CN113831779A - Composite wave-absorbing coating and preparation method thereof - Google Patents
Composite wave-absorbing coating and preparation method thereof Download PDFInfo
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- CN113831779A CN113831779A CN202110915757.3A CN202110915757A CN113831779A CN 113831779 A CN113831779 A CN 113831779A CN 202110915757 A CN202110915757 A CN 202110915757A CN 113831779 A CN113831779 A CN 113831779A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/32—Radiation-absorbing paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
- C09D175/04—Polyurethanes
- C09D175/08—Polyurethanes from polyethers
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Abstract
The invention relates to a composite wave-absorbing coating and a preparation method thereof, wherein the composite wave-absorbing coating consists of a wave absorber and a coating, the wave absorber of the composite wave-absorbing coating is made of a multi-element nano composite material, and the coating of the composite wave-absorbing coating is made of a single-component polyurethane interface agent; the preparation method of the composite wave-absorbing coating comprises the following steps: step 1, preparing graphene oxide, step 2, preparing polypyrrole, step 3, preparing carbonyl iron nanoparticles, step 4, preparing a graphene-loaded polypyrrole nanocomposite, step 5, preparing a single-component polyurethane interfacial agent, step 6, mechanically mixing and stirring the preparations of the steps 1, 2, 3 and 4, and step 7, adding the preparation of the step 5 into the step 6, and mixing and stirring by magnetic force; the wave-absorbing coating solves the problems of large density, narrow wave-absorbing frequency band, poor mechanical property and the like of the traditional wave-absorbing coating, is suitable for industrial large-scale production, and is particularly applied to the places with wide frequency band and strong wave-absorbing capability in the frequency range of 2-18GHz of radar waves.
Description
Technical Field
The invention belongs to the technical field of composite materials, and particularly relates to a composite wave-absorbing coating and a preparation method thereof.
Background
With the rapid development of electronic devices, radar stealth technology has become an important technical means for improving battlefield viability in weapon systems. The wave absorbing agent is taken as the core of radar stealth technology, and the high-performance wave absorbing coating with the characteristics of thinness, lightness, width and strength is developed and has been highly valued by various countries.
The wave-absorbing coating is generally formed by compounding a nano wave-absorbing auxiliary agent and a high-molecular coating, the nano wave-absorbing auxiliary agent is divided into a resistance type, a dielectric loss type and a magnetic loss type, and the nano wave-absorbing auxiliary agent has the main function of absorbing and attenuating electromagnetic waves. The traditional wave-absorbing auxiliary agent has the defects of high density, poor high-temperature resistance, poor corrosion resistance, poor impedance matching, narrow wave-absorbing frequency band and the like. The wave-absorbing nano additive with single loss type or single component can not meet the performance requirement. Therefore, the composite wave-absorbing nano-material prepared by utilizing the complementary advantages of various materials becomes a research direction.
The polymer coating is another important research direction of the wave-absorbing coating and has the functions of dispersing and bearing the wave-absorbing agent. The polymer coating may be classified into epoxy resin, acrylic resin, polyurethane, etc. according to the classification of the resin. The epoxy resin coating has excellent performances of strong adhesion, high temperature resistance and the like, and the curing process of the traditional epoxy resin material needs to be carried out in a high-temperature environment. The acrylic resin coating has excellent performances of low-temperature curing, high bonding strength and the like, but the plasticity of the acrylic resin coating is poor, and the application has certain limitation. The polyurethane coating has good durability and adhesion after being cured, has good adhesion on the surfaces of various substrates, and has more stable usability, stronger adhesion and other excellent performances compared with a single-component polyurethane coating in the operation process, so that the two-component polyurethane coating can be industrially produced and applied in a large scale.
Chinese patent application No. CN200610026686.7 discloses a water-based nano composite polyester polyurethane coating material and a preparation method thereof, wherein the coating material is prepared by crosslinking and curing water-based nano composite polyester resin with the molar ratio of NCO/OH of isocyanate and polyester resin being 1.0-3.0 and water-based closed polyisocyanate at 10-150 ℃ for 10 min-48 h; the water-based nano composite polyester resin is prepared by firstly adopting blending sonochemical synthesis reaction of nano particles and polyhydric alcohol, grafting the polyhydric alcohol on the surfaces of the nano particles, then blending, melting and in-situ polymerizing the nano particles, the polyhydric alcohol and carboxylic acid to obtain nano composite polyester resin, and then adding water after neutralizing with alkali; the nano composite polyester resin consists of nano particles, polyhydric alcohol, dihydroxy carboxylic acid and carboxylic acid, and simultaneously satisfies the following conditions that A, at least one nano particle with a nano particle diameter is contained; B. at least one of dihydric alcohol and trihydric alcohol with the molecular weight of 60-1000 is used as a polyol component; C. comprising a dihydroxy carboxylic acid; D. at least one carboxylic acid; the solid content of the used water-based nano composite polyester resin is 20-55 wt%, wherein the molecular weight of the nano composite polyester resin is 1000-50000, the acid value is 20-70 mgKOH/g, the hydroxyl value is 60-250 mgKOH/g, and the content of nano particles accounts for 1-15 wt% of the total weight of the nano composite polyester resin; but does not solve the problem that the polyester polyurethane coating is solidified under the condition of low temperature and has higher surface hardness and interface cohesiveness.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides a composite wave-absorbing coating and a preparation method thereof.
The composite wave-absorbing coating comprises a wave-absorbing agent and a coating, wherein the wave-absorbing agent is a multi-component nano composite material, the coating is a single-component polyurethane interface agent, and the weight ratio of the multi-component nano composite material to the single-component polyurethane interface agent is 4: 1.
Further, the multi-element nano composite material is prepared from 1-2 parts of graphene oxide, 1-2 parts of polypyrrole, 30-50 parts of carbonyl iron nanoparticles and 1-2 parts of graphene-loaded polypyrrole nano composite material.
Further, the multi-element nano composite material is prepared from graphene oxide, polypyrrole, carbonyl iron nanoparticles and a graphene-loaded polypyrrole nano composite material, wherein 1.5 parts of graphene oxide, 1.5 parts of polypyrrole, 40 parts of carbonyl iron nanoparticles and 1.5 parts of a graphene-loaded polypyrrole nano composite material.
The single-component polyurethane interface agent is further prepared from 50-150 parts of hydroxyl-terminated polyether polyol, 100-200 parts of propylene glycol monomethyl ether acetate, 30-50 parts of trimethylolpropane, 50-300 parts of diisocyanate and 100-400 parts of ethyl acetate.
Further, the single-component polyurethane interface agent is prepared from 100 parts of hydroxyl-terminated polyether polyol, 150 parts of propylene glycol monomethyl ether acetate, 40 parts of trimethylolpropane, 175 parts of diisocyanate and 250 parts of ethyl acetate.
The invention also provides a preparation method of the composite wave-absorbing coating, which comprises the following steps:
step 1, preparing graphene oxide:
step 1.1, taking a three-necked bottle, placing the three-necked bottle in an ice-water bath, adding 42-46 parts of concentrated sulfuric acid with the concentration of 98% into the three-necked bottle, magnetically stirring at the rotation speed of 400r/min, weighing 2-8 parts of graphite, 1-4 parts of sodium nitrate and 6-12 parts of potassium permanganate, adding into the three-necked bottle, mixing with the concentrated sulfuric acid, and stirring, wherein the speed ratio of adding the graphite and the sodium nitrate to the speed ratio of adding the potassium permanganate is 5: 1;
step 1.2, switching the ice-water bath in the step 1.1 into a warm water bath, weighing 86-90 parts of deionized water, adding the deionized water into a three-neck flask, raising the temperature of the warm water bath to 98 ℃, and adding 8-12 parts of hydrogen peroxide solution with the molar concentration of 2mol/L into the three-neck flask for oxidation reaction;
step 1.3, centrifugally cleaning the graphene oxide obtained in the step 1.2 at a centrifugal rate of 10000r/min, centrifuging for 15min, and then centrifugally cleaning a lower-layer precipitate until Ph is 7;
step 1.4, centrifugally cleaning the graphene oxide obtained in the step 1.3 until Ph is 7, adding deionized water for dilution, and adding 16-20 parts of hydrazine hydrate for reduction reaction at the temperature of 90 ℃;
step 1.5, centrifugally cleaning the graphene oxide obtained in the step 1.4 at a centrifugal rate of 10000r/min, centrifuging for 15min, and then carrying out multiple times of centrifugal cleaning on the lower-layer precipitate until Ph is 7 to obtain graphene oxide;
step 1.6, sealing and storing the graphene oxide prepared in the step 1.5 in an acetone solution for later use;
step 2, preparing polypyrrole:
step 2.1, weighing 1-5 parts of methyl orange, dissolving in 550-650 parts of deionized water, and placing on a magnetic stirring table at the rotating speed of 450 r/min;
step 2.2, weighing 8-20 parts of ferric chloride hexahydrate, adding into the step 2.1, continuously stirring for 40min, adding 2-5 parts of pyrrole, and polymerizing for 24h at room temperature;
step 2.3, centrifugally cleaning the reactant of the polymerization reaction in the step 2.2 at a centrifugal rate of 10000r/min, centrifuging for 15min, taking the lower-layer precipitate, and centrifugally cleaning until Ph is 7 to obtain polypyrrole;
step 2.4, sealing and storing the polypyrrole prepared in the step 2.3 in an acetone solution for later use;
step 3, preparing carbonyl iron nanoparticles:
step 3.1, weighing 6-10 parts of sponge iron, cleaning, crushing until the diameter is 3mm, grinding the crushed sponge iron into powder with the particle size of 50 microns by adopting a planetary ball mill, introducing H2Reducing, placing the reduced product in a synthesis reaction kettle, introducing CO, heating the synthesis reaction kettle to carry out synthesis reaction, and reducing pressure and cooling after the synthesis reaction to obtain Fe (CO)5A liquid;
step 3.2, mixing the Fe (CO) in the step 3.15The liquid is gasified in a pyrolysis furnace to form gaseous Fe (CO)5Gaseous Fe (CO) at 300 ℃ and a pressure of 1bar5Decomposing to form iron core;
step 3.3, performing ball milling treatment on the iron core in the step 3.2 for 90min to prepare carbonyl iron nanoparticles;
wherein the ball milling treatment is carried out for 90min under the conditions that the ball material mass ratio is 6:1 and the ball milling rotating speed is 35 r/min;
step 3.4, placing the carbonyl iron nanoparticles prepared in the step 3.3 in a sealing bag, and sealing and storing for later use;
step 4, preparing the graphene loaded polypyrrole nano composite material:
step 4.1, adding 10-15 parts of graphene oxide into 400-600 parts of deionized water, mechanically stirring until the graphene oxide is uniformly dispersed, adding 4-10 parts of ferric trichloride hexahydrate, and continuously stirring for 50min at the rotating speed of 350 r/min;
step 4.2, adding 1-5 parts of polypyrrole into the step 4.1, continuously mechanically stirring at the rotating speed of 450r/min, and polymerizing for 24 hours at room temperature;
step 4.3, centrifugally cleaning the reactant after the polymerization reaction in the step 4.2 at a centrifugal rate of 10000r/min, centrifuging for 15min, and then centrifugally cleaning the lower-layer precipitate until Ph is 7;
step 4.4, placing the reactant which is subjected to centrifugal cleaning in the step 4.3 until Ph is 7 into an oil bath pot, heating to 90 ℃, adding 16-20 parts of hydrazine hydrate solution, and reacting for 8 hours;
step 4.5, centrifugally cleaning the reactant stirred in the step 4.4 at a centrifugal rate of 10000r/min, centrifuging for 15min, then taking the lower-layer precipitate, and centrifugally cleaning until Ph is 7 to obtain the graphene-loaded polypyrrole nanocomposite;
step 4.6, storing the graphene-loaded polypyrrole nanocomposite material prepared in the step 4.5 in an acetone solution for later use;
step 5, preparing a single-component polyurethane interface agent:
step 5.1, weighing 50-150 parts of hydroxyl-terminated polyether polyol and 100-200 parts of propylene glycol methyl ether acetate, adding into a 500ml three-necked bottle, and mechanically or magnetically stirring at the rotating speed of 150 r/min;
step 5.2, heating the three-mouth bottle and stirring the mixture in the three-mouth bottle, and stopping heating when the temperature of the mixture in the three-mouth bottle is raised to 90 ℃;
step 5.3, weighing 30-50 parts of trimethylolpropane, adding the 30-50 parts of trimethylolpropane into the three-necked bottle in the step 5.2, mechanically or magnetically stirring at the rotating speed of 350r/min, heating the three-necked bottle after stirring at the heating temperature of 80-100 ℃, and placing the three-necked bottle in a vacuum of 0.092MPa for dehydration reaction for 1.5-2 h;
step 5.4, introducing air into the vacuum of 0.092MPa in the step 5.3, reducing the temperature of the mixture in the three-necked bottle to 60-65 ℃, weighing 50-300 parts of diisocyanate, adding the diisocyanate into the three-necked bottle, stirring mechanically or magnetically at the rotating speed of 300r/min, heating the three-necked bottle after stirring, increasing the temperature of the mixture in the three-necked bottle to 80-90 ℃, placing the three-necked bottle in the vacuum of 0.092MPa for dehydration reaction for 1.5-2 h, wherein the rotating speed of the dehydration reaction is 500 r/min;
step 5.5, cooling the mixture obtained after the dehydration reaction in the step 5.4 to 28-32 ℃, weighing 100-400 parts of ethyl acetate, adding the ethyl acetate into a three-necked bottle, mechanically or magnetically stirring at the rotating speed of 300r/min, placing the three-necked bottle in a vacuum of 0.092MPa after stirring, and performing the dehydration reaction for 0.5-1 h to obtain the single-component polyurethane interfacial agent;
step 5.6, placing the single-component polyurethane interface agent prepared in the step 5.5 in a glass volumetric flask for sealing and storing;
step 6, mechanically mixing and stirring the preparations obtained in the steps 1, 2, 3 and 4 at the rotating speed of 500r/min, and performing ultrasonic modification after stirring for 5min, wherein ultrasonic treatment is performed for 45min by using water bath ultrasonic treatment with the power of 180W;
and 7, adding the preparation obtained in the step 5 into the step 6, magnetically mixing and stirring at the rotating speed of 700r/min, removing bubbles by using ultrasound after stirring for 7min, and performing ultrasonic treatment for 90min by using a water bath with the power of 250W to obtain the composite wave-absorbing coating.
Further, the hydroxyl-terminated polyether polyol in step 5 is one of difunctional polyoxypropylene ether and difunctional polyoxyethylene ether having an average molecular weight of 1000.
Further, the diisocyanate in step 5 is one of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate, and norbornane dimethylene isocyanate.
Further, the propylene glycol methyl ether acetate in the step 5 is selected from one of toluene, xylene, ethyl acetate, butyl acetate and propylene glycol methyl ether propionate.
Further, the ethyl acetate in the step 5 is selected from one of methyl propionate, dimethyl carbonate, ethyl propionate, ethylene glycol ethyl ether acetate and methyl acetate.
Compared with the prior art, the invention has the beneficial effects that: the composite wave-absorbing coating comprises a wave-absorbing agent and a coating, wherein the wave-absorbing agent of the composite wave-absorbing coating is a multi-component nano composite material, the coating of the composite wave-absorbing coating is a single-component polyurethane interface agent, the multi-component nano composite material comprises a multi-component system of carbonyl iron nano particles, polypyrrole and graphene, and the single-component polyurethane interface agent serving as the coating of the wave-absorbing coating can meet the requirement of curing in a low-temperature environment and has the characteristics of high surface hardness, high interface bonding strength and the like; the multi-element nano composite material and the single-component polyurethane interface agent are prepared by a traditional mechanical or magnetic stirring process, the process is simple, the prepared wave-absorbing coating is suitable for 2 hours, the problems of high density, narrow wave-absorbing frequency band, poor mechanical property and the like of the traditional wave-absorbing coating are solved, and the wave-absorbing coating is suitable for industrial large-scale production and is particularly applied to occasions with frequency bands wide and strong wave-absorbing capacity in the frequency range of 2-18GHz of radar waves.
Detailed Description
In order to solve the problems of large density, narrow wave-absorbing frequency band, poor mechanical property and the like of the traditional wave-absorbing coating, the invention provides a composite wave-absorbing coating which comprises a wave-absorbing agent and a coating, wherein the wave-absorbing agent of the composite wave-absorbing coating is a multi-component nano composite material, the coating of the composite wave-absorbing coating is a single-component polyurethane interface agent, and the weight ratio of the multi-component nano composite material to the single-component polyurethane interface agent is 4: 1.
Further, the multi-element nano composite material is prepared from 1-2 parts of graphene oxide, 1-2 parts of polypyrrole, 30-50 parts of carbonyl iron nanoparticles and 1-2 parts of graphene-loaded polypyrrole nano composite material.
Further, the multi-element nano composite material is prepared from graphene oxide, polypyrrole, carbonyl iron nanoparticles and a graphene-loaded polypyrrole nano composite material, wherein 1.5 parts of graphene oxide, 1.5 parts of polypyrrole, 40 parts of carbonyl iron nanoparticles and 1.5 parts of a graphene-loaded polypyrrole nano composite material.
The single-component polyurethane interface agent is further prepared from 50-150 parts of hydroxyl-terminated polyether polyol, 100-200 parts of propylene glycol monomethyl ether acetate, 30-50 parts of trimethylolpropane, 50-300 parts of diisocyanate and 100-400 parts of ethyl acetate.
Further, the single-component polyurethane interface agent is prepared from 100 parts of hydroxyl-terminated polyether polyol, 150 parts of propylene glycol monomethyl ether acetate, 40 parts of trimethylolpropane, 175 parts of diisocyanate and 250 parts of ethyl acetate.
The invention also provides a preparation method of the composite wave-absorbing coating, which comprises the following steps:
step 1, preparing graphene oxide:
step 1.1, taking a three-necked bottle, placing the three-necked bottle in an ice-water bath, adding 42-46 parts of concentrated sulfuric acid with the concentration of 98% into the three-necked bottle, magnetically stirring at the rotation speed of 400r/min, weighing 2-8 parts of graphite, 1-4 parts of sodium nitrate and 6-12 parts of potassium permanganate, adding into the three-necked bottle, mixing with the concentrated sulfuric acid, and stirring, wherein the speed ratio of adding the graphite and the sodium nitrate to the speed ratio of adding the potassium permanganate is 5: 1;
step 1.2, switching the ice-water bath in the step 1.1 into a warm water bath, weighing 86-90 parts of deionized water, adding the deionized water into a three-neck flask, raising the temperature of the warm water bath to 98 ℃, and adding 8-12 parts of hydrogen peroxide solution with the molar concentration of 2mol/L into the three-neck flask for oxidation reaction;
step 1.3, centrifugally cleaning the graphene oxide obtained in the step 1.2 at a centrifugal rate of 10000r/min, centrifuging for 15min, and then centrifugally cleaning a lower-layer precipitate until Ph is 7;
step 1.4, centrifugally cleaning the graphene oxide obtained in the step 1.3 until Ph is 7, adding deionized water for dilution, and adding 16-20 parts of hydrazine hydrate for reduction reaction at the temperature of 90 ℃;
step 1.5, centrifugally cleaning the graphene oxide obtained in the step 1.4 at a centrifugal rate of 10000r/min, centrifuging for 15min, and then carrying out multiple times of centrifugal cleaning on the lower-layer precipitate until Ph is 7 to obtain graphene oxide;
step 1.6, sealing and storing the graphene oxide prepared in the step 1.5 in an acetone solution for later use;
step 2, preparing polypyrrole:
step 2.1, weighing 1-5 parts of methyl orange, dissolving in 550-650 parts of deionized water, and placing on a magnetic stirring table at the rotating speed of 450 r/min;
step 2.2, weighing 8-20 parts of ferric chloride hexahydrate, adding into the step 2.1, continuously stirring for 40min, adding 2-5 parts of pyrrole, and polymerizing for 24h at room temperature;
step 2.3, centrifugally cleaning the reactant of the polymerization reaction in the step 2.2 at a centrifugal rate of 10000r/min, centrifuging for 15min, taking the lower-layer precipitate, and centrifugally cleaning until Ph is 7 to obtain polypyrrole;
step 2.4, sealing and storing the polypyrrole prepared in the step 2.3 in an acetone solution for later use;
step 3, preparing carbonyl iron nanoparticles:
step 3.1, weighing 6-10 parts of sponge iron, cleaning, crushing until the diameter is 3mm, grinding the crushed sponge iron into powder with the particle size of 50 microns by adopting a planetary ball mill, introducing H2Reducing, placing the reduced product in a synthesis reaction kettle, introducing CO, heating the synthesis reaction kettle to carry out synthesis reaction, and reducing pressure and cooling after the synthesis reaction to obtain Fe (CO)5A liquid;
step 3.2, mixing the Fe (CO) in the step 3.15The liquid is gasified in a pyrolysis furnace to form gaseous Fe (CO)5Gaseous Fe (CO) at 300 ℃ and a pressure of 1bar5Decomposing to form iron core;
step 3.3, performing ball milling treatment on the iron core in the step 3.2 for 90min to prepare carbonyl iron nanoparticles;
wherein the ball milling treatment is carried out for 90min under the conditions that the ball material mass ratio is 6:1 and the ball milling rotating speed is 35 r/min;
step 3.4, placing the carbonyl iron nanoparticles prepared in the step 3.3 in a sealing bag, and sealing and storing for later use;
step 4, preparing the graphene loaded polypyrrole nano composite material:
step 4.1, adding 10-15 parts of graphene oxide into 400-600 parts of deionized water, mechanically stirring until the graphene oxide is uniformly dispersed, adding 4-10 parts of ferric trichloride hexahydrate, and continuously stirring for 50min at the rotating speed of 350 r/min;
step 4.2, adding 1-5 parts of polypyrrole into the step 4.1, continuously mechanically stirring at the rotating speed of 450r/min, and polymerizing for 24 hours at room temperature;
step 4.3, centrifugally cleaning the reactant after the polymerization reaction in the step 4.2 at a centrifugal rate of 10000r/min, centrifuging for 15min, and then centrifugally cleaning the lower-layer precipitate until Ph is 7;
step 4.4, placing the reactant which is subjected to centrifugal cleaning in the step 4.3 until Ph is 7 into an oil bath pot, heating to 90 ℃, adding 16-20 parts of hydrazine hydrate solution, and reacting for 8 hours;
step 4.5, centrifugally cleaning the reactant stirred in the step 4.4 at a centrifugal rate of 10000r/min, centrifuging for 15min, then taking the lower-layer precipitate, and centrifugally cleaning until Ph is 7 to obtain the graphene-loaded polypyrrole nanocomposite;
step 4.6, storing the graphene-loaded polypyrrole nanocomposite material prepared in the step 4.5 in an acetone solution for later use;
step 5, preparing a single-component polyurethane interface agent:
step 5.1, weighing 50-150 parts of hydroxyl-terminated polyether polyol and 100-200 parts of propylene glycol methyl ether acetate, adding into a 500ml three-necked bottle, and mechanically or magnetically stirring at the rotating speed of 150 r/min;
step 5.2, heating the three-mouth bottle and stirring the mixture in the three-mouth bottle, and stopping heating when the temperature of the mixture in the three-mouth bottle is raised to 90 ℃;
step 5.3, weighing 30-50 parts of trimethylolpropane, adding the 30-50 parts of trimethylolpropane into the three-necked bottle in the step 5.2, mechanically or magnetically stirring at the rotating speed of 350r/min, heating the three-necked bottle after stirring at the heating temperature of 80-100 ℃, and placing the three-necked bottle in a vacuum of 0.092MPa for dehydration reaction for 1.5-2 h;
step 5.4, introducing air into the vacuum of 0.092MPa in the step 5.3, reducing the temperature of the mixture in the three-necked bottle to 60-65 ℃, weighing 50-300 parts of diisocyanate, adding the diisocyanate into the three-necked bottle, stirring mechanically or magnetically at the rotating speed of 300r/min, heating the three-necked bottle after stirring, increasing the temperature of the mixture in the three-necked bottle to 80-90 ℃, placing the three-necked bottle in the vacuum of 0.092MPa for dehydration reaction for 1.5-2 h, wherein the rotating speed of the dehydration reaction is 500 r/min;
step 5.5, cooling the mixture obtained after the dehydration reaction in the step 5.4 to 28-32 ℃, weighing 100-400 parts of ethyl acetate, adding the ethyl acetate into a three-necked bottle, mechanically or magnetically stirring at the rotating speed of 300r/min, placing the three-necked bottle in a vacuum of 0.092MPa after stirring, and performing the dehydration reaction for 0.5-1 h to obtain the single-component polyurethane interfacial agent;
step 5.6, placing the single-component polyurethane interface agent prepared in the step 5.5 in a glass volumetric flask for sealing and storing;
step 6, mechanically mixing and stirring the preparations obtained in the steps 1, 2, 3 and 4 at the rotating speed of 500r/min, and performing ultrasonic modification after stirring for 5min, wherein ultrasonic treatment is performed for 45min by using water bath ultrasonic treatment with the power of 180W;
and 7, adding the preparation obtained in the step 5 into the step 6, magnetically mixing and stirring at the rotating speed of 700r/min, removing bubbles by using ultrasound after stirring for 7min, and performing ultrasonic treatment for 90min by using a water bath with the power of 250W to obtain the composite wave-absorbing coating.
Further, the hydroxyl-terminated polyether polyol in step 5 is one of difunctional polyoxypropylene ether and difunctional polyoxyethylene ether having an average molecular weight of 1000.
Further, the diisocyanate in step 5 is one of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate, and norbornane dimethylene isocyanate.
Further, the propylene glycol methyl ether acetate in the step 5 is selected from one of toluene, xylene, ethyl acetate, butyl acetate and propylene glycol methyl ether propionate.
Further, the ethyl acetate in the step 5 is selected from one of methyl propionate, dimethyl carbonate, ethyl propionate, ethylene glycol ethyl ether acetate and methyl acetate.
Finally, it should be understood that the above-mentioned embodiments are merely preferred embodiments of the present invention, and not intended to limit the present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. The composite wave-absorbing coating is characterized by comprising a wave-absorbing agent and a coating;
the wave absorbing agent of the composite wave absorbing coating is a multi-element nano composite material;
the coating of the composite wave-absorbing coating adopts a single-component polyurethane interface agent;
the ratio of the weight parts of the multi-component nano composite material to the weight parts of the single-component polyurethane interface agent is 4: 1.
2. The composite wave-absorbing coating of claim 1, wherein the multi-element nanocomposite is prepared from graphene oxide, polypyrrole, carbonyl iron nanoparticles, and graphene-loaded polypyrrole nanocomposite;
1-2 parts of graphene oxide, 1-2 parts of polypyrrole, 30-50 parts of carbonyl iron nanoparticles and 1-2 parts of a graphene-loaded polypyrrole nanocomposite;
the single-component polyurethane interface agent is prepared from hydroxyl-terminated polyether polyol, propylene glycol monomethyl ether acetate, trimethylolpropane, diisocyanate and ethyl acetate;
wherein, the hydroxyl-terminated polyether polyol is 50-150 parts, the propylene glycol methyl ether acetate is 100-200 parts, the trimethylolpropane is 30-50 parts, the diisocyanate is 50-300 parts, and the ethyl acetate is 100-400 parts.
3. A preparation method of the composite wave-absorbing coating of claim 1, comprising the following steps:
step 1, preparing graphene oxide;
step 2, preparing polypyrrole;
step 3, preparing carbonyl iron nanoparticles;
step 4, preparing the graphene loaded polypyrrole nano composite material;
step 5, preparing a single-component polyurethane interface agent;
step 6, mechanically mixing and stirring the preparations obtained in the steps 1, 2, 3 and 4;
and 7, adding the preparation obtained in the step 5 into the step 6, and mixing and stirring the mixture by magnetic force to obtain the composite wave-absorbing coating.
4. The preparation method of the composite wave-absorbing coating according to claim 3, wherein the step of preparing the graphene oxide in the step 1 is as follows:
step 1.1, taking a three-necked bottle, placing the three-necked bottle in an ice-water bath, adding 42-46 parts of concentrated sulfuric acid with the concentration of 98% into the three-necked bottle, magnetically stirring at the rotating speed of 400r/min, weighing 2-8 parts of graphite, 1-4 parts of sodium nitrate and 6-12 parts of potassium permanganate, adding into the three-necked bottle, and mixing with the concentrated sulfuric acid;
wherein the speed ratio of adding graphite and sodium nitrate to adding potassium permanganate is 5: 1;
step 1.2, switching the ice-water bath in the step 1.1 into a warm water bath, weighing 86-90 parts of deionized water, adding the deionized water into a three-neck flask, raising the temperature of the warm water bath to 98 ℃, and adding 8-12 parts of hydrogen peroxide solution with the molar concentration of 2mol/L into the three-neck flask for oxidation reaction;
step 1.3, centrifugally cleaning the graphene oxide obtained in the step 1.2 at a centrifugal rate of 10000r/min, centrifuging for 15min, and then centrifugally cleaning a lower-layer precipitate until Ph is 7;
step 1.4, centrifugally cleaning the graphene oxide obtained in the step 1.3 until Ph is 7, adding deionized water to dilute the graphene oxide, and adding 16-20 parts of hydrazine hydrate to perform a reduction reaction at the temperature of 90 ℃;
step 1.5, centrifugally cleaning the graphene oxide obtained in the step 1.4 at a centrifugal rate of 10000r/min, centrifuging for 15min, and then carrying out multiple times of centrifugal cleaning on the lower-layer precipitate until Ph is 7 to obtain graphene oxide;
and step 1.6, sealing and storing the graphene oxide prepared in the step 1.5 in an acetone solution for later use.
5. The preparation method of the composite wave-absorbing coating according to claim 3, wherein the polypyrrole is prepared in the step 2 by the following steps:
step 2.1, weighing 1-5 parts of methyl orange, dissolving in 550-650 parts of deionized water, and placing on a magnetic stirring table at the rotating speed of 450 r/min;
step 2.2, weighing 8-20 parts of ferric chloride hexahydrate, adding into the step 2.1, continuously stirring for 40min, adding 2-5 parts of pyrrole, and polymerizing for 24h at room temperature;
step 2.3, centrifugally cleaning the reactant of the polymerization reaction in the step 2.2 at a centrifugal rate of 10000r/min, centrifuging for 15min, taking the lower-layer precipitate, and centrifugally cleaning until Ph is 7 to obtain polypyrrole;
and 2.4, sealing and storing the polypyrrole prepared in the step 2.3 in an acetone solution for later use.
6. The preparation method of the composite wave-absorbing coating according to claim 3, wherein the step of preparing the carbonyl iron nanoparticles in the step 3 is as follows:
step 3.1, weighing 6-10 parts of sponge iron, cleaning, crushing until the diameter is 3mm, grinding the crushed sponge iron into powder with the particle size of 50 microns by adopting a planetary ball mill, introducing H2Reducing, placing the reduced product in a synthesis reaction kettle, introducing CO, heating the synthesis reaction kettle to carry out synthesis reaction, and reducing pressure and cooling after the synthesis reaction to obtain Fe (CO)5A liquid;
step 3.2, mixing the Fe (CO) in the step 3.15The liquid is gasified in a pyrolysis furnace to form gaseous Fe (CO)5Gaseous Fe (CO) at 300 ℃ and a pressure of 1bar5Decomposing to form iron core;
step 3.3, performing ball milling treatment on the iron core in the step 3.2 for 90min to prepare carbonyl iron nanoparticles;
wherein the ball milling treatment is carried out for 90min under the conditions that the ball material mass ratio is 6:1 and the ball milling rotating speed is 35 r/min;
and 3.4, placing the carbonyl iron nanoparticles prepared in the step 3.3 into a sealing bag, and sealing and storing for later use.
7. The preparation method of the composite wave-absorbing coating according to claim 3, wherein the step of preparing the graphene-loaded polypyrrole nanocomposite in the step 4 is as follows:
step 4.1, adding 10-15 parts of graphene oxide into 400-600 parts of deionized water, mechanically stirring until the graphene oxide is uniformly dispersed, adding 4-10 parts of ferric trichloride hexahydrate, and continuously stirring for 50min at the rotating speed of 350 r/min;
step 4.2, adding 1-5 parts of pyrrole into the step 4.1, continuously mechanically stirring at the rotating speed of 450r/min, and polymerizing for 24 hours at room temperature;
step 4.3, centrifugally cleaning the reactant after the polymerization reaction in the step 4.2 at a centrifugal rate of 10000r/min, centrifuging for 15min, and then centrifugally cleaning the lower-layer precipitate until Ph is 7;
step 4.4, placing the reactant which is subjected to centrifugal cleaning in the step 4.3 until Ph is 7 into an oil bath pot, heating to 90 ℃, adding 16-20 parts of hydrazine hydrate solution, and reacting for 8 hours;
step 4.5, centrifugally cleaning the reactant stirred in the step 4.4 at a centrifugal rate of 10000r/min, centrifuging for 15min, then taking the lower-layer precipitate, and centrifugally cleaning until Ph is 7 to obtain the graphene-loaded polypyrrole nanocomposite;
and 4.6, storing the graphene-loaded polypyrrole nano composite material prepared in the step 4.5 in an acetone solution for later use.
8. A preparation method of the composite wave-absorbing coating according to claim 3, wherein the step of preparing the single-component polyurethane interface agent in the step 5 is as follows:
step 5.1, weighing 50-150 parts of hydroxyl-terminated polyether polyol PPG-1000 and 100-200 parts of propylene glycol methyl ether acetate PMA, adding into a 500ml three-necked bottle, and mechanically or magnetically stirring at the rotation speed of 150 r/min;
step 5.2, heating the three-mouth bottle and stirring the mixture in the three-mouth bottle, and stopping heating when the temperature of the mixture in the three-mouth bottle is raised to 90 ℃;
step 5.3, weighing 30-50 parts of trimethylolpropane, adding the 30-50 parts of trimethylolpropane into the three-necked bottle in the step 5.2, mechanically or magnetically stirring at the rotating speed of 350r/min, heating the three-necked bottle after stirring at the heating temperature of 80-100 ℃, and placing the three-necked bottle in a vacuum of 0.092MPa for dehydration reaction for 1.5-2 h;
step 5.4, introducing air into the vacuum of 0.092MPa in the step 5.3, reducing the temperature of the mixture in the three-necked bottle to 60-65 ℃, weighing 50-300 parts of diisocyanate, adding the diisocyanate into the three-necked bottle, stirring mechanically or magnetically at the rotating speed of 300r/min, heating the three-necked bottle after stirring, increasing the temperature of the mixture in the three-necked bottle to 80-90 ℃, placing the three-necked bottle in the vacuum of 0.092MPa for dehydration reaction for 1.5-2 h, wherein the rotating speed of the dehydration reaction is 500 r/min;
step 5.5, cooling the mixture obtained after the dehydration reaction in the step 5.4 to 28-32 ℃, weighing 100-400 parts of ethyl acetate, adding the ethyl acetate into a three-necked bottle, mechanically or magnetically stirring at the rotating speed of 300r/min, placing the three-necked bottle in a vacuum of 0.092MPa after stirring, and performing the dehydration reaction for 0.5-1 h to obtain the single-component polyurethane interfacial agent;
and 5.6, placing the single-component polyurethane interface agent prepared in the step 5.5 into a glass volumetric flask for sealing and storing.
9. The preparation method of the composite wave-absorbing coating according to claim 3, wherein the rotation speed of mechanical mixing and stirring in the step 6 is 500r/min, and ultrasonic modification is adopted after stirring for 5 min;
wherein, the ultrasound adopts water bath ultrasound treatment with power of 180W for 45 min;
in the step 7, the rotating speed of magnetic mixing stirring is 700r/min, and bubbles are removed by adopting ultrasonic after stirring for 7 min;
wherein, the ultrasound adopts water bath ultrasound treatment with power of 250W for 90 min.
10. The preparation method of the composite wave-absorbing coating according to claim 8, wherein the hydroxyl-terminated polyether polyol in step 5 is one of difunctional polyoxypropylene ether and difunctional polyoxyethylene ether with an average molecular weight of 1000;
the diisocyanate in the step 5 is one of diphenylmethane diisocyanate, toluene diisocyanate, isophorone diisocyanate, hexamethylene diisocyanate, 1, 5-naphthalene diisocyanate and norbornane dimethylene isocyanate;
the propylene glycol methyl ether acetate in the step 5 is selected from one of toluene, xylene, ethyl acetate, butyl acetate and propylene glycol methyl ether propionate;
the ethyl acetate in the step 5 is selected from one of methyl propionate, dimethyl carbonate, ethyl propionate, ethylene glycol ethyl ether acetate and methyl acetate.
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| CN108456294A (en) * | 2018-02-01 | 2018-08-28 | 青岛科技大学 | A kind of polyurethane elastomer and preparation method thereof that high temperature-resistant grease is ageing-resistant |
| CN109750493A (en) * | 2019-01-18 | 2019-05-14 | 中国航发北京航空材料研究院 | A kind of preparation method of graphene electromagnetic shielding composite material |
| CN110205096A (en) * | 2019-06-13 | 2019-09-06 | 青岛科凯达橡塑有限公司 | A kind of controllable micropore absorbing meta-material and its preparation method and application |
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| CN108456294A (en) * | 2018-02-01 | 2018-08-28 | 青岛科技大学 | A kind of polyurethane elastomer and preparation method thereof that high temperature-resistant grease is ageing-resistant |
| CN109750493A (en) * | 2019-01-18 | 2019-05-14 | 中国航发北京航空材料研究院 | A kind of preparation method of graphene electromagnetic shielding composite material |
| CN110205096A (en) * | 2019-06-13 | 2019-09-06 | 青岛科凯达橡塑有限公司 | A kind of controllable micropore absorbing meta-material and its preparation method and application |
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