CN113214638A - Wave-absorbing heat-conducting flexible composite material and preparation method thereof - Google Patents
Wave-absorbing heat-conducting flexible composite material and preparation method thereof Download PDFInfo
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Abstract
The invention relates to the technical field of wave-absorbing composite materials and discloses a wave-absorbing heat-conducting flexible composite material, hollow nano-zinc oxide has large specific surface area and pore structure, wave-absorbing capability is improved, the forbidden bandwidth and the dielectric constant of the zinc oxide are changed by manganese doping, the wave-absorbing frequency band and the wave-absorbing capability are expanded, the wave-absorbing effect can be improved by carbon nano tubes, the carbon nano tubes are uniformly dispersed in a polyurethane material after grafting, improves the dispersibility of the carbon nano tube, improves the hardness, the flexibility and the toughness of the composite material, ensures that the impedance matching of the polyurethane is moderate, the heat-conducting property and the wave-absorbing property of the polyurethane matrix are improved, the inorganic nano particles on the polyurethane are wrapped by the silicon rubber through heating and curing, the silicon rubber has good toughness, elasticity and wave-absorbing property, the flexibility and the wave-absorbing property of the wave-absorbing material are improved, and the prepared composite material is the wave-absorbing material with excellent heat-conducting property and flexibility.
Description
Technical Field
The invention relates to the technical field of wave-absorbing composite materials, in particular to a wave-absorbing heat-conducting flexible composite material and a preparation method thereof.
Background
The wave-absorbing material is a material capable of absorbing and attenuating incident electromagnetic waves, can convert absorbed electromagnetic energy into heat energy or energy in other forms and consume the heat energy to enable the electromagnetic waves to disappear, is generally applied to the military field in 20 ages, such as military stealth technology, radar detection and infrared detection reduction and the like, is different from the application in the military field, along with the rapid development of the current electronic industry technology, electromagnetic radiation becomes new environmental pollution, and the research and development of the wave-absorbing material also has important application value and research significance in the civil field.
The wave-absorbing material has various types, in engineering application, the wave-absorbing material is required to have high absorption rate to electromagnetic waves in a wider frequency band, and simultaneously has the properties of light weight, high temperature resistance and the like, so that a great number of products are expanded, including flexible wave-absorbing material, heat-conducting wave-absorbing material, high-frequency band wave-absorbing material and the like, wherein silicon rubber and the like have excellent toughness and flexibility due to long branched chains, can be bent and cut at will, are good raw materials for preparing the flexible wave-absorbing material, can effectively realize large-amplitude stretching of the wave-absorbing material mixed with inorganic materials under the protection of a silicon rubber polydimethylsiloxane layer, can effectively absorb waves due to nanometer size effect and lattice motion, can effectively absorb waves due to interaction among electrons and electron scattering and lattice defect, and the like caused by common nanometer zinc oxide, The nano molybdenum disulfide and the like can effectively change the electromagnetic parameters and wave-absorbing capacity of metal oxides by doping transition metals such as manganese and iron, common nano zinc oxide, carbon nano tubes and the like have good heat conduction and wave-absorbing effects, the carbon nano tubes are also wave-absorbing materials with high flexibility and high conductivity, and polyurethane, the carbon nano tubes and the zinc oxide are compounded to obtain the composite material which is an excellent wave-absorbing and heat-conducting composite material.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the wave-absorbing heat-conducting flexible composite material and the preparation method thereof, and the silicon rubber is endowed with good wave-absorbing performance.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: a wave-absorbing heat-conducting flexible composite material comprises the following components in parts by weight:
(1) adding a carboxylated carbon nanotube and polytetrahydrofuran ether glycol into a butanediol solvent, stirring and mixing uniformly in a nitrogen atmosphere, adding tetrabutyl titanate, reacting, and obtaining a polytetrahydrofuran grafted carbon nanotube after the reaction is finished;
(2) adding hexamethylene diisocyanate, polytetrahydrofuran ether glycol and polytetrahydrofuran grafted carbon nano tubes into an N, N-dimethylformamide solvent, heating in a nitrogen atmosphere, stirring and mixing uniformly, adding dibutyltin dilaurate to perform a polymerization reaction, and after the reaction is finished, washing, centrifuging and drying to obtain carbon nano tube grafted hyperbranched polyurethane;
(3) adding zinc nitrate and urea into a mixed solvent of deionized water and ethanol, stirring and mixing uniformly, keeping the temperature for 1-2 hours, centrifuging to obtain a precipitate, adding manganese nitrate, stirring and mixing uniformly, reacting, adjusting the pH to 8-10 by using ammonia water after the reaction is finished, cooling to room temperature, washing, centrifuging, and drying to obtain a Mn-doped nano ZnO hollow sphere precursor;
(4) adding the Mn-doped nano ZnO hollow sphere precursor into a tubular furnace, calcining in a nitrogen atmosphere, and cooling after the calcination is finished to obtain the Mn-doped nano ZnO hollow sphere;
(5) adding the carbon nano tube grafted hyperbranched polyurethane into a deionized water solvent, uniformly dispersing and mixing by ultrasonic, adding Mn-doped nano ZnO hollow spheres, dispersing under a high-speed shearing condition to obtain a mixed solution, pouring the mixed solution into a mould, drying and stripping to obtain the Mn-doped nano ZnO hollow sphere-based carbon nano tube grafted hyperbranched polyurethane;
(6) adding silica gel polydimethylsiloxane and a curing agent dibutyltin dilaurate into an ethyl acetate solvent, stirring and mixing uniformly to prepare a solution, immersing Mn-doped nano ZnO hollow sphere-based carbon nanotube grafted hyperbranched polyurethane into the solution, vacuumizing bubbles, and heating and curing to obtain the wave-absorbing heat-conducting flexible composite material.
Preferably, the mass ratio of the carboxylated carbon nanotubes, the polytetrahydrofuran ether glycol and the tetrabutyl titanate in the step (1) is 100:250-400: 2-5.
Preferably, the temperature of the reaction in the step (1) is 180-240 ℃, and the reaction time is 6-12 h.
Preferably, the mass ratio of the hexamethylene diisocyanate, the polytetrahydrofuran ether glycol, the dibutyltin dilaurate and the polytetrahydrofuran grafted carbon nano tube in the step (2) is 225-375:600-900:0.5-1.5: 100.
Preferably, the temperature of the polymerization reaction in the step (2) is 70-90 ℃, and the time of the polymerization reaction is 3-6 h.
Preferably, the mass ratio of the zinc nitrate to the urea to the manganese nitrate in the step (3) is 100:40-55: 5-15.
Preferably, the reaction temperature in the step (3) is 80-100 ℃, and the reaction time is 6-12 h.
Preferably, the calcination temperature in the step (4) is 550-650 ℃, and the calcination time is 3-6 h.
Preferably, the mass ratio of the carbon nanotube grafted hyperbranched polyurethane to the Mn doped nano ZnO hollow sphere in the step (5) is 100: 20-40.
Preferably, the mass ratio of the polydimethylsiloxane, the dibutyltin dilaurate and the Mn-doped nano ZnO hollow sphere-based carbon nanotube grafted hyperbranched polyurethane in the step (6) is 100:12-24: 8-15.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the wave-absorbing heat-conducting flexible composite material is prepared by the steps of performing esterification reaction on carboxyl on a carboxylated carbon nanotube and hydroxyl on polytetrahydrofuran ether glycol to obtain a polytetrahydrofuran grafted carbon nanotube, performing polymerization reaction on hexamethylene diisocyanate, polytetrahydrofuran ether glycol and the polytetrahydrofuran grafted carbon nanotube serving as reaction raw materials in an N, N-dimethylformamide solvent under the action of a dibutyltin dilaurate catalyst to obtain carbon nanotube grafted hyperbranched polyurethane, performing reaction on zinc nitrate in a mixed solvent of deionized water and ethanol under the action of a urea precipitant to obtain a precipitate, adding manganese nitrate, adjusting pH by using ammonia water after the reaction is finished to obtain a precursor, calcining in a tubular furnace to obtain Mn-doped nano ZnO hollow spheres, and finally mixing the carbon nanotube grafted hyperbranched polyurethane and the Mn-doped nano ZnO hollow spheres in a deionized water solvent, and drying and stripping in a mould to obtain the wave-absorbing heat-conducting flexible composite material.
The wave-absorbing heat-conducting flexible composite material is characterized in that nano zinc oxide is an n-type semiconductor material with excellent piezoelectricity and photoelectricity, the wave-absorbing performance is excellent, hollow zinc oxide has a large specific surface area and a pore structure, the wave-absorbing capacity of the hollow zinc oxide can be effectively improved, when only the nano zinc oxide is used as a wave-absorbing matrix, the wave-absorbing capacity is weak, the wave-absorbing wave band is narrow, the forbidden bandwidth and the dielectric constant of the zinc oxide are effectively changed by doping the zinc oxide with manganese, the wave-absorbing frequency band and the wave-absorbing capacity are enlarged, the carbon nano tube is used as a carbon series wave-absorbing material, has a series of advantages of light weight, wide source, high flexibility, good toughness, strong heat-conducting property and the like, the wave-absorbing effect can be effectively improved by grafting the nano carbon tube to a flexible polyurethane material through in-situ polymerization, the wave-absorbing effect of the grafted nano carbon tube is uniformly dispersed in the polyurethane material, and the dispersibility of the nano carbon tube is effectively improved, meanwhile, the hardness and flexibility of the composite material are improved, the toughness is improved, the impedance matching of polyurethane is moderate, the heat conducting property and the wave absorbing property of a polyurethane matrix are improved, the polyurethane material can be used as an electromagnetic wave transmitting material and can effectively absorb electromagnetic waves, the silicone rubber polydimethylsiloxane is cured by heating and effectively wraps inorganic nano particles on the polyurethane, the flexibility and the wave absorbing property of the wave absorbing material are effectively improved due to the good toughness, elasticity and wave absorbing property of the silicone rubber polydimethylsiloxane, the carbon nano tube grafted polyurethane is used as the matrix, Mn-doped hollow nano zinc oxide and the carbon nano tube grafted polyurethane are compounded and then mixed with the polydimethylsiloxane, and the prepared composite material is the wave absorbing material with excellent heat conducting property and flexibility.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: the preparation method of the wave-absorbing heat-conducting flexible composite material comprises the following steps:
(1) adding a butanediol solvent into a reaction bottle, adding a carboxylated carbon nanotube and polytetrahydrofuran ether glycol, stirring and mixing uniformly in a nitrogen atmosphere, adding tetrabutyl titanate, reacting at 180-240 ℃ at the mass ratio of 100:250-400:2-5, and obtaining a polytetrahydrofuran grafted carbon nanotube after the reaction is finished;
(2) adding an N, N-dimethylformamide solvent into a reaction bottle, then adding hexamethylene diisocyanate, polytetrahydrofuran ether glycol and polytetrahydrofuran grafted carbon nano tubes, heating and heating in a nitrogen atmosphere, uniformly stirring and mixing, adding dibutyltin dilaurate, wherein the mass ratio of the added hexamethylene diisocyanate, the polytetrahydrofuran ether glycol, the dibutyltin dilaurate and the polytetrahydrofuran grafted carbon nano tubes is 225-375:600-900:0.5-1.5:100, carrying out polymerization reaction at 70-90 ℃, wherein the polymerization reaction time is 3-6h, and after the reaction is finished, washing, centrifuging and drying to obtain the carbon nano tube grafted hyperbranched polyurethane;
(3) adding a mixed solvent of deionized water and ethanol into a reaction bottle, adding zinc nitrate and urea, stirring and mixing uniformly, keeping the temperature for 1-2h, centrifuging to obtain a precipitate, adding manganese nitrate, wherein the mass ratio of the added zinc nitrate to the added urea to the added manganese nitrate is 100:40-55:5-15, stirring and mixing uniformly, reacting at 80-100 ℃ for 6-12h, adjusting the pH to 8-10 by using ammonia water after the reaction is finished, cooling to room temperature, washing by using deionized water, centrifuging, and drying to obtain a Mn-doped nano ZnO hollow sphere precursor;
(4) adding a Mn-doped nano ZnO hollow sphere precursor into a tubular furnace, calcining in a nitrogen atmosphere at the temperature of 550-650 ℃, for 3-6h, and cooling after the calcination to obtain the Mn-doped nano ZnO hollow sphere;
(5) adding a deionized water solvent and the carbon nano tube grafted hyperbranched polyurethane into a reaction bottle, uniformly mixing by ultrasonic dispersion, adding Mn doped nano ZnO hollow spheres, wherein the mass ratio of the added carbon nano tube grafted hyperbranched polyurethane to the Mn doped nano ZnO hollow spheres is 100:20-40, dispersing under a high-speed shearing condition to obtain a mixed solution, pouring the mixed solution into a polytetrafluoroethylene mold, drying and stripping to obtain the Mn doped nano ZnO hollow sphere based carbon nano tube grafted hyperbranched polyurethane;
(6) adding an ethyl acetate solvent, silica gel polydimethylsiloxane and a curing agent dibutyltin dilaurate into a reaction bottle, stirring and mixing uniformly to prepare a solution, then soaking Mn-doped nano ZnO hollow sphere-based carbon nanotube grafted hyperbranched polyurethane into the solution, wherein the mass ratio of the added polydimethylsiloxane, dibutyltin dilaurate and Mn-doped nano ZnO hollow sphere-based carbon nanotube grafted hyperbranched polyurethane is 100:12-24:8-15, vacuumizing bubbles, and heating and curing to obtain the wave-absorbing heat-conducting flexible composite material.
Example 1
(1) Adding a butanediol solvent into a reaction bottle, adding a carboxylated carbon nanotube and polytetrahydrofuran ether glycol, stirring and mixing uniformly in a nitrogen atmosphere, adding tetrabutyl titanate, reacting the added carboxylated carbon nanotube, polytetrahydrofuran ether glycol and tetrabutyl titanate at the mass ratio of 100:250:2 at 180 ℃, wherein the reaction time is 6 hours, and obtaining the polytetrahydrofuran grafted carbon nanotube after the reaction is finished;
(2) adding an N, N-dimethylformamide solvent into a reaction bottle, then adding hexamethylene diisocyanate, polytetrahydrofuran ether glycol and polytetrahydrofuran grafted carbon nano tubes, heating and heating in a nitrogen atmosphere, uniformly stirring and mixing, adding dibutyltin dilaurate, wherein the mass ratio of the added hexamethylene diisocyanate, the polytetrahydrofuran ether glycol, the dibutyltin dilaurate to the polytetrahydrofuran grafted carbon nano tubes is 225:600:0.5:100, carrying out polymerization reaction at 70 ℃, the time of the polymerization reaction is 3 hours, and after the reaction is finished, washing, centrifuging and drying to obtain the carbon nano tube grafted hyperbranched polyurethane;
(3) adding a mixed solvent of deionized water and ethanol into a reaction bottle, adding zinc nitrate and urea, stirring and mixing uniformly, keeping the temperature for 1h, centrifuging to obtain a precipitate, adding manganese nitrate, wherein the mass ratio of the added zinc nitrate to the added urea to the added manganese nitrate is 100:40:5, stirring and mixing uniformly, reacting at 80 ℃ for 6h, adjusting the pH to 8 by using ammonia water after the reaction is finished, cooling to room temperature, washing by using deionized water, centrifuging, and drying to obtain a Mn-doped nano ZnO hollow sphere precursor;
(4) adding a Mn-doped nano ZnO hollow sphere precursor into a tubular furnace, calcining in a nitrogen atmosphere at 550 ℃ for 3h, and cooling after calcining to obtain a Mn-doped nano ZnO hollow sphere;
(5) adding a deionized water solvent and the carbon nano tube grafted hyperbranched polyurethane into a reaction bottle, uniformly mixing by ultrasonic dispersion, adding Mn doped nano ZnO hollow spheres, wherein the mass ratio of the added carbon nano tube grafted hyperbranched polyurethane to the Mn doped nano ZnO hollow spheres is 100:20, dispersing under a high-speed shearing condition to obtain a mixed solution, pouring the mixed solution into a polytetrafluoroethylene mold, drying and stripping to obtain the Mn doped nano ZnO hollow sphere based carbon nano tube grafted hyperbranched polyurethane;
(6) adding an ethyl acetate solvent, silica gel polydimethylsiloxane and a curing agent dibutyltin dilaurate into a reaction bottle, uniformly stirring and mixing to prepare a solution, then soaking the Mn-doped nano ZnO hollow sphere-based carbon nanotube grafted hyperbranched polyurethane into the solution, wherein the mass ratio of the added polydimethylsiloxane, dibutyltin dilaurate to the Mn-doped nano ZnO hollow sphere-based carbon nanotube grafted hyperbranched polyurethane is 100:12:8, vacuumizing bubbles, and heating and curing to obtain the wave-absorbing and heat-conducting flexible composite material.
Example 2
(1) Adding a butanediol solvent into a reaction bottle, adding a carboxylated carbon nanotube and polytetrahydrofuran ether glycol, stirring and mixing uniformly in a nitrogen atmosphere, adding tetrabutyl titanate, reacting at 200 ℃ for 8 hours, and obtaining a polytetrahydrofuran grafted carbon nanotube after the reaction is finished, wherein the mass ratio of the added carboxylated carbon nanotube, the polytetrahydrofuran ether glycol and the tetrabutyl titanate is 100:300: 3;
(2) adding an N, N-dimethylformamide solvent into a reaction bottle, then adding hexamethylene diisocyanate, polytetrahydrofuran ether glycol and polytetrahydrofuran grafted carbon nano tubes, heating and heating in a nitrogen atmosphere, uniformly stirring and mixing, adding dibutyltin dilaurate, wherein the mass ratio of the added hexamethylene diisocyanate, the polytetrahydrofuran ether glycol, the dibutyltin dilaurate to the polytetrahydrofuran grafted carbon nano tubes is 280:700:0.8:100, carrying out polymerization reaction at 75 ℃, the time of the polymerization reaction is 4 hours, and after the reaction is finished, washing, centrifuging and drying to obtain the carbon nano tube grafted hyperbranched polyurethane;
(3) adding a mixed solvent of deionized water and ethanol into a reaction bottle, adding zinc nitrate and urea, stirring and mixing uniformly, keeping the temperature for 1.5 hours, centrifuging to obtain a precipitate, adding manganese nitrate, wherein the mass ratio of the added zinc nitrate to the added urea to the added manganese nitrate is 100:45:8, stirring and mixing uniformly, reacting at 85 ℃ for 8 hours, adjusting the pH to 9 by using ammonia water after the reaction is finished, cooling to room temperature, washing by using deionized water, centrifuging, and drying to obtain a Mn-doped nano ZnO hollow sphere precursor;
(4) adding a Mn-doped nano ZnO hollow sphere precursor into a tubular furnace, calcining in a nitrogen atmosphere at 580 ℃ for 4h, and cooling after calcining to obtain a Mn-doped nano ZnO hollow sphere;
(5) adding a deionized water solvent and the carbon nano tube grafted hyperbranched polyurethane into a reaction bottle, uniformly mixing by ultrasonic dispersion, adding Mn doped nano ZnO hollow spheres, wherein the mass ratio of the added carbon nano tube grafted hyperbranched polyurethane to the Mn doped nano ZnO hollow spheres is 100:25, dispersing under a high-speed shearing condition to obtain a mixed solution, pouring the mixed solution into a polytetrafluoroethylene mold, drying and stripping to obtain the Mn doped nano ZnO hollow sphere based carbon nano tube grafted hyperbranched polyurethane;
(6) adding an ethyl acetate solvent, silica gel polydimethylsiloxane and a curing agent dibutyltin dilaurate into a reaction bottle, uniformly stirring and mixing to prepare a solution, then soaking the Mn-doped nano ZnO hollow sphere-based carbon nanotube grafted hyperbranched polyurethane into the solution, wherein the mass ratio of the added polydimethylsiloxane, dibutyltin dilaurate and Mn-doped nano ZnO hollow sphere-based carbon nanotube grafted hyperbranched polyurethane is 100:15:10, vacuumizing bubbles, and heating and curing to obtain the wave-absorbing and heat-conducting flexible composite material.
Example 3
(1) Adding a butanediol solvent into a reaction bottle, adding a carboxylated carbon nanotube and polytetrahydrofuran ether glycol, stirring and mixing uniformly in a nitrogen atmosphere, adding tetrabutyl titanate, reacting the added carboxylated carbon nanotube, polytetrahydrofuran ether glycol and tetrabutyl titanate at the mass ratio of 100:350:4 at 220 ℃, wherein the reaction time is 10 hours, and obtaining the polytetrahydrofuran grafted carbon nanotube after the reaction is finished;
(2) adding an N, N-dimethylformamide solvent into a reaction bottle, then adding hexamethylene diisocyanate, polytetrahydrofuran ether glycol and polytetrahydrofuran grafted carbon nano tubes, heating and heating in a nitrogen atmosphere, uniformly stirring and mixing, adding dibutyltin dilaurate, wherein the mass ratio of the added hexamethylene diisocyanate, the polytetrahydrofuran ether glycol, the dibutyltin dilaurate to the polytetrahydrofuran grafted carbon nano tubes is 350:850:1.2:100, carrying out polymerization reaction at 85 ℃, the time of the polymerization reaction is 5 hours, and after the reaction is finished, washing, centrifuging and drying to obtain the carbon nano tube grafted hyperbranched polyurethane;
(3) adding a mixed solvent of deionized water and ethanol into a reaction bottle, adding zinc nitrate and urea, stirring and mixing uniformly, keeping the temperature for 1.5 hours, centrifuging to obtain a precipitate, adding manganese nitrate, wherein the mass ratio of the added zinc nitrate to the added urea to the added manganese nitrate is 100:50:12, stirring and mixing uniformly, reacting at 90 ℃ for 10 hours, adjusting the pH to 9 by using ammonia water after the reaction is finished, cooling to room temperature, washing by using deionized water, centrifuging, and drying to obtain a Mn-doped nano ZnO hollow sphere precursor;
(4) adding a Mn-doped nano ZnO hollow sphere precursor into a tubular furnace, calcining in a nitrogen atmosphere at the temperature of 600 ℃ for 5h, and cooling after calcining to obtain a Mn-doped nano ZnO hollow sphere;
(5) adding a deionized water solvent and the carbon nano tube grafted hyperbranched polyurethane into a reaction bottle, uniformly mixing by ultrasonic dispersion, adding Mn doped nano ZnO hollow spheres, wherein the mass ratio of the added carbon nano tube grafted hyperbranched polyurethane to the Mn doped nano ZnO hollow spheres is 100:35, dispersing under a high-speed shearing condition to obtain a mixed solution, pouring the mixed solution into a polytetrafluoroethylene mold, drying and stripping to obtain the Mn doped nano ZnO hollow sphere based carbon nano tube grafted hyperbranched polyurethane;
(6) adding an ethyl acetate solvent, silica gel polydimethylsiloxane and a curing agent dibutyltin dilaurate into a reaction bottle, uniformly stirring and mixing to prepare a solution, then soaking the Mn-doped nano ZnO hollow sphere-based carbon nanotube grafted hyperbranched polyurethane into the solution, wherein the mass ratio of the added polydimethylsiloxane, dibutyltin dilaurate to the Mn-doped nano ZnO hollow sphere-based carbon nanotube grafted hyperbranched polyurethane is 100:20:12, vacuumizing bubbles, and heating and curing to obtain the wave-absorbing and heat-conducting flexible composite material.
Example 4
(1) Adding a butanediol solvent into a reaction bottle, adding a carboxylated carbon nanotube and polytetrahydrofuran ether glycol, stirring and mixing uniformly in a nitrogen atmosphere, adding tetrabutyl titanate, reacting at 240 ℃ for 12 hours, and obtaining a polytetrahydrofuran grafted carbon nanotube after the reaction is finished, wherein the mass ratio of the added carboxylated carbon nanotube, the polytetrahydrofuran ether glycol and the tetrabutyl titanate is 100:400: 5;
(2) adding an N, N-dimethylformamide solvent into a reaction bottle, then adding hexamethylene diisocyanate, polytetrahydrofuran ether glycol and polytetrahydrofuran grafted carbon nano tubes, heating and heating in a nitrogen atmosphere, uniformly stirring and mixing, adding dibutyltin dilaurate, wherein the mass ratio of the added hexamethylene diisocyanate, the polytetrahydrofuran ether glycol, the dibutyltin dilaurate to the polytetrahydrofuran grafted carbon nano tubes is 375:900:1.5:100, carrying out polymerization reaction at 90 ℃, the time of the polymerization reaction is 6 hours, and after the reaction is finished, washing, centrifuging and drying to obtain the carbon nano tube grafted hyperbranched polyurethane;
(3) adding a mixed solvent of deionized water and ethanol into a reaction bottle, adding zinc nitrate and urea, stirring and mixing uniformly, keeping the temperature for 2 hours, centrifuging to obtain a precipitate, adding manganese nitrate, wherein the mass ratio of the added zinc nitrate to the added urea to the added manganese nitrate is 100:55:15, stirring and mixing uniformly, reacting at 100 ℃, wherein the reaction time is 12 hours, adjusting the pH to 10 by using ammonia water after the reaction is finished, cooling to room temperature, washing by using deionized water, centrifuging, and drying to obtain a Mn-doped nano ZnO hollow sphere precursor;
(4) adding a Mn-doped nano ZnO hollow sphere precursor into a tubular furnace, calcining in a nitrogen atmosphere at the temperature of 650 ℃ for 6h, and cooling after calcining to obtain a Mn-doped nano ZnO hollow sphere;
(5) adding a deionized water solvent and the carbon nano tube grafted hyperbranched polyurethane into a reaction bottle, uniformly mixing by ultrasonic dispersion, adding Mn doped nano ZnO hollow spheres, wherein the mass ratio of the added carbon nano tube grafted hyperbranched polyurethane to the Mn doped nano ZnO hollow spheres is 100:40, dispersing under a high-speed shearing condition to obtain a mixed solution, pouring the mixed solution into a polytetrafluoroethylene mold, drying and stripping to obtain the Mn doped nano ZnO hollow sphere based carbon nano tube grafted hyperbranched polyurethane;
(6) adding an ethyl acetate solvent, silica gel polydimethylsiloxane and a curing agent dibutyltin dilaurate into a reaction bottle, uniformly stirring and mixing to prepare a solution, then soaking the Mn-doped nano ZnO hollow sphere-based carbon nanotube grafted hyperbranched polyurethane into the solution, wherein the mass ratio of the added polydimethylsiloxane, dibutyltin dilaurate and Mn-doped nano ZnO hollow sphere-based carbon nanotube grafted hyperbranched polyurethane is 100:24:15, vacuumizing bubbles, and heating and curing to obtain the wave-absorbing and heat-conducting flexible composite material.
Comparative example 1
(1) Adding a butanediol solvent into a reaction bottle, adding a carboxylated carbon nanotube and polytetrahydrofuran ether glycol, stirring and mixing uniformly in a nitrogen atmosphere, adding tetrabutyl titanate, reacting at 200 ℃ for 10 hours, and obtaining a polytetrahydrofuran grafted carbon nanotube after the reaction is finished, wherein the mass ratio of the added carboxylated carbon nanotube, the polytetrahydrofuran ether glycol to the tetrabutyl titanate is 100:320: 3.5;
(2) adding an N, N-dimethylformamide solvent into a reaction bottle, then adding hexamethylene diisocyanate, polytetrahydrofuran ether glycol and polytetrahydrofuran grafted carbon nano tubes, heating and heating in a nitrogen atmosphere, uniformly stirring and mixing, adding dibutyltin dilaurate, wherein the mass ratio of the added hexamethylene diisocyanate, the polytetrahydrofuran ether glycol, the dibutyltin dilaurate and the polytetrahydrofuran grafted carbon nano tubes is 320:750:1.2:100, carrying out polymerization reaction at 80 ℃, the time of the polymerization reaction is 4 hours, and after the reaction is finished, washing, centrifuging and drying to obtain the carbon nano tube grafted hyperbranched polyurethane;
(3) adding an ethyl acetate solvent, silica gel polydimethylsiloxane and a curing agent dibutyltin dilaurate into a reaction bottle, stirring and mixing uniformly to prepare a solution, immersing the carbon nanotube grafted hyperbranched polyurethane into the solution, wherein the mass ratio of the added polydimethylsiloxane, dibutyltin dilaurate to the carbon nanotube grafted hyperbranched polyurethane is 100:18:10, vacuumizing to remove bubbles, and heating and curing to obtain the wave-absorbing heat-conducting flexible composite material.
Comparative example 2
(1) Adding a mixed solvent of deionized water and ethanol into a reaction bottle, adding zinc nitrate and urea, stirring and mixing uniformly, keeping the temperature for 1.5 hours, centrifuging to obtain a precipitate, adding manganese nitrate, wherein the mass ratio of the added zinc nitrate to the added urea to the added manganese nitrate is 100:48:10, stirring and mixing uniformly, reacting at 90 ℃ for 10 hours, adjusting the pH to 9 by using ammonia water after the reaction is finished, cooling to room temperature, washing by using deionized water, centrifuging, and drying to obtain a Mn-doped nano ZnO hollow sphere precursor;
(2) adding a Mn-doped nano ZnO hollow sphere precursor into a tubular furnace, calcining in a nitrogen atmosphere at the temperature of 600 ℃ for 4h, and cooling after calcining to obtain a Mn-doped nano ZnO hollow sphere;
(3) adding an ethyl acetate solvent, silica gel polydimethylsiloxane and a curing agent dibutyltin dilaurate into a reaction bottle, stirring and mixing uniformly to prepare a solution, immersing the Mn-doped nano ZnO hollow sphere into the solution, wherein the mass ratio of the added polydimethylsiloxane, dibutyltin dilaurate to the Mn-doped nano ZnO hollow sphere is 100:18:12, vacuumizing to remove bubbles, and heating and curing to obtain the wave-absorbing heat-conducting flexible composite material.
The wave-absorbing and heat-conducting flexible composite materials in the synthesized examples and comparative examples are cut into sample pieces with the diameter of 50mm and the thickness of 6mm, heat conductivity coefficient measurement is carried out on a FOX50 type heat flow meter, the test is that the temperature of two contact surfaces is 70 ℃ and 90 ℃, three groups of samples of each type are respectively tested, and an average value is taken.
The wave-absorbing capacity of the wave-absorbing heat-conducting flexible composite materials in the synthesized examples and comparative examples is tested on an N5230 type vector network analyzer by adopting a test method of an arc method, the frequency range of the tested electromagnetic parameters is 2-18GHz, each group is tested for three times respectively, and the average value is obtained.
Claims (10)
1. A wave-absorbing heat-conducting flexible composite material is characterized in that: the wave-absorbing heat-conducting flexible composite material and the preparation method are as follows:
(1) adding a carboxylated carbon nanotube and polytetrahydrofuran ether glycol into a butanediol solvent, stirring and mixing uniformly in a nitrogen atmosphere, adding tetrabutyl titanate, reacting, and obtaining a polytetrahydrofuran grafted carbon nanotube after the reaction is finished;
(2) adding hexamethylene diisocyanate, polytetrahydrofuran ether glycol and polytetrahydrofuran grafted carbon nano tubes into an N, N-dimethylformamide solvent, heating in a nitrogen atmosphere, stirring and mixing uniformly, adding dibutyltin dilaurate to perform a polymerization reaction, and after the reaction is finished, washing, centrifuging and drying to obtain carbon nano tube grafted hyperbranched polyurethane;
(3) adding zinc nitrate and urea into a mixed solvent of deionized water and ethanol, stirring and mixing uniformly, keeping the temperature for 1-2 hours, centrifuging to obtain a precipitate, adding manganese nitrate, stirring and mixing uniformly, reacting, adjusting the pH to 8-10 by using ammonia water after the reaction is finished, cooling to room temperature, washing, centrifuging, and drying to obtain a Mn-doped nano ZnO hollow sphere precursor;
(4) adding the Mn-doped nano ZnO hollow sphere precursor into a tubular furnace, calcining in a nitrogen atmosphere, and cooling after the calcination is finished to obtain the Mn-doped nano ZnO hollow sphere;
(5) adding the carbon nano tube grafted hyperbranched polyurethane into a deionized water solvent, uniformly dispersing and mixing by ultrasonic, adding Mn-doped nano ZnO hollow spheres, dispersing under a high-speed shearing condition to obtain a mixed solution, pouring the mixed solution into a mould, drying and stripping to obtain the Mn-doped nano ZnO hollow sphere-based carbon nano tube grafted hyperbranched polyurethane;
(6) adding silica gel polydimethylsiloxane and a curing agent dibutyltin dilaurate into an ethyl acetate solvent, stirring and mixing uniformly to prepare a solution, immersing Mn-doped nano ZnO hollow sphere-based carbon nanotube grafted hyperbranched polyurethane into the solution, vacuumizing bubbles, and heating and curing to obtain the wave-absorbing heat-conducting flexible composite material.
2. The wave-absorbing heat-conducting flexible composite material according to claim 1, characterized in that: the mass ratio of the carboxylated carbon nanotubes, the polytetrahydrofuran ether glycol and the tetrabutyl titanate in the step (1) is 100:250-400: 2-5.
3. The wave-absorbing heat-conducting flexible composite material according to claim 1, characterized in that: the reaction temperature in the step (1) is 180-240 ℃, and the reaction time is 6-12 h.
4. The wave-absorbing heat-conducting flexible composite material according to claim 1, characterized in that: in the step (2), the mass ratio of the hexamethylene diisocyanate to the polytetrahydrofuran ether glycol to the dibutyltin dilaurate to the polytetrahydrofuran grafted carbon nano tube is 225-375:600-900:0.5-1.5: 100.
5. The wave-absorbing heat-conducting flexible composite material according to claim 1, characterized in that: the temperature of the polymerization reaction in the step (2) is 70-90 ℃, and the time of the polymerization reaction is 3-6 h.
6. The wave-absorbing heat-conducting flexible composite material according to claim 1, characterized in that: the mass ratio of the zinc nitrate to the urea to the manganese nitrate in the step (3) is 100:40-55: 5-15.
7. The wave-absorbing heat-conducting flexible composite material according to claim 1, characterized in that: the reaction temperature in the step (3) is 80-100 ℃, and the reaction time is 6-12 h.
8. The wave-absorbing heat-conducting flexible composite material according to claim 1, characterized in that: the calcining temperature in the step (4) is 550-650 ℃, and the calcining time is 3-6 h.
9. The wave-absorbing heat-conducting flexible composite material according to claim 1, characterized in that: the mass ratio of the carbon nanotube grafted hyperbranched polyurethane to the Mn doped nano ZnO hollow sphere in the step (5) is 100: 20-40.
10. The wave-absorbing heat-conducting flexible composite material according to claim 1, characterized in that: the mass ratio of the polydimethylsiloxane, the dibutyltin dilaurate and the Mn-doped nano ZnO hollow sphere-based carbon nanotube grafted hyperbranched polyurethane in the step (6) is 100:12-24: 8-15.
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