CN104962185A - Graphene-loaded nanometer Fe3O4/aqueous polyurethane composite magnetic conductive wave absorbing coating material and preparation method thereof - Google Patents

Graphene-loaded nanometer Fe3O4/aqueous polyurethane composite magnetic conductive wave absorbing coating material and preparation method thereof Download PDF

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CN104962185A
CN104962185A CN201510296728.8A CN201510296728A CN104962185A CN 104962185 A CN104962185 A CN 104962185A CN 201510296728 A CN201510296728 A CN 201510296728A CN 104962185 A CN104962185 A CN 104962185A
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graphene
magnetic conductive
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aqueous polyurethane
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CN104962185B (en
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罗晓民
葛炳辉
冯见艳
曹敏
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Shaanxi University of Science and Technology
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Shaanxi University of Science and Technology
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Abstract

The invention relates to a graphene-loaded nanometer Fe3O4/aqueous polyurethane composite magnetic conductive wave absorbing coating material and a preparation method thereof. A polymer composite material utilizing a carbon material as a filler has unique advantages in the field of electromagnetic shielding. Graphene as a two-dimensional nanometer carbon material has excellent electrical, mechanical and thermodynamic properties and has excellent electromagnetic shielding material potential. The graphene-loaded nanometer Fe3O4/aqueous polyurethane composite magnetic conductive wave absorbing coating material is prepared from a high-molecular organic resin, graphene-loaded Fe3O4 composite magnetic conductive nanoparticles, an organic solvent, a dispersant and an antifoaming agent. The graphene-loaded Fe3O4 composite magnetic conductive nanoparticle is prepared from graphite, concentrated sulfuric acid, sodium nitrate, potassium permanganate, ferric trichloride, ferrous sulphate, sodium hydroxide and hydrazine hydrate. The graphene-loaded nanometer Fe3O4/aqueous polyurethane composite magnetic conductive wave absorbing coating material has the characteristics of good conductivity, macro-magnetism and high stability and has a certain electromagnetic shielding function.

Description

Graphene-supported nanometer Fe 3o 4/ aqueous polyurethane composite magnetic conductive wave-absorbing coating material and preparation method thereof
Technical field
the present invention relates to a kind of microwave absorbing coating, be specifically related to a kind of graphene-supported nanometer Fe 3o 4/ aqueous polyurethane composite magnetic conductive wave-absorbing coating material and preparation method thereof.
Background technology
Along with developing rapidly of electrified universal and telecommunications industry, electromagnetic energy is widely used in the every field of national economy, for daily life brings great convenience.But numerous hertzian wave causes normal electromagnetism ecotope disorderly, bring serious ecological environment problem, electromagnetic radiation being considered as a kind of new source of pollution in the world, being called electromagnetic radiation pollution, is the fourth-largest pollution after atmospheric pollution, water pollutions, noise pollution.At present, effectively suppress electromagnetic radiation, leakage, interference and improve electromagnetic environment, mainly based on conductivity type electromagnetic shielding.Conventional absorbing material mainly obtains with composite algorithm, there is the advantage of oneself uniqueness in electromagnetic shielding field as the polymer composite of filler using carbon material, Graphene is as a kind of novel two-dimensional nano carbon material, have extremely excellent electricity, mechanics and thermomechanical property, the performance of these excellences makes Graphene after forming matrix material with macromolecular material, have the splendid potential quality as electromagnetic shielding material.
Summary of the invention
The object of this invention is to provide a kind of graphene-supported nanometer Fe 3o 4/ aqueous polyurethane composite magnetic conductive wave-absorbing coating material and preparation method thereof, good conductivity, has macroscopic magnetization, and stability is high.
The technical solution adopted in the present invention is:
Graphene-supported nanometer Fe 3o 4/ aqueous polyurethane composite magnetic conductive wave-absorbing coating material, is characterized in that:
Prepared by the component of following mass parts:
Polymer organic resin 60-75 part;
Graphene-supported Fe 3o 4composite magnetic conductive nanoparticle 1-10 part;
Organic solvent 20-30 part;
Dispersion agent 0.1-0.5 part;
Defoamer 0.1-0.5 part.
Described polymer organic resin is waterborne polyurethane resin.
Described graphene-supported Fe 3o 4composite magnetic conductive nanoparticle is obtained by following component:
Graphite 2-3g;
Massfraction is the vitriol oil 60-120mL of 98%;
SODIUMNITRATE 1-2g;
Potassium permanganate 6-9g;
Iron trichloride 0.38-0.94g;
Ferrous sulfate 0.22-0.56g;
Volumetric molar concentration is the sodium hydroxide solution 5-15mL of 1mol/L;
Hydrazine hydrate 1-3mL;
Water 290-450mL.
Described organic solvent is DMF, acetone or dehydrated alcohol.
Described dispersion agent is palmityl trimethyl ammonium chloride or dodecyl sulphate diethanolamine salt.
Described defoamer is methyl-silicone oil, siloxanes or tributyl phosphate.
Graphene-supported nanometer Fe 3o 4the preparation method of/aqueous polyurethane composite magnetic conductive wave-absorbing coating material, is characterized in that:
Realized by following steps:
1) graphene-supported Fe 3o 4the preparation of composite magnetic conductive nanoparticle organic solution:
(1) preparation of graphene oxide:
Be the vitriol oil of 98% by 2-3g graphite, 60-120mL massfraction, the mixing of 1-2g SODIUMNITRATE is placed in ice-water bath and stirs, add 6-9g potassium permanganate again and continue reaction, at room temperature react again and add the water of 90-150mL, be oxidized thoroughly at 95-100 DEG C and obtain graphite oxide, more ultrasonic stripping high speed centrifugation obtains graphene oxide water solution;
(2) graphene-supported nanometer Fe is prepared 3o 4:
First with 200-300mL water, 40-60mL graphene oxide solution is diluted, with iron trichloride and ferrous sulfate for molysite, add iron trichloride 0.38-0.94g, ferrous sulfate 0.22-0.56g, using the 5-15mL volumetric molar concentration NaOH solution that is 1mol/L as precipitation agent, at 50-60 DEG C, react 30min; And then add 1-3mL hydrazine hydrate, react 3-5h at the temperature of 90 ± 5 DEG C after, take out naturally cooling;
(3) be separated:
After being neutrality with the separation of magnetic decantation, distilled water wash to product mixture, filtration under diminished pressure, obtains graphene-supported Fe 3o 4composite magnetic conductive nanoparticle;
(4) aftertreatment:
1) by the graphene-supported Fe of preparation 3o 4after composite magnetic conductive nanoparticle 1-10 mass parts organic solvent washing, ultrasonic disperse is in the organic solvent of 20-30 mass parts, obtains graphene-supported Fe 3o 4composite magnetic conductive nanoparticle organic solution;
2) at the graphene-supported Fe of gained 3o 4add 60-75 mass parts polymer organic resin, 0.1-0.5 mass parts dispersion agent, 0.1-0.5 mass parts defoamer in composite magnetic conductive nanoparticle organic solution, be mixed together ultrasonic disperse, high shear agitation, film obtains product.
In (4) of step 1), organic solvent is DMF, acetone or dehydrated alcohol;
Step 2) in, polymer organic resin is waterborne polyurethane resin, and dispersion agent is palmityl trimethyl ammonium chloride or dodecyl sulphate diethanolamine salt, and defoamer is methyl-silicone oil, siloxanes or tributyl phosphate.
The present invention has the following advantages:
The present invention is first by graphene-supported Fe 3o 4composite magnetic conductive nanoparticle is applied in waterborne polyurethane resin, and has prepared a kind of magnetic conductive microwave absorbing coating.This coating not only has graphene-supported Fe 3o 4the magnetic of composite magnetic conductive nanoparticle, electroconductibility, microwave absorbing property, also have the advantages such as aqueous polyurethane is nontoxic, free from environmental pollution, high strength, fastness to rubbing.Compared with traditional coated material, the coating that the present invention relates to is a kind of microwave absorbing coating of double dielectric loss and magnetic loss, and this is unique a kind of microwave absorbing coating having two kinds of losses concurrently in current aqueous polyurethane coating.Organic solvent usage quantity in this coating greatly reduces, and has certain feature of environmental protection.And its preparation method is simple, can be applicable to multiple field.
The nanoparticulate fillers adopted-graphene-supported Fe 3o 4composite magnetic conductive nanoparticle, in its preparation process, directly the nanoparticle of compound ultrasonic disperse after organic solvent washing several times, in organic solvent, can be reduced the reunion of composite particles in process of vacuum drying, the dispersiveness of nanoparticle in aqueous polyurethane can be improved.Its actual measurement specific conductivity is suitable with Graphene, and nanoparticle is by Graphene and magnetite (Fe 3o 4) two phase composites, make it have very strong macroscopic magnetization, can by common attraction.Therefore prepared coating not only has magnetic conductive, also has and inhales ripple usefulness.
In addition, through characterization test, composite granule is have special microtexture, Fe at microcosmic 3o 4graphene film Rotating fields, in graphenic surface, wrapped up by particle absorption, and its entirety is still in flakey.Graphene-supported nanometer Fe 3o 4the organic solution of composite particles and macromolecule resin have consistency well, and therefore compound coating of the present invention has good stability and dispersion effect.
Accompanying drawing explanation
Fig. 1 is graphene-supported nanometer Fe 3o 4the XRD figure spectrum of composite magnetic conductive nanoparticle.
Known by atlas analysis, prepared powder has Graphene, Fe 3o 4with a small amount of residual graphene oxide composition be not reduced.
Fig. 2 is graphene-supported nanometer Fe 3o 4the scanning electron microscope of composite magnetic conductive powder stuffing and transmission electron microscope photo.(a is 300nm level, and b is 500nm level)
As can be seen from stereoscan photograph, prepared powder is crystalloid, and crystalline diameter is in tens nanometers, and size ratio is more even.More can illustrate that Z 250 is carried on Graphene from transmission electron microscope photo, instead of only be gathered on the surface of Graphene coacervate.
Fig. 3 is graphene-supported Fe 3o 4the dispersion in organic solvent of magnetic conductive powder and the displaying (a is the phenomenon when not adding magnetic field, and b is the phenomenon under the action of a magnetic field after 25s) of magnetic thereof.
Embodiment
Below in conjunction with embodiment, the present invention will be described in detail.
The graphene-supported nanometer Fe of the one that the present invention relates to 3o 4/ aqueous polyurethane composite magnetic conductive wave-absorbing coating material and preparation method thereof, having prepared one first also holds concurrently electric based on water-base polyurethane material, the microwave absorbing coating of magnetic loss, relative to conventional washcoat material, aqueous polyurethane coating has environmental protection, the advantage such as nontoxic, this preparation method of composite coating is simple, and multiple field can be applied to, and be by vibration in phase and the mutual characteristic propagated of vertical electric field and magnetic field according to hertzian wave self, adopt Graphene as the electrical loss medium of matrix material, and nano-scale magnetic Z 250 is carried on Graphene, guarantee that matrix material in use provides magnetic loss medium and the stability of self, by itself and water polyurethane base volume recombination, thus obtained there is magnetic and conducting function, hold concurrently electric, magnetic loss also has the compound coating of absorptive function to the hertzian wave of certain frequency scope.
The graphene-supported nanometer Fe that the present invention relates to 3o 4/ aqueous polyurethane composite magnetic conductive wave-absorbing coating material, prepared by the component of following mass parts:
Polymer organic resin 60-75 part;
Graphene-supported Fe 3o 4composite magnetic conductive nanoparticle 1-10 part;
Organic solvent 20-30 part;
Dispersion agent 0.1-0.5 part;
Defoamer 0.1-0.5 part.
Wherein:
Described polymer organic resin is waterborne polyurethane resin.
Described graphene-supported Fe 3o 4composite magnetic conductive nanoparticle is obtained by following component:
Graphite 2-3g;
Massfraction is the vitriol oil 60-120mL of 98%;
SODIUMNITRATE 1-2g;
Potassium permanganate 6-9g;
Iron trichloride 0.38-0.94g;
Ferrous sulfate 0.22-0.56g;
Volumetric molar concentration is the sodium hydroxide solution 5-15mL of 1mol/L;
Hydrazine hydrate 1-3mL;
Water 290-450mL.
Described organic solvent is DMF, acetone or dehydrated alcohol.
Described dispersion agent is palmityl trimethyl ammonium chloride or dodecyl sulphate diethanolamine salt.
Described defoamer is methyl-silicone oil, siloxanes or tributyl phosphate.
Above-mentioned graphene-supported nanometer Fe 3o 4the preparation method of/aqueous polyurethane composite magnetic conductive wave-absorbing coating material, is realized by following steps:
1) graphene-supported Fe 3o 4the preparation of composite magnetic conductive nanoparticle organic solution:
(1) preparation of graphene oxide:
Be the vitriol oil of 98% by 2-3g graphite, 60-120mL massfraction, the mixing of 1-2g SODIUMNITRATE is placed in ice-water bath and stirs, add 6-9g potassium permanganate again and continue reaction, at room temperature react again and add the water of 90-150mL, be oxidized thoroughly at 95-100 DEG C and obtain graphite oxide, more ultrasonic stripping high speed centrifugation obtains graphene oxide water solution;
(2) graphene-supported nanometer Fe is prepared 3o 4:
First with 200-300mL water, 40-60mL graphene oxide solution is diluted, with iron trichloride and ferrous sulfate for molysite, add iron trichloride 0.38-0.94g, ferrous sulfate 0.22-0.56g, using the 5-15mL volumetric molar concentration NaOH solution that is 1mol/L as precipitation agent, at 50-60 DEG C, react 30min; And then add 1-3mL hydrazine hydrate, react 3-5h at the temperature of 90 ± 5 DEG C after, take out naturally cooling;
(3) be separated:
After being neutrality with the separation of magnetic decantation, distilled water wash to product mixture, filtration under diminished pressure, obtains graphene-supported Fe 3o 4composite magnetic conductive nanoparticle;
(4) aftertreatment:
1) by the graphene-supported Fe of preparation 3o 4after composite magnetic conductive nanoparticle 1-10 mass parts organic solvent washing, ultrasonic disperse is in the organic solvent of 20-30 mass parts, obtains graphene-supported Fe 3o 4composite magnetic conductive nanoparticle organic solution;
2) at the graphene-supported Fe of gained 3o 4add 60-75 mass parts polymer organic resin, 0.1-0.5 mass parts dispersion agent, 0.1-0.5 mass parts defoamer in composite magnetic conductive nanoparticle organic solution, be mixed together ultrasonic disperse, high shear agitation, film obtains product.
In above-mentioned steps:
In (4) of step 1), organic solvent is DMF, acetone or dehydrated alcohol;
Step 2) in, polymer organic resin is waterborne polyurethane resin, and dispersion agent is palmityl trimethyl ammonium chloride or dodecyl sulphate diethanolamine salt, and defoamer is methyl-silicone oil, siloxanes or tributyl phosphate.
Embodiment 1:
1) graphene-supported Fe 3o 4the preparation of composite magnetic conductive nanoparticle organic solution:
(1) preparation of graphene oxide:
Be the vitriol oil of 98% by 2g graphite, 120mL massfraction, the mixing of 1g SODIUMNITRATE is placed in ice-water bath and stirs, add 9g potassium permanganate again and continue reaction, at room temperature react again and add the water of 90mL, be oxidized thoroughly at 100 DEG C and obtain graphite oxide, more ultrasonic stripping high speed centrifugation obtains graphene oxide water solution;
(2) graphene-supported nanometer Fe is prepared 3o 4:
First with 200mL water, 60mL graphene oxide solution is diluted, with iron trichloride and ferrous sulfate for molysite, add iron trichloride 0.38g, ferrous sulfate 0.56g, using the 5mL volumetric molar concentration NaOH solution that is 1mol/L as precipitation agent, reacts 30min at 60 DEG C; And then add 1mL hydrazine hydrate, react 3h at the temperature of 95 DEG C after, take out naturally cooling;
(3) be separated:
After being neutrality with the separation of magnetic decantation, distilled water wash to product mixture, filtration under diminished pressure, obtains graphene-supported Fe 3o 4composite magnetic conductive nanoparticle;
(4) aftertreatment:
1) by the graphene-supported Fe of preparation 3o 4after composite magnetic conductive nanoparticle 10 mass parts organic solvent washing, ultrasonic disperse is in the organic solvent of 20 mass parts, obtains graphene-supported Fe 3o 4composite magnetic conductive nanoparticle organic solution;
2) at the graphene-supported Fe of gained 3o 4add 75 mass parts polymer organic resins, 0.1 mass parts dispersion agent, 0.5 mass parts defoamer in composite magnetic conductive nanoparticle organic solution, be mixed together ultrasonic disperse, high shear agitation, film obtains product.
In above-mentioned steps:
In (4) of step 1), organic solvent is DMF;
Step 2) in, polymer organic resin is waterborne polyurethane resin, and dispersion agent is palmityl trimethyl ammonium chloride, and defoamer is methyl-silicone oil.
Embodiment 2:
1) graphene-supported Fe 3o 4the preparation of composite magnetic conductive nanoparticle organic solution:
(1) preparation of graphene oxide:
Be the vitriol oil of 98% by 2.5g graphite, 90mL massfraction, the mixing of 1.5g SODIUMNITRATE is placed in ice-water bath and stirs, add 7.5g potassium permanganate again and continue reaction, at room temperature react again and add the water of 120mL, be oxidized thoroughly at 97 DEG C and obtain graphite oxide, more ultrasonic stripping high speed centrifugation obtains graphene oxide water solution;
(2) graphene-supported nanometer Fe is prepared 3o 4:
First with 250mL water, 50mL graphene oxide solution is diluted, with iron trichloride and ferrous sulfate for molysite, add iron trichloride 0.66g, ferrous sulfate 0.39g, using the 10mL volumetric molar concentration NaOH solution that is 1mol/L as precipitation agent, reacts 30min at 55 DEG C; And then add 2mL hydrazine hydrate, react 4h at the temperature of 90 DEG C after, take out naturally cooling;
(3) be separated:
After being neutrality with the separation of magnetic decantation, distilled water wash to product mixture, filtration under diminished pressure, obtains graphene-supported Fe 3o 4composite magnetic conductive nanoparticle;
(4) aftertreatment:
1) by the graphene-supported Fe of preparation 3o 4after composite magnetic conductive nanoparticle 5 mass parts organic solvent washing, ultrasonic disperse is in the organic solvent of 25 mass parts, obtains graphene-supported Fe 3o 4composite magnetic conductive nanoparticle organic solution;
2) at the graphene-supported Fe of gained 3o 4add 70 mass parts polymer organic resins, 0.3 mass parts dispersion agent, 0.3 mass parts defoamer in composite magnetic conductive nanoparticle organic solution, be mixed together ultrasonic disperse, high shear agitation, film obtains product.
In above-mentioned steps:
In (4) of step 1), organic solvent is acetone;
Step 2) in, polymer organic resin is waterborne polyurethane resin, and dispersion agent is palmityl trimethyl ammonium chloride, and defoamer is siloxanes.
Embodiment 3:
1) graphene-supported Fe 3o 4the preparation of composite magnetic conductive nanoparticle organic solution:
(1) preparation of graphene oxide:
Be the vitriol oil of 98% by 3g graphite, 60mL massfraction, the mixing of 2g SODIUMNITRATE is placed in ice-water bath and stirs, add 6g potassium permanganate again and continue reaction, at room temperature react again and add the water of 150mL, be oxidized thoroughly at 95 DEG C and obtain graphite oxide, more ultrasonic stripping high speed centrifugation obtains graphene oxide water solution;
(2) graphene-supported nanometer Fe is prepared 3o 4:
First with 300mL water, 40mL graphene oxide solution is diluted, with iron trichloride and ferrous sulfate for molysite, add iron trichloride 0.94g, ferrous sulfate 0.22g, using the 15mL volumetric molar concentration NaOH solution that is 1mol/L as precipitation agent, reacts 30min at 50 DEG C; And then add 3mL hydrazine hydrate, react 5h at the temperature of 85 DEG C after, take out naturally cooling;
(3) be separated:
After being neutrality with the separation of magnetic decantation, distilled water wash to product mixture, filtration under diminished pressure, obtains graphene-supported Fe 3o 4composite magnetic conductive nanoparticle;
(4) aftertreatment:
1) by the graphene-supported Fe of preparation 3o 4after composite magnetic conductive nanoparticle 1 mass parts organic solvent washing, ultrasonic disperse is in the organic solvent of 30 mass parts, obtains graphene-supported Fe 3o 4composite magnetic conductive nanoparticle organic solution;
2) at the graphene-supported Fe of gained 3o 4add 60 mass parts polymer organic resins, 0.5 mass parts dispersion agent, 0.1 mass parts defoamer in composite magnetic conductive nanoparticle organic solution, be mixed together ultrasonic disperse, high shear agitation, film obtains product.
In above-mentioned steps:
In (4) of step 1), organic solvent is dehydrated alcohol;
Step 2) in, polymer organic resin is waterborne polyurethane resin, and dispersion agent is dodecyl sulphate diethanolamine salt, and defoamer is tributyl phosphate.
Composite coating is coated in polyfluortetraethylene plate surface (coat-thickness 20-40 micron), its body resistivity is measured by standard four probe method, being converted into specific conductivity is 5.65-0.015S/m, be 5.13-0.018S/m by its specific conductivity of coating prepared by Graphene filler under equal conditions, both electric conductivity difference are little.In addition, paint is become the circular membrane of diameter 10cm, dry rear film can be picked up by common magnet, shows the magnetic of some strength.And measured by 8501C model vector network analyzer, this magnetic conductive coating is between 8-12.4GHz frequency, and electromagnetic interference (EMI) effectiveness of shielding reaches 34dB.
Content of the present invention is not limited to cited by embodiment, and the conversion of those of ordinary skill in the art by reading specification sheets of the present invention to any equivalence that technical solution of the present invention is taked, is claim of the present invention and contains.

Claims (8)

1. graphene-supported nanometer Fe 3o 4/ aqueous polyurethane composite magnetic conductive wave-absorbing coating material, is characterized in that:
Prepared by the component of following mass parts:
Polymer organic resin 60-75 part;
Graphene-supported Fe 3o 4composite magnetic conductive nanoparticle 1-10 part;
Organic solvent 20-30 part;
Dispersion agent 0.1-0.5 part;
Defoamer 0.1-0.5 part.
2. graphene-supported nanometer Fe according to claim 1 3o 4/ aqueous polyurethane composite magnetic conductive wave-absorbing coating material, is characterized in that:
Described polymer organic resin is waterborne polyurethane resin.
3. graphene-supported nanometer Fe according to claim 2 3o 4/ aqueous polyurethane composite magnetic conductive wave-absorbing coating material, is characterized in that:
Described graphene-supported Fe 3o 4composite magnetic conductive nanoparticle is obtained by following component:
Graphite 2-3g;
Massfraction is the vitriol oil 60-120mL of 98%;
SODIUMNITRATE 1-2g;
Potassium permanganate 6-9g;
Iron trichloride 0.38-0.94g;
Ferrous sulfate 0.22-0.56g;
Volumetric molar concentration is the sodium hydroxide solution 5-15mL of 1mol/L;
Hydrazine hydrate 1-3mL;
Water 290-450mL.
4. graphene-supported nanometer Fe according to claim 3 3o 4/ aqueous polyurethane composite magnetic conductive wave-absorbing coating material, is characterized in that:
Described organic solvent is DMF, acetone or dehydrated alcohol.
5. graphene-supported nanometer Fe according to claim 4 3o 4/ aqueous polyurethane composite magnetic conductive wave-absorbing coating material, is characterized in that:
Described dispersion agent is palmityl trimethyl ammonium chloride or dodecyl sulphate diethanolamine salt.
6. graphene-supported nanometer Fe according to claim 5 3o 4/ aqueous polyurethane composite magnetic conductive wave-absorbing coating material, is characterized in that:
Described defoamer is methyl-silicone oil, siloxanes or tributyl phosphate.
7. graphene-supported nanometer Fe 3o 4the preparation method of/aqueous polyurethane composite magnetic conductive wave-absorbing coating material, is characterized in that:
Realized by following steps:
1) graphene-supported Fe 3o 4the preparation of composite magnetic conductive nanoparticle organic solution:
(1) preparation of graphene oxide:
Be the vitriol oil of 98% by 2-3g graphite, 60-120mL massfraction, the mixing of 1-2g SODIUMNITRATE is placed in ice-water bath and stirs, add 6-9g potassium permanganate again and continue reaction, at room temperature react again and add the water of 90-150mL, be oxidized thoroughly at 95-100 DEG C and obtain graphite oxide, more ultrasonic stripping high speed centrifugation obtains graphene oxide water solution;
(2) graphene-supported nanometer Fe is prepared 3o 4:
First with 200-300mL water, 40-60mL graphene oxide solution is diluted, with iron trichloride and ferrous sulfate for molysite, add iron trichloride 0.38-0.94g, ferrous sulfate 0.22-0.56g, using the 5-15mL volumetric molar concentration NaOH solution that is 1mol/L as precipitation agent, at 50-60 DEG C, react 30min; And then add 1-3mL hydrazine hydrate, react 3-5h at the temperature of 90 ± 5 DEG C after, take out naturally cooling;
(3) be separated:
After being neutrality with the separation of magnetic decantation, distilled water wash to product mixture, filtration under diminished pressure, obtains graphene-supported Fe 3o 4composite magnetic conductive nanoparticle;
(4) aftertreatment:
1) by the graphene-supported Fe of preparation 3o 4after composite magnetic conductive nanoparticle 1-10 mass parts organic solvent washing, ultrasonic disperse is in the organic solvent of 20-30 mass parts, obtains graphene-supported Fe 3o 4composite magnetic conductive nanoparticle organic solution;
2) at the graphene-supported Fe of gained 3o 4add 60-75 mass parts polymer organic resin, 0.1-0.5 mass parts dispersion agent, 0.1-0.5 mass parts defoamer in composite magnetic conductive nanoparticle organic solution, be mixed together ultrasonic disperse, high shear agitation, film obtains product.
8. graphene-supported nanometer Fe according to claim 7 3o 4the preparation method of/aqueous polyurethane composite magnetic conductive wave-absorbing coating material, is characterized in that:
In (4) of step 1), organic solvent is DMF, acetone or dehydrated alcohol;
Step 2) in, polymer organic resin is waterborne polyurethane resin, and dispersion agent is palmityl trimethyl ammonium chloride or dodecyl sulphate diethanolamine salt, and defoamer is methyl-silicone oil, siloxanes or tributyl phosphate.
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