CN110041739B - Oversized graphene aqueous slurry for efficient corrosion prevention and preparation method thereof - Google Patents
Oversized graphene aqueous slurry for efficient corrosion prevention and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ultra-large graphene aqueous slurry for efficient corrosion prevention and a preparation method thereof, and the ultra-large graphene aqueous slurry for efficient corrosion prevention is prepared by reducing ultra-large graphene oxide in situ by using a reducing agent, and carrying out block copolymerization on the surface of graphene to form a water dispersible modification layer on a molecular level, wherein the mass ratio of the reducing agent to the ultra-large graphene oxide is (8-15): 1, the reducing agent is a mixture of a hydrophilic electroactive polymer monomer and a hydrophobic electroactive polymer monomer, the reducing agent is carried out in situ in a mixed solution, and the mixed solution comprises deionized water and an organic solvent. According to the super-large-size graphene water-based slurry for efficient corrosion prevention and the preparation method thereof, the prepared graphene dispersion slurry has wide applicability, is suitable for a water-based epoxy resin system, a water-based acrylic resin system and a water-based polyurethane system, and saves a large amount of cost for large-scale production.
Description
Technical Field
The invention relates to the technical field of graphene molecular level functional modification, in particular to an ultra-large graphene aqueous slurry for high-efficiency corrosion prevention and a preparation method thereof.
Background
Graphene, a novel two-dimensional material, is attracting attention because of its excellent physical and chemical properties. At present, graphene is widely applied to the fields of photoelectric devices, sensors, novel functional composite materials and energy storage. At present, the problems of poor dispersibility, easy stacking of sheets and the like easily exist in the using process of graphene, which is one of the bottlenecks limiting further industrial application of graphene. A large number of research results show that the problems of poor graphene dispersibility and easy stacking are in a certain relationship with the structure of graphene, a large number of oxygen-containing functional groups (epoxy groups, hydroxyl groups, carboxyl groups and other functional groups) and defects are easily formed on the lamellar structure of graphene in the preparation process of graphene, and interaction force is easily generated among the functional groups and the defects to cause the stacking phenomenon; however, in view of the existence of the oxygen-containing functional group of the lamellar structure, researchers remove the oxygen-containing functional group on the lamellar structure of the graphene to a certain extent by a reduction method, but easily damage the conjugated structure of the graphene in the reduction process, and simultaneously cause new defects and holes on the surface of the graphene, so that the intrinsic excellent physicochemical properties of the reduced graphene and the graphene still have great difference, and the dispersibility of the reduced graphene in the actual use process is not expected. However, most researchers have adopted a method of improving the dispersibility of graphene in water by performing a functionalization reaction such as ring opening, esterification, and amidation of an oxygen-containing functional group on the surface of a graphene lamellar structure (as described in document 1), and reducing the occurrence of stacking phenomenon between graphene by utilizing intercalation of small molecules between graphene.
The graphene is also referred to as another commercial application, namely that the graphene is compounded with a composite material to prepare a coating for metal corrosion prevention. The graphene has a unique two-dimensional honeycomb lamellar structure, a large specific surface area and excellent thermal stability and chemical stability, so that an effective physical barrier layer can be formed after the graphene is compounded with an aqueous resin system, and water vapor and corrosive media are effectively prevented from permeating. At present, the most technologies are adopted in the using process of the coating, namely, the graphene is directly added into a resin system, but the technical problems of poor graphene dispersibility and the like exist; secondly, some functionalized graphene is added into a coating system, but the added graphene is generally poor in compatibility with the system or the functionalized graphene is complicated in preparation process and increased in production cost; more importantly, a large amount of defects which cannot be repaired exist on the surface of some functionalized graphene, so that the physical barrier effect of the graphene added into the coating as an anti-corrosion coating is reduced, and the application range of the graphene is greatly limited.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides the oversized graphene aqueous slurry for efficient corrosion prevention and the preparation method thereof, and solves the problems that the physical barrier effect of graphene added into a coating as an anticorrosive coating is high, and the application range of the graphene aqueous slurry is greatly limited.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: the super-large-size graphene oxide aqueous slurry for efficient corrosion prevention is prepared by reducing super-large-size graphene oxide in situ by using a reducing agent, carrying out block copolymerization on the surface of graphene to form a water dispersible modification layer on a molecular layer, wherein the mass ratio of the reducing agent to the super-large-size graphene oxide is (8-15): 1, the reducing agent is a mixture of a hydrophilic electroactive polymer monomer and a hydrophobic electroactive polymer monomer, the reducing agent is used for reducing the super-large-size graphene oxide in situ in a mixed solution, the mixed solution comprises deionized water and an organic solvent, and the mass ratio of the deionized water to the organic solvent is 1: (0.25-3), the mass concentration of the oversized graphene oxide is 0.05-5mg/ml, the thickness of the oversized graphene oxide is 0.34-1 nm, and the sheet diameter is 20-100 microns.
Preferably, the mass ratio of the reducing agent to the oversized graphene oxide is (10-12): 1, the mass ratio of the deionized water to the organic solvent is 1: (1-2), the mass concentration of the oversized graphene oxide is preferably 1-2 mg/ml.
Preferably, the organic solvent is one or more of ethanol, methanol, propylene glycol, isopropanol, N-dimethylformamide and N, N-dimethylacetamide in any mass ratio.
Preferably, the hydrophilic monomer is one or more of m-aminobenzenesulfonic acid, sodium m-aminobenzenesulfonate, lithium m-aminobenzenesulfonate, potassium m-aminobenzenesulfonate, o-aminobenzenesulfonic acid, sodium o-aminobenzenesulfonate, lithium o-aminobenzenesulfonate, m-aminobenzeneboric acid, sodium m-aminobenzenesulfonate, potassium m-aminobenzeneborate, lithium m-aminobenzeneborate, m-aminobenzeneboric acid hydrochloride, o-aminobenzeneboric acid, sodium o-aminobenzeneborate, potassium o-aminobenzeneborate, lithium o-aminobenzeneborate, o-aminobenzeneboric acid hydrochloride, m-aminobenzenephosphoric acid, sodium m-aminophenylphosphate, potassium m-aminobenzenephosphate, lithium m-aminobenzenephosphate, o-aminobenzenephosphoric acid, sodium o-aminobenzenephosphate, potassium o-aminobenzenephosphate and lithium o-aminobenzenephosphate in any mass ratio.
Preferably, the hydrophobic monomer is one or more of aniline, pyrrole, methylaniline, ethylaniline, methylpyrrole and ethylpyrrole in any mass ratio.
A preparation method of oversized graphene water-based slurry for efficient corrosion prevention comprises the following steps:
1) weighing the oversized graphene oxide according to the mass ratio of the reducing agent to the oversized graphene oxide, and adding the oversized graphene oxide into the mixture in a mass ratio of 1: (0.25-3) ultrasonically dispersing in deionized water and an organic solvent for 30min to form a uniform graphene oxide dispersion liquid;
2) weighing a reducing agent in the formula mass according to the mass ratio of the reducing agent to the oversized graphene oxide, and adding the reducing agent into the dispersion liquid prepared in the step 1); wherein, the reducing agent comprises a hydrophilic active monomer and a hydrophobic active monomer according to a mass ratio of 1: (0.3-3), magnetically stirring the mixture to form uniform dispersion liquid;
3) transferring the uniform dispersion liquid prepared in the step 2) into a three-neck flask, and reacting at the temperature of 60-120 ℃ for 18-72 h to form a black dispersion liquid;
4) transferring the completely reacted dispersion liquid obtained in the step 3) into a sand core funnel by adopting a mass ratio of 1: 4: 1, repeatedly washing the mixed solution of acetone, deionized water and ethyl acetate;
5) and transferring the modified oversized graphene filter cake into water, and dispersing to form the oversized graphene water-based slurry for efficient corrosion prevention.
Preferably, in the step 3), the reaction temperature of reducing the oversized graphene oxide in situ by using a reducing agent is 80-95 ℃, and the reaction time is 24-36 h.
Preferably, the dispersion in the step 5) adopts any method and combination of ultrasound, high-speed stirring, grinding dispersion and the like, and the concentration of the slurry obtained in the step 5) is one thousandth to one hundredth.
(III) advantageous effects
The invention provides an oversized graphene aqueous slurry for efficient corrosion prevention and a preparation method thereof. Compared with the prior art, the invention has the following characteristics and technical advantages:
1. according to the method, a hydrophilic electrochemically active polymer monomer and a hydrophobic electrochemically active polymer monomer are selected as reducing agents to realize the reduction of the graphene oxide with the oversized size, the block copolymerization is carried out on the surface of the graphene with the oversized size in situ, and the thickness of a modified layer formed on the surface of the graphene by the copolymer is controlled by controlling the reaction temperature, the reaction time and the proportion of an organic solvent and deionized water; secondly, due to the existence of electrostatic physical adsorption and conjugation, the copolymer grows along the surface plane of the graphene to form a two-dimensional sheet layered structure; furthermore, because the molecular level hydrophilic-hydrophobic conjugated block copolymer exists on the surface of the graphene, the stacking effect between graphene layers is weakened, so that the dispersion effect of the graphene in an aqueous system is improved;
2. after the graphene surface modified molecular layer conjugated block copolymer is added into a water-based paint system, the physical shielding effect of a graphene lamellar structure can be fully utilized, the surface modified conjugated block copolymer has better conductivity, and after the graphene surface modified molecular layer conjugated block copolymer is added into the paint system, a passivation layer can be quickly formed on the metal surface in the presence of a corrosive medium, so that the corrosion resistance of the coating is further improved;
3. in the preparation process of the graphene water dispersion slurry, safe and pollution-free water, ethanol, methanol, propylene glycol, isopropanol and the like are used as reaction solvents, no additional oxidant is needed to initiate polymerization of a molecular level polymer, and high temperature and long-time reaction are not needed, so that a large amount of cost is saved for large-scale production;
4. the prepared graphene dispersion slurry has wide applicability, and is suitable for a water-based epoxy resin system, a water-based acrylic resin system and a water-based polyurethane system;
5. the coating has the advantages that a small amount of graphene dispersion slurry is added into a water-based anticorrosive coating system, SO that the anticorrosive performance, the adhesive force and the storage stability of the water-based coating can be effectively improved, the large-size graphene has a good lamellar spreading effect in a resin system after being modified by a conjugated block copolymer molecular layer, the physical barrier effect of resin can be improved, in addition, the surface of the conjugated block copolymer modified by the graphene surface is electronegative in the presence of a corrosive medium, the conjugated block copolymer is selective to ions, and can prevent Cl-, SO 42-and other anions from permeating into the coating system, SO that the barrier performance is effectively improved, wherein the surface drying time of the water-based anticorrosive coating added with the super-large-size graphene dispersion slurry is 45min, the coating is dried for 5h, the coating is not damaged in a 50cm drop hammer impact resistance test, and has a small amount of cracks in a 2mm flexibility test, the salt spray resistance can reach 4500h, the adhesive force is 6MPa, the coating does not delaminate after being placed at room temperature for 3 months, and the performance is obviously improved compared with that of the coating without the water-based anticorrosive coating.
Drawings
FIG. 1 is a scanning electron microscope image of conjugated block copolymer molecule level modified oversized graphene prepared in example 5 of the present invention;
FIG. 2 is a transmission electron microscope image of oversized graphene modified at the molecular level by a conjugated block copolymer prepared in example 5 of the invention;
FIG. 3 is a Raman spectrum of conjugated block copolymer modified at molecular level of oversized graphene prepared in example 5 of the present invention;
FIG. 4 is an X-ray photoelectron spectrum of a conjugated block copolymer modified at the molecular level of oversized graphene prepared in example 5 of the present invention;
fig. 5 is a coating polarization curve diagram of oversized graphene slurry prepared according to the proportion of examples 1, 2, 3, 4, 5 and 6 of the invention after being added into a water-based anticorrosive coating.
Detailed Description
In order to make the technical means, the creation characteristics, the achievement purposes and the effects of the invention easily understood, the invention is further described with reference to the specific embodiments.
Example 1
Weighing 0.1g of graphene oxide, adding the graphene oxide into 100mL of deionized water, and performing ultrasonic dispersion to form 1mg/mL of graphene oxide aqueous dispersion; according to the mass ratio of 1: 1, weighing hydrophilic monomer and hydrophobic monomer (the total mass of the monomers is 1g), and adding the monomers into 50mL of a mixture with the volume ratio of 1: 0.25 of deionized water and ethanol mixed solution is stirred and dissolved uniformly, transferred to graphene oxide aqueous dispersion, stirred and dispersed uniformly again, transferred to a three-neck flask, and magnetically stirred at 90 ℃ to react for 24 hours; and then repeatedly centrifuging and washing the product by using a mixed solution of acetone, deionized water and ethyl acetate (the mass ratio is 1: 4: 1), thereby obtaining the conjugated block copolymer molecule layer modified oversized graphene.
And adding the prepared oversized graphene slurry into a water-based epoxy coating, and dispersing at a high speed to form a uniform system for a standby spray plate.
The graphene slurry prepared in the embodiment is added into a water-based epoxy coating, the obtained coating is coated on a steel plate with the surface roughness reaching Sa2.5, the film thickness is controlled to be 60 micrometers, experiments and detection show that the surface drying time of the coating is 1.5h, the actual drying time is 9h, a small amount of damage is caused to the 50cm drop hammer impact resistance experiment coating, a small amount of cracks are caused in a 2mm flexibility test, a salt spray resistance experiment can reach 1500h, and the adhesive force is 2.8 MPa.
Example 2
Weighing 0.15g of graphene oxide, adding the graphene oxide into 100mL of deionized water, and performing ultrasonic dispersion to form 1.5mg/mL of graphene oxide aqueous dispersion; according to the mass ratio of 1: 3 weighing hydrophilic monomer and hydrophobic monomer (the total mass of the monomers is 1.2g), adding the mixture to 50mL of a mixture with the volume ratio of 1: 1, stirring and dissolving the mixture of deionized water and ethanol uniformly, transferring the mixture into graphene water dispersion, stirring and dispersing uniformly again, transferring the mixture into a three-neck flask, and reacting for 30 hours under the condition of 80 ℃ and magnetic stirring; and then repeatedly centrifuging and washing the product by using a mixed solution of acetone, deionized water and ethyl acetate (the mass ratio is 1: 4: 1), thereby obtaining the conjugated block copolymer molecule layer modified oversized graphene.
And adding the prepared oversized graphene slurry into a water-based epoxy coating, and dispersing at a high speed to form a uniform system for a standby spray plate.
The graphene slurry prepared in the embodiment is added into a water-based epoxy coating, the obtained coating is coated on a steel plate with the surface roughness reaching Sa2.5, the film thickness is controlled to be 60 micrometers, experiments and detection show that the surface drying time of the coating is 1.2h, the actual drying time is 7.5h, a small amount of damage is caused to the 50cm drop hammer impact resistance experiment coating, a small amount of cracks are caused in a 2mm flexibility test, a salt spray resistance experiment can reach 2200h, and the adhesive force is 3.1 MPa.
Example 3
Weighing 0.2g of graphene oxide, adding the graphene oxide into 100mL of deionized water, and performing ultrasonic dispersion to form 2mg/mL of graphene oxide aqueous dispersion; according to the mass ratio of 1: 2 weighing hydrophilic monomers and hydrophobic monomers (the total mass of the monomers is 3g), and adding the monomers into a 50mL solution with a volume ratio of 1: 2, stirring and dissolving the mixture evenly in the deionized water and ethanol mixed solution, transferring the mixture into graphene water dispersion, stirring and dispersing evenly again, transferring the mixture into a three-mouth flask, magnetically stirring the mixture at 95 ℃, and reacting for 36 hours; and then repeatedly centrifuging and washing the product by using a mixed solution of acetone, deionized water and ethyl acetate (mass ratio of 1: 4: 1), thereby obtaining the conjugated block copolymer molecule layer modified oversized graphene.
And adding the prepared oversized graphene slurry into a water-based epoxy coating, and dispersing at a high speed to form a uniform system for a standby spray plate.
The graphene slurry prepared in the embodiment is added into a water-based epoxy coating, the obtained coating is coated on a steel plate with the surface roughness reaching Sa2.5, the film thickness is controlled to be 60 micrometers, experiments and detection prove that the surface drying time of the coating is 1h, the actual drying time is 6h, the coating is not damaged in a 50cm drop hammer impact resistance experiment, no crack is generated in a 2mm flexibility test, a salt spray resistance experiment can reach 3100h, and the adhesive force is 4.6 MPa.
Example 4
Weighing 0.15g of graphene oxide, adding the graphene oxide into 100mL of deionized water, and performing ultrasonic dispersion to form 1.5mg/mL of graphene oxide aqueous dispersion; according to a molar ratio of 1: 0.3 hydrophilic monomers and hydrophobic monomers (1.8 g total mass of monomers) were weighed and added to 50mL of a 1: 3, stirring and dissolving the deionized water and ethanol mixed solution uniformly, transferring the solution into graphene water dispersion, stirring and dispersing uniformly again, transferring the solution into a three-neck flask, and reacting for 30 hours under the condition of 90 ℃ and magnetic stirring; and then repeatedly centrifuging and washing the product by using a mixed solution of acetone, deionized water and ethyl acetate (the mass ratio is 1: 4: 1), thereby obtaining the conjugated block copolymer molecule level modified oversized graphene.
And adding the prepared oversized graphene slurry into a water-based epoxy coating, and dispersing at a high speed to form a uniform system for a standby spray plate.
The graphene slurry prepared in the embodiment is added into a water-based epoxy coating, the obtained coating is coated on a steel plate with the surface roughness reaching Sa2.5, the film thickness is controlled to be 60 micrometers, the surface drying time of the coating is 1.2h, the actual drying time is 7h, the coating is not damaged in a 50cm drop hammer impact resistance experiment, no crack is generated in a 2mm flexibility test, the salt spray resistance experiment can reach 2900h, and the adhesive force is 4.1 MPa.
Example 5
(1) Weighing 0.1g of graphene oxide, adding the graphene oxide into 100mL of deionized water, and performing ultrasonic dispersion to form 1mg/mL of graphene oxide aqueous dispersion; according to a molar ratio of 1: 2, weighing a hydrophilic monomer and a hydrophobic monomer (the total mass of the monomers is 0.9g), and adding the monomers into 50mL of the mixture in a volume ratio of 1: 1, stirring and dissolving the mixture of deionized water and ethanol uniformly, transferring the mixture into graphene water dispersion, stirring and dispersing uniformly again, transferring the mixture into a three-neck flask, and reacting for 24 hours under the condition of 85 ℃ and magnetic stirring; and then repeatedly centrifuging and washing the product by using a mixed solution of acetone, deionized water and ethyl acetate (the mass ratio is 1: 4: 1), thereby obtaining the conjugated block copolymer molecule layer modified oversized graphene.
And adding the prepared oversized graphene slurry into a water-based epoxy coating, and dispersing at a high speed to form a uniform system for a standby spray plate.
The graphene slurry prepared in the embodiment is added into a water-based epoxy coating, the obtained coating is coated on a steel plate with the surface roughness reaching Sa2.5, the film thickness is controlled to be 60 micrometers, the surface drying time of the coating is 45min through experiments and detection, the actual drying time is 5h, the coating is not damaged in a 50cm drop hammer impact resistance experiment, no crack is generated in a 2mm flexibility test, the salt spray resistance experiment can reach 4500h, and the adhesive force is 6 MPa.
Example 6
(1) Weighing 0.15g of graphene oxide, adding the graphene oxide into 100mL of deionized water, and performing ultrasonic dispersion to form 1.5mg/mL of graphene oxide aqueous dispersion; according to a molar ratio of 1: 1.5 hydrophilic monomer and hydrophobic monomer (total monomer mass is 1.65g) are weighed and added into 50mL volume ratio 1: 2, stirring and dissolving the mixture evenly in a deionized water and ethanol mixed solution, transferring the mixture into a graphene aqueous dispersion, stirring and dispersing evenly again, transferring the mixture into a three-neck flask, and reacting for 30 hours under the condition of 90 ℃ and magnetic stirring; and then repeatedly centrifuging and washing the product by using a mixed solution of acetone, deionized water and ethyl acetate (the mass ratio is 1: 4: 1), thereby obtaining the conjugated block copolymer molecule level modified oversized graphene.
And adding the prepared oversized graphene slurry into a water-based epoxy coating, and dispersing at a high speed to form a uniform system for a standby spray plate.
The graphene slurry prepared in the embodiment is added into a water-based epoxy coating, the obtained coating is coated on a steel plate with the surface roughness reaching Sa2.5, the film thickness is controlled to be 60 micrometers, the surface drying time of the coating is 1.5min through experiments and detection, the actual drying time is 7h, the coating is not damaged in a 50cm drop hammer impact resistance experiment, a small amount of cracks exist in a 2mm flexibility test, the salt spray resistance experiment can reach 3500h, and the adhesive force is 4.8 MPa.
Comparative example
The aqueous epoxy coating used in the above examples was used for comparison, and the oversized graphene dispersion paste was not added for comparison.
The coating obtained in the embodiment is coated on a steel plate with the surface roughness reaching Sa2.5, the film thickness is controlled to be 60 micrometers, and experiments and detection show that the surface drying time of the coating is 2 hours, the actual drying time is 8 hours, 50cm drop hammer impact resistance shows that the coating is damaged, 2mm flexibility tests show that cracks exist, a salt spray resistance test shows that 1500 hours exist, and the adhesive force is 3.2 MPa.
The foregoing shows and describes the general principles and broad features of the present invention and advantages thereof. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are given by way of illustration of the principles of the present invention, and that various changes and modifications may be made without departing from the spirit and scope of the invention as defined by the appended claims. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (5)
1. The utility model provides a high-efficient anticorrosive super large size graphite alkene aqueous slurry which characterized in that: reducing oversized graphene oxide in situ by using a reducing agent, and carrying out block copolymerization on the surface of the graphene to form a water dispersible modification layer on a molecular layer, wherein the mass ratio of the reducing agent to the oversized graphene oxide is (8-15): 1, the reducing agent is a mixture of a hydrophilic electroactive polymer monomer and a hydrophobic electroactive polymer monomer, the reducing agent is carried out in situ reduction of the oversized graphene oxide in a mixed solution, the mixed solution comprises deionized water and an organic solvent, and the mass ratio of the deionized water to the organic solvent is 1: (0.25-3), the mass concentration of the oversized graphene oxide is 0.05-5mg/ml, the thickness of the oversized graphene oxide is 0.34-1 nm, and the sheet diameter is 20-100 microns;
the preparation method of the oversized graphene aqueous slurry for efficient corrosion prevention comprises the following steps:
1) weighing the oversized graphene oxide according to the mass ratio of the reducing agent to the oversized graphene oxide, and adding the oversized graphene oxide into the mixture in a mass ratio of 1: (0.25-3) ultrasonically dispersing in deionized water and an organic solvent for 30min to form a uniform graphene oxide dispersion liquid;
2) weighing a reducing agent in the formula mass according to the mass ratio of the reducing agent to the oversized graphene oxide, and adding the reducing agent into the dispersion liquid prepared in the step 1); wherein, in the reducing agent, the mass ratio of the hydrophilic electroactive polymer monomer to the hydrophobic electroactive polymer monomer is 1: (0.3-3), magnetically stirring the mixture to form uniform dispersion liquid;
3) transferring the uniform dispersion liquid prepared in the step 2) into a three-neck flask, and reacting at the temperature of 60-120 ℃ for 18-72 h to form a black dispersion liquid;
4) transferring the completely reacted dispersion liquid obtained in the step 3) into a sand core funnel by adopting a mass ratio of 1: 4: 1, repeatedly washing the mixed solution of acetone, deionized water and ethyl acetate;
5) transferring the modified oversized graphene filter cake into water, and dispersing to form oversized graphene water-based slurry for efficient corrosion prevention;
the hydrophilic electroactive polymer monomer is one or more of m-aminobenzene sulfonic acid, sodium m-aminobenzene sulfonate, lithium m-aminobenzene sulfonate, potassium m-aminobenzene sulfonate, o-aminobenzene sulfonic acid, sodium o-aminobenzene sulfonate, lithium o-aminobenzene sulfonate, potassium o-aminobenzene sulfonate, m-aminobenzene boric acid, sodium m-aminobenzene borate, potassium m-aminobenzene borate, lithium m-aminobenzene borate hydrochloride, o-aminobenzene boric acid, sodium o-aminobenzene borate, potassium o-aminobenzene borate, lithium o-aminobenzene borate, hydrochloride o-aminobenzene boric acid, m-aminobenzene phosphoric acid, sodium m-aminobenzene phosphate, potassium m-aminobenzene phosphate, lithium m-aminobenzene phosphate, o-aminobenzene phosphoric acid, sodium o-aminobenzene phosphate, potassium o-aminobenzene phosphate and lithium o-aminobenzene phosphate in any mass ratio;
the hydrophobic electroactive polymer monomer is one or more of aniline, pyrrole, methylaniline, ethylaniline, methylpyrrole and ethylpyrrole in any mass ratio.
2. The aqueous slurry of oversized graphene for efficient corrosion prevention according to claim 1, wherein: the mass ratio of the reducing agent to the oversized graphene oxide is (10-12): 1, the mass ratio of the deionized water to the organic solvent is 1: (1-2), wherein the mass concentration of the oversized graphene oxide is 1-2 mg/ml.
3. The aqueous slurry of oversized graphene for efficient corrosion prevention according to claim 1, wherein: the organic solvent is one or more of ethanol, methanol, propylene glycol, isopropanol, N-dimethylformamide and N, N-dimethylacetamide in any mass ratio.
4. The aqueous slurry of oversized graphene for efficient corrosion prevention according to claim 1, wherein: the reaction temperature of reducing the oversized graphene oxide in situ by the reducing agent in the step 3) is 80-95 ℃, and the reaction time is 24-36 h.
5. The aqueous slurry of oversized graphene for efficient corrosion prevention according to claim 4, wherein: the dispersion in the step 5) adopts any combination of ultrasonic, high-speed stirring and grinding dispersion, and the concentration of the slurry obtained in the step 5) is one thousandth to one hundredth.
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| CN102275902A (en) * | 2010-06-12 | 2011-12-14 | 中国科学院金属研究所 | Method for preparing graphene material by reducing graphene oxide |
| CN103390511A (en) * | 2013-07-30 | 2013-11-13 | 河海大学 | Preparation method for graphene oxide/polypyrrole composite material of lamellar microstructure |
| CN106496552A (en) * | 2016-11-10 | 2017-03-15 | 过冬 | A kind of preparation method of the poly- aminobenzenesulfonic acid of ternary nano composite material Graphene polyaniline |
| CN108441077A (en) * | 2018-04-17 | 2018-08-24 | 常州市润金木环保科技有限公司 | Aqueous heavy anti-corrosion paint and preparation method thereof |
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