CN115216175A - Graphite water-based dispersion liquid for water-based epoxy anticorrosive paint and preparation method thereof - Google Patents
Graphite water-based dispersion liquid for water-based epoxy anticorrosive paint and preparation method thereof Download PDFInfo
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Classifications
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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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/61—Additives non-macromolecular inorganic
-
- 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
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
-
- 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
- C09D5/08—Anti-corrosive paints
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/68—Particle size between 100-1000 nm
-
- 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
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/66—Additives characterised by particle size
- C09D7/69—Particle size larger than 1000 nm
Abstract
The invention discloses a graphene aqueous dispersion liquid for an aqueous epoxy anticorrosive paint and a preparation method thereof, and relates to the technical field of graphene material dispersion. The preparation method comprises the following steps: and adding amino graphene quantum dot powder serving as a dispersing agent into the graphene pre-wetting liquid, and uniformly dispersing to obtain the graphene aqueous dispersion liquid. According to the invention, the amino graphene quantum dots are used as the aqueous dispersing agent of graphene, the quantum dots have pi bonds and amino groups, can be well combined with graphene, can have good solubility in water, can effectively improve the dispersibility of graphene, and can not introduce non-graphene impurities into a dispersion liquid, so that the performance of the nano characteristics of graphene in the anticorrosive coating is well preserved.
Description
Technical Field
The invention relates to the technical field of graphene material dispersion, in particular to a graphite water-based dispersion liquid for a water-based epoxy anticorrosive paint and a preparation method thereof.
Background
For a long time, in order to reduce the economic loss caused by metal corrosion, people invent a plurality of anticorrosion measures, and the coating anticorrosion is widely applied due to the characteristics of simple and convenient construction, economy and applicability, no restriction of equipment area and shape, certain decorative effect and the like. In recent years, with the progress of science and technology and the development of society, people have increasingly strengthened environmental protection consciousness, and as the traditional solvent-based anticorrosive paint contains flammable and explosive toxic substances and has high content of Volatile Organic Compounds (VOC), laws and regulations for limiting VOC emission are successively made by countries around the world, and the production and sale of the solvent-based anticorrosive paint are reduced. The water-based epoxy anticorrosive paint has the advantages of high adhesion of a coating film to a base material, excellent chemical resistance, hardness and wear resistance of the coating film, good matching property with other finish paint, mainly takes water as a dispersion medium, is a safe, nontoxic and environment-friendly paint, and has become a hotspot of current research.
Graphene (Graphene) has a unique two-dimensional structure and excellent performance, and shows great potential in improving the corrosion resistance of the coating. Firstly, a physical barrier layer can be formed between metal and an active medium by a stable sp2 hybrid structure of graphene, so that diffusion and permeation are prevented; secondly, graphene has good thermal and chemical stability, and can be stable at high temperature (up to 1500 ℃), and in corrosive or oxidative gas and liquid environments. In addition, the good electric conduction and heat conduction performance of the graphene provides favorable conditions for the metal service environment. Graphene is the thinnest material so far, the influence on the base metal can be ignored, and the graphene also has high strength and good tribology performance, so that the conductivity or the salt spray resistance can be improved, the thickness of the coating can be further reduced, the adhesive force to the base material is increased, and the wear resistance of the coating is improved.
However, due to the special large pi-bond conjugated electronic structure of graphene, large van der waals force exists between the layers of graphene, so that the graphene is poor in compatibility with water, a solvent and a polymer, and the van der waals force between the layers inevitably enables the graphene sheets to be agglomerated and stacked again, so that the graphene sheets are difficult to disperse to form a stable solution. How to improve the dispersibility of the graphene in the water-based epoxy anticorrosive paint and the compatibility of the graphene with other materials has very important theoretical and practical significance.
In order to break through the bottleneck technology, graphene aqueous dispersion liquid is obtained by adopting the technologies such as graphene liquid phase stripping, graphene surface modification and dispersion and the like at the present stage. However, in the preparation processes of the technologies, a dispersion auxiliary agent (such as a surfactant, a PH regulator, a modifier and the like) is required to be added to modify graphene, and foreign non-graphene impurities are introduced into a dispersion system, so that not only is the exertion of the nano characteristics of the graphene in the anticorrosive paint prevented, but also adverse side reactions or side effects are caused in the application, and the industrial development of the graphene water-based epoxy anticorrosive paint is restricted.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a graphene aqueous dispersion liquid for an aqueous epoxy anticorrosive paint and a preparation method thereof, so as to overcome the technical problems of the prior art that the graphene is dispersed in the aqueous epoxy anticorrosive paint, foreign non-graphene impurities are introduced in the dispersion process, and the like.
The invention is realized by the following steps:
in a first aspect, the present invention provides a method for preparing an aqueous graphene dispersion, the method comprising the steps of:
and adding amino graphene quantum dot powder serving as a dispersing agent into the graphene pre-wetting liquid, and uniformly dispersing to obtain the graphene aqueous dispersion liquid.
In a second aspect, the invention provides the graphene aqueous dispersion prepared by the preparation method of the graphene aqueous dispersion.
In a third aspect, the invention provides an application of the graphene aqueous dispersion in an aqueous epoxy anticorrosive paint.
The invention has the following beneficial effects:
1. the method takes the graphene to be dispersed and the water-based epoxy curing agent as precursors and amino hydrothermal reaction modifiers to prepare the amino graphene quantum dot powder, and raw materials are locally available and are convenient and easy to obtain;
2. the graphene can be effectively pre-wetted in water by grinding through a sand mill, and the particle size of the graphene can be processed to a fineness range meeting the requirement of the coating;
3. according to the invention, the amino graphene quantum dots are used as the aqueous dispersing agent of graphene, the quantum dots have pi bonds and amino groups, can be well combined with graphene, can have good solubility in water, can effectively improve the dispersibility of graphene, and can not introduce non-graphene impurities into a dispersion liquid, so that the performance of the nano characteristics of graphene in the anticorrosive coating is well preserved.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.
Fig. 1 is a state of an aqueous graphene dispersion prepared in example 1 of the present invention after standing;
fig. 2 is a morphology of the aqueous graphene dispersion prepared in comparative example 1 of the present invention after standing;
fig. 3 is a morphology of the aqueous graphene dispersion prepared in comparative example 2 of the present invention after standing.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.
In view of the defects of the graphene-containing aqueous epoxy anticorrosive paint in the prior art, the amino graphene quantum dots are firstly used as the graphene aqueous dispersant, and the inventor creatively discovers that the amino graphene quantum dots are used as the graphene aqueous dispersant, and the quantum dots have pi bonds and amino groups, so that the amino graphene quantum dots can be well combined with graphene, have good solubility in water, can effectively improve the dispersibility of the graphene, and can not introduce non-graphene impurities into a dispersion liquid, thereby well preserving the performance of the nano characteristics of the graphene in the anticorrosive paint.
Based on this, some embodiments of the present invention provide a method for preparing an aqueous graphene dispersion, the method comprising the steps of:
and adding amino graphene quantum dot powder serving as a dispersing agent into the graphene pre-wetting liquid, and uniformly dispersing to obtain the graphene aqueous dispersion liquid.
In an alternative embodiment, the concentration of graphene in the aqueous graphene dispersion is from 5mg/ml to 100mg/ml.
In an alternative embodiment, the mass ratio of the amino graphene quantum dot powder to the graphene in the aqueous graphene dispersion is from 0.005 to 0.05.
In an alternative embodiment, the dispersing step comprises sonication, standing and high pressure homogenization; the ultrasonic treatment time is 60-480min; standing for 5-10min; the high-pressure homogenizing operation method is to homogenize for 2-4 times under the pressure of 80-120 MPa.
In an alternative embodiment, the preparation of the amino graphene quantum dot powder comprises the following steps:
preparing graphene powder to be dispersed into a graphene oxide aqueous solution, adding a water-based epoxy curing agent into the graphene oxide aqueous solution, carrying out amino hydrothermal reaction, and then carrying out separation and purification to obtain amino graphene quantum dot powder.
In an alternative embodiment, the mass ratio of the aqueous epoxy curing agent to the aqueous graphene oxide solution is 1:1-1:5.
In an alternative embodiment, the temperature of the amino hydrothermal reaction is 100-200 ℃, and the reaction time is more than or equal to 5h.
In an alternative embodiment, the method of separation and purification comprises dialysis, wherein the dialysis membrane has a molecular weight of 3000 to 8000.
In an alternative embodiment, the particle size of the aminographene quantum dot powder is 1 to 20nm.
In an alternative embodiment, the mass ratio of nitrogen atoms to carbon atoms in the aminographene quantum dot powder is 1:5-1.
In an alternative embodiment, the graphene is any one of single-layer graphene, double-layer graphene, few-layer graphene and multi-layer graphene or a combination of at least two of the single-layer graphene, the double-layer graphene and the multi-layer graphene, and the sheet diameter of the graphene is 1 μm to 150 μm;
the number of the few-layer graphene layers is 3-4, and the number of the multi-layer graphene layers is 5-10.
In an alternative embodiment, the aqueous epoxy curing agent is any one of an aqueous polyamide curing agent, an aqueous polyamide-polyamine curing agent, an aqueous polyamine-epoxy adduct curing agent, and an aqueous mannich base-epoxy adduct curing agent.
In an alternative embodiment, the preparation of the graphene pre-wetting fluid comprises the following steps: and adding water into the graphene powder, and grinding to obtain the graphene pre-wetting liquid.
In an alternative embodiment, the conditions for milling are: the grinding speed is 1000-2500rpm/min, and the stirring time is 120-480min.
In an alternative embodiment, the mass ratio of the graphene powder to water is 1:9-1.
In an alternative embodiment, the average particle size D50 of the graphene particles in the graphene pre-wetting fluid is in the range of 0.5 μm D50 3 μm.
Some embodiments of the present invention provide an aqueous graphene dispersion prepared by the above method for preparing an aqueous graphene dispersion.
Some embodiments of the invention provide application of the graphene aqueous dispersion liquid in an aqueous epoxy anticorrosive paint.
The features and properties of the present invention are described in further detail below with reference to examples.
Example 1
The embodiment provides a preparation method of a graphene aqueous dispersion liquid for an aqueous epoxy anticorrosive paint. The method comprises the following specific steps:
(1) Preparing graphene to be dispersed into a graphene oxide aqueous solution by adopting an improved Hummers method, adding a water-based polyamide curing agent into the graphene oxide aqueous solution with the mass ratio of 1:1, fully stirring to obtain a uniformly mixed dispersion, transferring the dispersion into a hydrothermal reaction kettle, carrying out amino hydrothermal reaction for 5 hours at the temperature of 100 ℃, and cooling to room temperature to obtain a tawny solution; filtering the yellowish brown solution by using a 0.02 mu m Anopore inorganic membrane to remove undissolved large particles, centrifuging at 12000rpm for 20min, dialyzing by using a dialysis membrane with the molecular weight of 3000 to obtain a supernatant, concentrating the supernatant by using a rotary evaporator, and freeze-drying to obtain amino graphene quantum dot powder with the particle size of 1-20nm, wherein the mass ratio of nitrogen atoms to carbon atoms of the amino graphene quantum dot powder is 1:5 as shown by XPS test;
(2) Adding graphene powder and water into a sanding device according to the mass ratio of 1; testing the graphene pre-wetting liquid by using a Malvern laser particle size analyzer to obtain that the average particle size D50 of graphene particles in the wetting liquid is 0.5 mu m;
(3) And (3) adding the amino graphene quantum dot powder obtained in the step (1) as a dispersing agent into the graphene pre-wetting liquid obtained in the step (2), wherein the mass ratio of the amino graphene quantum dot powder to graphene is 0.005. The aqueous graphene dispersion was allowed to stand for 6 months, and no precipitation was observed, as shown in fig. 1. And testing the dried aqueous graphene dispersion liquid by using an element analyzer to obtain the performance parameters shown in table 1.
Table 1 test results of aqueous graphene dispersions
Example 2
The embodiment provides a preparation method of a graphene aqueous dispersion for an aqueous epoxy anticorrosive paint. The method comprises the following specific steps:
(1) Preparing graphene to be dispersed into a graphene oxide aqueous solution by adopting an improved Hummers method, adding a water-based epoxy curing agent triethylene tetramine into the graphene oxide aqueous solution according to a mass ratio of 1:3, fully stirring to obtain a uniformly mixed dispersion, transferring the dispersion into a hydrothermal reaction kettle, carrying out amino hydrothermal reaction for 8 hours at the temperature of 150 ℃, and cooling to room temperature to obtain a tawny solution; filtering undissolved large particles of the tawny solution by using a 0.02 mu m Anopore inorganic membrane, centrifuging at 12000rpm for 20min, dialyzing by using a dialysis membrane with the molecular weight of 5000 to obtain a supernatant, concentrating the supernatant by using a rotary evaporator, and freeze-drying to obtain amino graphene quantum dot powder with the particle size of 1-20nm, wherein XPS (X-ray diffraction) tests show that the mass ratio of nitrogen atoms to carbon atoms of the amino graphene quantum dot powder is 1;
(2) Adding graphene powder and water into a sanding device according to the mass ratio of 1 to 99 for grinding, adjusting the sanding speed to 1800rpm, and stirring for 300min to fully wet the surface of graphene to obtain a graphene pre-wetting solution; testing the graphene pre-wetting liquid by using a Malvern laser particle size analyzer to obtain that the average particle size D50 of graphene particles in the wetting liquid is 1.5 mu m;
(3) Adding the amino graphene quantum dot powder obtained in the step (1) as a dispersing agent into the graphene pre-wetting liquid obtained in the step (2), wherein the mass ratio of the amino graphene quantum dot powder to graphene is 0.025:1, carrying out ultrasonic reaction for 270min, standing for 8min, carrying out high-pressure homogenizer treatment, and homogenizing for 3 times under the pressure of 100Mpa to obtain the graphene aqueous dispersion liquid with the concentration of 10 mg/ml. The aqueous graphene dispersion was allowed to stand for 6 months, and no precipitation was observed. And testing the dried aqueous graphene dispersion liquid by using an element analyzer to obtain the performance parameters shown in table 2.
Table 2 test results of aqueous graphene dispersions
| Element(s) | Content (wt.) |
| C | 97.48wt％ |
| N | 0.33wt％ |
| H | 0.18wt％ |
| O | 0.56wt％ |
| S | 0.50wt％ |
| Others | 0.95wt％ |
Example 3
The embodiment provides a preparation method of a graphene aqueous dispersion liquid for an aqueous epoxy anticorrosive paint. The method comprises the following specific steps:
(1) Preparing graphene to be dispersed into a graphene oxide aqueous solution by adopting an improved Hummers method, adding a phenolic aldehyde curing agent into the graphene oxide aqueous solution with the mass ratio of 1:5, fully stirring to obtain a uniformly mixed dispersion, transferring the dispersion into a hydrothermal reaction kettle, carrying out amino hydrothermal reaction for 10 hours at the temperature of 200 ℃, and cooling to room temperature to obtain a tawny solution; filtering undissolved large particles of the tawny solution by using an Anopore inorganic membrane with the particle size of 0.02 mu m, centrifuging at 12000rpm for 20min, dialyzing by using a dialysis membrane with the molecular weight of 8000 to obtain a supernatant, concentrating the supernatant by using a rotary evaporator, and freeze-drying to obtain amino graphene quantum dot powder with the particle size of 1-20nm, wherein XPS (X-ray diffraction) tests show that the mass ratio of nitrogen atoms to carbon atoms of the amino graphene quantum dot powder is 1;
(2) Adding graphene powder and water into a sanding device according to the mass ratio of 1:9 for grinding, adjusting the sanding speed to be 2500rpm, and stirring for 480min to fully wet the surface of graphene so as to obtain a graphene pre-wetting solution; testing the graphene pre-wetting liquid by using a Malvern laser particle size analyzer to obtain that the average particle size D50 of graphene particles in the wetting liquid is 3 mu m;
(3) Adding the amino graphene quantum dot powder obtained in the step (1) as a dispersing agent into the graphene pre-wetting liquid obtained in the step (2), wherein the mass ratio of the amino graphene quantum dot powder to graphene is 0.05:1, carrying out ultrasonic reaction for 480min, standing for 10min, carrying out high-pressure homogenizer treatment, and homogenizing for 4 times under the pressure of 120Mpa to obtain the graphene aqueous dispersion liquid with the concentration of 100mg/ml. The aqueous graphene dispersion was allowed to stand for 6 months, and no precipitation was observed. And testing the dried aqueous graphene dispersion liquid by using an element analyzer to obtain the performance parameters shown in table 3.
Table 3 test results of aqueous graphene dispersions
| Element(s) | Content (wt.) |
| C | 97.91wt％ |
| N | 0.52wt％ |
| H | 0.37wt％ |
| O | 0.43wt％ |
| S | 0.51wt％ |
| Others (C) | 0.26wt％ |
Comparative example 1
(1) Adding graphene powder and water into a sanding device according to the mass ratio of 1; testing the graphene pre-wetting liquid by using a Malvern laser particle size analyzer to obtain that the average particle size D50 of graphene particles in the wetting liquid is 0.5 mu m;
(2) And (2) carrying out ultrasonic reaction on the graphene pre-wetting liquid obtained in the step (1) for 60min, standing for 5min, carrying out high-pressure homogenizer treatment, and homogenizing for 2 times under the pressure of 80MPa, thereby obtaining the graphene aqueous dispersion liquid with the concentration of 5 mg/ml. The aqueous graphene dispersion was allowed to stand for about 5 days, and a precipitate was observed, as shown in fig. 2. And testing the dried aqueous graphene dispersion liquid by using an element analyzer to obtain the performance parameters shown in table 4.
Table 4 test results of aqueous graphene dispersions
| Element(s) | Content (wt.) |
| C | 97.35wt％ |
| N | 0.13wt％ |
| H | 0.63wt％ |
| O | 0.75wt％ |
| S | 0.39wt％ |
| Others (C) | 0.75wt％ |
As can be seen from table 4, the carbon content in graphene is substantially unchanged, which indicates that no non-graphene impurity is introduced, and the nitrogen content is reduced because no amino graphene quantum dots are added as a dispersant.
Comparative example 2
(1) Adding graphene powder and water into a sanding device according to the mass ratio of 1 to 99 for grinding, adjusting the sanding speed to 1800rpm, and stirring for 300min to fully wet the surface of graphene to obtain a graphene pre-wetting solution; testing the graphene pre-wetting liquid by using a Malvern laser particle size analyzer to obtain that the average particle size D50 of graphene particles in the wetting liquid is 1.5 mu m;
(2) Adding a surfactant sodium dodecyl sulfate serving as a dispersing agent into the graphene pre-wetting liquid obtained in the step (1), wherein the mass ratio of the sodium dodecyl sulfate to the graphene is 0.025:1, carrying out ultrasonic reaction for 270min, standing for 8min, carrying out high-pressure homogenizer treatment, and homogenizing for 3 times under the pressure of 100Mpa to obtain the graphene aqueous dispersion liquid with the concentration of 10 mg/ml. The aqueous graphene dispersion was allowed to stand for 6 months and the dispersion almost completely precipitated, leaving only a small portion of the suspension above, as shown in fig. 3. And testing the dried aqueous graphene dispersion liquid by using an element analyzer to obtain the performance parameters shown in table 5.
Table 5 test results of aqueous graphene dispersions
| Element(s) | Content (wt.) |
| C | 95.11wt％ |
| N | 0.10wt％ |
| H | 0.18wt％ |
| O | 2.56wt％ |
| S | 1.50wt％ |
| Others (C) | 0.55wt％ |
As is clear from table 5, the content of carbon in graphene decreases, the content of oxygen and sulfur increases, and the amount of non-graphene impurities increases.
By comparing examples 1 to 3 with comparative examples 1 to 2, in comparative example 1, the non-graphene impurity can be not introduced into the graphene aqueous dispersion liquid obtained without adding the dispersant, but the stability is poor; comparative example 2, the aqueous graphene dispersion obtained by adding the surfactant can improve the stability of the dispersion to a certain extent, but the introduced non-graphene impurities are more. The aqueous graphene dispersion liquid obtained by using the amino graphene quantum dots as the dispersing agent can keep the dispersion liquid stable for a long time on the premise of not introducing non-graphene impurities.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A preparation method of a graphene aqueous dispersion liquid is characterized by comprising the following steps:
and adding amino graphene quantum dot powder serving as a dispersing agent into the graphene pre-wetting liquid, and uniformly dispersing to obtain the graphene aqueous dispersion liquid.
2. The method according to claim 1, wherein the concentration of graphene in the aqueous graphene dispersion is 5mg/mL to 100mg/mL.
3. The preparation method according to claim 1, wherein the mass ratio of the amino graphene quantum dot powder to the graphene in the aqueous graphene dispersion is from 0.005 to 0.05.
4. The method of claim 1, wherein the dispersing step comprises sonication, standing, and high pressure homogenization;
the ultrasonic time is 60-480min; the standing time is 5-10min; the high-pressure homogenizing operation method is to homogenize for 2 to 4 times under the pressure of 80 to 120 MPa.
5. The preparation method of claim 1, wherein the preparation of the amino graphene quantum dot powder comprises the following steps:
preparing graphene powder to be dispersed into a graphene oxide aqueous solution, adding an amino-containing waterborne epoxy curing agent into the graphene oxide aqueous solution, carrying out amino hydrothermal reaction, and then carrying out separation and purification to obtain amino graphene quantum dot powder;
preferably, the mass ratio of the aqueous epoxy curing agent to the graphene oxide aqueous solution is 1:1-1:5;
preferably, the temperature of the amino hydrothermal reaction is 100-200 ℃, and the reaction time is more than or equal to 5h;
preferably, the method for separation and purification comprises dialysis, wherein the molecular weight of a dialysis membrane of the dialysis is 3000-8000;
preferably, the particle size of the amino graphene quantum dot powder is 1-20nm;
preferably, the mass ratio of nitrogen atoms to carbon atoms in the amino graphene quantum dot powder is 1:5-1.
6. The preparation method of claim 5, wherein the graphene is any one of single-layer graphene, double-layer graphene, few-layer graphene and multi-layer graphene or a combination of at least two of the single-layer graphene, the double-layer graphene and the multi-layer graphene, and the size of the sheet diameter of the graphene is 1 μm-150 μm;
the number of the few-layer graphene layers is 3-4, and the number of the multi-layer graphene layers is 5-10.
7. The method according to claim 5, wherein the aqueous epoxy curing agent is any one of an aqueous polyamide curing agent, an aqueous polyamide-polyamine curing agent, an aqueous polyamine-epoxy adduct curing agent, and an aqueous Mannich base-epoxy adduct curing agent.
8. The preparation method according to claim 1, wherein the preparation of the graphene pre-wetting solution comprises the following steps: adding water into the graphene powder, and grinding to obtain graphene pre-wetting liquid;
preferably, the conditions of the grinding are: the grinding speed is 1000-2500rpm/min, and the stirring time is 120-480min;
preferably, the mass ratio of the graphene powder to water is 1:9-1;
preferably, the average particle size D50 of the graphene particles in the graphene pre-wetting liquid is within the range of 0.5 [ mu ] m & lt/gtD 50 & lt/gt3 [ mu ] m.
9. The aqueous graphene dispersion prepared by the method for preparing an aqueous graphene dispersion according to any one of claims 1 to 8.
10. Use of the aqueous graphene dispersion according to claim 9 in an aqueous epoxy anticorrosive coating.
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