2 and CoCl2 after ultrasonic dispersion is uniform, heating the solution to 50 ℃, magnetically stirring the solution at a constant speed for reaction for 1 hour, adding NaOH to continue to react for 2 hours, wherein the mass ratio of the polystyrene microspheres to the ZnCl2 to the CoCl2 to the NaOH is 80:99:1:120, centrifugally separating the solution to remove the solvent, washing a solid product by using distilled water and ethanol, placing the dried solid product in a muffle furnace, heating the solution to 540 ℃ at a heating rate of 1 ℃/min, and calcining the calcined product for 2 hours, namely the cobalt-doped zinc oxide hollow microsphere component 1;
(3) preparing cobalt-doped zinc oxide modified graphene 1: adding distilled water, graphene oxide and a cobalt-doped zinc oxide hollow microsphere component 1 into a reaction bottle, wherein the mass ratio of the distilled water to the graphene oxide to the cobalt-doped zinc oxide hollow microsphere component 1 is 1:6, placing the reaction bottle into a constant-temperature ultrasonic instrument, performing ultrasonic dispersion uniformly, centrifuging and washing the solution to remove the solvent, and fully drying to obtain cobalt-doped zinc oxide modified graphene 1;
(4) preparing a porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 1: adding a mixed solvent of triethylamine and N, N-dimethylformamide into a reaction bottle, wherein the volume ratio of the mixed solvent to the mixed solvent is 1:1, adding 52 parts of cobalt-doped zinc oxide modified graphene component 1, placing the graphene component 1 into a constant-temperature ultrasonic instrument, adding 32 parts of 9, 10-dibromoanthracene and 14 parts of p-diethynylbenzene after uniform ultrasonic dispersion, stirring and dissolving, adding 1.5 parts of catalyst tetrakis (triphenylphosphine) palladium and 0.5 part of promoter cuprous iodide, heating to 75-95 ℃, uniformly stirring and reacting for 60-80h, placing the solution into an ice water bath, adding distilled water until a large amount of precipitate is separated out, filtering the solution to remove the solvent, washing a solid product with distilled water and diethyl ether, and fully drying to prepare the porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 1;
(5) preparing a wave-absorbing material 1 of a cobalt-doped zinc oxide-polymer-based carbon material: and (3) placing the porous super-crosslinked polymer coated cobalt-doped zinc oxide composite material 1 in an atmosphere resistance furnace, heating to 720 ℃ at the heating rate of 3 ℃/min, and carrying out heat preservation and calcination for 2h to obtain a calcined product, namely the cobalt-doped zinc oxide-polymer-based carbon material wave-absorbing material 1.
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