CN109294317B - Preparation method of bifunctional ligand dispersed graphene for coating - Google Patents
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- 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
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- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
- C09D163/10—Epoxy resins modified by unsaturated compounds
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- 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
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Abstract
The invention relates to the field of preparation of dispersed graphene, in particular to a preparation method of bifunctional ligand dispersed graphene for a coating, which comprises the following steps: (1) mixing an oxide and a bifunctional ligand in a pigment or a filler used in the coating in a solvent, and adding graphene while stirring by a magnetic stirrer to obtain a mixed solution; (2) continuously stirring the mixed solution obtained in the step (1) for 1-3 hours, centrifuging and drying to obtain oxide-graphene; (3) and (3) adding the oxide-graphene prepared in the step (2) into a liquid to be used, dispersing by using a high-speed stirrer, and then adding resin to obtain a coating application system with highly dispersed graphene.
Description
Technical Field
The invention relates to the field of preparation of dispersed graphene, in particular to a preparation method of bifunctional ligand dispersed graphene for a coating.
Background
Graphene is an important new material, and has attractive application prospects in the fields of energy sources, transparent conductive materials, field emission devices, gas sensors, lithium ion batteries, solar batteries, catalysis and corrosion prevention due to the excellent two-dimensional structure and semiconductor structure of the graphene after being mixed with oxides, but due to the property of easy agglomeration, the graphene causes too much addition amount, weakened performance and the like during use. Therefore, the method for improving the dispersion degree of the graphene in the oxide has important significance.
Due to the characteristic that two-dimensional materials are easy to cause lamination agglomeration, research and research in the industry are continuously carried out to improve the dispersion of graphene in oxides, but the adopted means are relatively complex and are limited by the characteristic that water has larger polarity, and the dispersion of graphene in a water phase is a well-known problem. For example, patent documents CN201611089238.1, CN201610858709.4, and CN201710572790.4 adopt the technical means of the surfactant, but when such dispersing means is adopted, there is no chemical bond acting force between the dispersant and the oxide and graphene, and the dispersion of graphene is not easy to control; in the prior art, silane coupling agents are also used as connecting agents (d.yu, et.al.surf.coat.technol.2017,326, 207-215). although graphene and oxide are chemically bonded, due to the limitation of easy hydrolysis performance of the silane coupling agents, the graphene and oxide can only be applied in non-aqueous systems, and the application limitation is also caused, such as the limitation of application in aqueous coatings.
Therefore, the technical problem that the simple method for improving the dispersion degree of the graphene in the coating is still a technical problem in the prior art can be found, and particularly, no method suitable for a water-phase environment-friendly system exists.
Disclosure of Invention
Therefore, aiming at the above content, the invention provides a preparation method of bifunctional ligand dispersed graphene for coating, which solves the defects that the technical means for improving the dispersibility of graphene in oxide in the prior art is complex and is not suitable for an aqueous phase system.
In order to achieve the purpose, the invention is realized by the following technical scheme:
a preparation method of bifunctional ligand dispersed graphene for a coating comprises the following steps:
(1) mixing an oxide and a bifunctional ligand in a pigment or a filler used in the coating in a solvent, adding graphene while stirring by a magnetic stirrer to obtain a mixed solution, controlling the rotating speed of the magnetic stirrer to be 500-800 rpm, the temperature to be 10-50 ℃, and the stirring time to be 10-30 minutes, wherein the molar ratio of the oxide to the bifunctional ligand to the graphene is 10:1:0.05-10:50:5, wherein the total molar concentration of the oxide, the bifunctional ligand and the graphene is 0.001-2 mol/L, and the graphene is prepared by an oxidation-reduction method or a combustion method and contains carbon-oxygen bond defects;
(2) continuously stirring the mixed solution obtained in the step (1) for 1-3 hours at the rotating speed of 500-;
(3) and (3) adding the oxide-graphene prepared in the step (2) into the liquid to be used, dispersing by using a high-speed stirrer, wherein the rotating speed of the high-speed stirrer is 1500-.
The further improvement is that the functional group in the bifunctional ligand is one or two of amino, carboxylic acid group, sulfate radical, phosphate radical and Schiff base. The further improvement is that the bifunctional ligand is para aminobenzoic acid or terephthalic acid or lysine.
The further improvement is that the oxide is any one of silicon dioxide, titanium dioxide, cerium dioxide and ferric oxide.
The further improvement is that the solvent is any one of water, ethanol, isopropanol and dimethyl sulfoxide.
By adopting the technical scheme, the invention has the beneficial effects that:
1. the method has the advantages that the bifunctional ligand is adopted to disperse the graphene in the oxide, the process route is simple and convenient, the energy consumption is low, the yield is high, and the macro preparation of the graphene with different proportions can be realized.
2. The graphene can be used in a water phase system, the prepared graphene dispersion system is stable, and the dispersion degree of the graphene can be easily improved by introducing a bifunctional ligand.
3. The prepared graphene-oxide dispersion system has excellent performance, and can effectively improve the corrosion resistance of the material after being used for epoxy acrylic acid water-based paint.
Drawings
Fig. 1 is a field emission scanning electron micrograph of the silica-graphene dispersion prepared in example 1;
fig. 2 is a photograph of the silica-graphene dispersion prepared in example 2 after centrifugation;
fig. 3 is a photograph of the titanium dioxide-graphene dispersion prepared in example 3 after centrifugation;
fig. 4 is a field emission scanning electron micrograph of the silica-graphene dispersion prepared in example 4;
fig. 5 is a polarization graph of silica-graphene dispersions prepared in example 5 and comparative example;
fig. 6 is a field emission scanning electron micrograph of the iron oxide-graphene dispersion prepared in example 6;
fig. 7 is a photograph of a silica-graphene prepared in comparative example after centrifugation;
FIG. 8 is a schematic view of the preparation flow of example 1 and comparative example.
Detailed Description
The following detailed description will be provided for the embodiments of the present invention with reference to specific embodiments, so that how to apply the technical means to solve the technical problems and achieve the technical effects can be fully understood and implemented.
Unless otherwise indicated, the techniques employed in the examples are conventional and well known to those skilled in the art, and the reagents and products employed are also commercially available. The source, trade name and if necessary the constituents of the reagents used are indicated at the first appearance.
Example 1
Referring to fig. 8, a method for preparing bifunctional ligand dispersed graphene for coating includes the following steps:
(1) taking 11050 liters of pure water as a solvent, sequentially adding 10 moles of silicon dioxide and 1 mole of para aminobenzoic acid under the condition of magnetic stirring, stirring for 10 minutes by using a magnetic stirrer, and adding 0.05 mole of graphene in the stirring process to obtain a mixed solution, wherein the rotating speed of the magnetic stirrer is 800 revolutions per minute, and the temperature is 10 ℃; the graphene is prepared by an oxidation-reduction method and contains carbon-oxygen bond defects;
(2) stirring the mixed solution obtained in the step (1) for 3 hours at the rotating speed of a magnetic stirrer of 500 revolutions per minute and at the temperature of 10 ℃, centrifuging and drying to obtain silicon dioxide-graphene, wherein the centrifuging speed is 5000 revolutions per minute, the centrifuging time is 10 minutes, centrifuging is carried out for three times, and the silicon dioxide-graphene obtained is washed by pure water between two centrifuging operations at intervals, the drying temperature is 120 ℃, and the drying time is 12 hours; the oxide-graphene is a composite which apparently has no delamination phenomenon;
(3) and (3) adding the silicon dioxide-graphene prepared in the step (2) into a liquid to be used, dispersing by using a high-speed stirrer, wherein the rotating speed of the high-speed stirrer is 1500 rpm, and then adding resin to obtain a coating application system with highly dispersed graphene.
Referring to fig. 1, it can be seen that graphene is uniformly dispersed on the surface of silica, and there is no significant agglomeration of graphene.
Example 2
A preparation method of bifunctional ligand dispersed graphene for a coating comprises the following steps:
(1) taking 65 liters of ethanol as a solvent, sequentially adding 10 moles of silicon dioxide and 50 moles of lysine under the condition of magnetic stirring, stirring for 20 minutes by using a magnetic stirrer, and adding 5 moles of graphene during the stirring process to obtain a mixed solution, wherein the rotating speed of the magnetic stirrer is 600 revolutions per minute, and the temperature is 25 ℃; the graphene is prepared by a combustion method and contains carbon-oxygen bond defects;
(2) stirring the mixed solution obtained in the step (1) for 2 hours at the rotating speed of a magnetic stirrer of 600 revolutions per minute and at the temperature of 25 ℃, performing centrifugal operation at the centrifugal speed of 8000 revolutions per minute and the centrifugal time of 8 minutes for three times, washing the obtained oxide-graphene with pure water between every two centrifugal operations, and then drying the oxide-graphene to obtain the oxide-graphene, wherein the drying temperature is 50 ℃ and the drying time is 36 hours;
(3) and (3) adding the oxide-graphene prepared in the step (2) into a liquid to be used, dispersing by using a high-speed stirrer, wherein the rotating speed of the high-speed stirrer is 1800 rpm, and then adding resin to obtain a coating application system with highly dispersed graphene.
Referring to fig. 2, it can be seen that the apparent graphene is not delaminated and is uniformly dispersed on the surface of the silica.
Example 3
A preparation method of bifunctional ligand dispersed graphene for a coating comprises the following steps:
(1) taking 320 liters of pure water as a solvent, sequentially adding 10 moles of titanium dioxide and 20 moles of para aminobenzoic acid under the condition of magnetic stirring, stirring for 5 minutes by using a magnetic stirrer, and adding 2 moles of graphene during the stirring process to obtain a mixed solution, wherein the rotating speed of the magnetic stirrer is 800 revolutions per minute, and the temperature is 50 ℃; the graphene is prepared by an oxidation-reduction method and contains carbon-oxygen bond defects;
(2) stirring the mixed solution obtained in the step (1) for 1 hour, carrying out centrifugal operation at the rotating speed of a magnetic stirrer of 800 revolutions per minute and the temperature of 50 ℃, wherein the centrifugal speed is 10000 revolutions per minute, the centrifugal time is 10 minutes, centrifuging is carried out for three times, washing the obtained titanium dioxide-graphene with pure water between two centrifugal operations at intervals, and then drying to obtain the titanium dioxide-graphene, wherein the drying temperature is 80 ℃, and the drying time is 15 hours;
(3) and (3) adding the titanium dioxide-graphene prepared in the step (2) into a liquid to be used, dispersing by using a high-speed stirrer, wherein the rotating speed of the high-speed stirrer is 1800 rpm, and then adding resin to obtain a coating application system with highly dispersed graphene.
Referring to fig. 3, it can be seen that the apparent graphene is not delaminated and is uniformly dispersed on the surface of the titanium dioxide.
Example 4
A preparation method of bifunctional ligand dispersed graphene for a coating comprises the following steps:
(1) taking 1000 liters of ethanol as a solvent, sequentially adding 10 moles of silicon dioxide and 10 moles of lysine under the condition of magnetic stirring, stirring for 10 minutes by using a magnetic stirrer, and adding 1 mole of graphene during the stirring process to obtain a mixed solution, wherein the rotating speed of the magnetic stirrer is 600 revolutions per minute, and the temperature is 25 ℃; the graphene is prepared by a combustion method and contains carbon-oxygen bond defects
(2) Stirring the mixed solution obtained in the step (1) for 2 hours at the rotating speed of a magnetic stirrer of 600 revolutions per minute and at the temperature of 25 ℃, performing centrifugal operation at the centrifugal speed of 5000 revolutions per minute and the centrifugal time of 10 minutes for three times, washing the obtained silicon dioxide-graphene with pure water between every two centrifugal operations, and then drying the silicon dioxide-graphene to obtain the silicon dioxide-graphene, wherein the drying temperature is 100 ℃, and the drying time is 20 hours;
(3) and (3) adding the silicon dioxide-graphene prepared in the step (2) into a liquid to be used, dispersing by using a high-speed stirrer, wherein the rotating speed of the high-speed stirrer is 2000 rpm, and then adding resin to obtain a coating application system with highly dispersed graphene.
Referring to fig. 4, it can be seen that graphene is uniformly dispersed on the surface of silica without the occurrence of bulk agglomeration.
Example 5
A preparation method of bifunctional ligand dispersed graphene for a coating comprises the following steps:
(1) taking 27 liters of isopropanol as a solvent, sequentially adding 10 moles of silicon dioxide and 40 moles of para aminobenzoic acid under the condition of magnetic stirring, stirring for 10 minutes by using a magnetic stirrer, and adding 4 moles of graphene during the stirring process to obtain a mixed solution, wherein the rotating speed of the magnetic stirrer is 800 revolutions per minute, and the temperature is 25 ℃; the graphene is prepared by a combustion method and contains carbon-oxygen bond defects;
(2) stirring the mixed solution obtained in the step (1) for 2 hours, carrying out centrifugal operation at the rotating speed of a magnetic stirrer of 800 revolutions per minute and the temperature of 25 ℃, wherein the centrifugal speed is 5000 revolutions per minute, the centrifugal time is 10 minutes, centrifuging is carried out for three times, washing the obtained silicon dioxide-graphene with pure water between every two centrifugal operations, and then drying to obtain the silicon dioxide-graphene, wherein the drying temperature is 110 ℃, and the drying time is 13 hours;
(3) 0.5g of the prepared silicon dioxide-graphene composite is dispersed into 10ml of pure water, then 40ml of epoxy acrylic emulsion is added, and a paint film is prepared after high-speed dispersion and stirring at 2000 rpm, so that a uniformly dispersed graphene modified coating film can be obtained.
Referring to fig. 5, which includes polarization curves of low carbon steel, pure resin, and the silica-graphene coating film prepared in example 5, it can be seen that the corrosion resistance of the oxide-graphene coating material modified with bifunctional groups is greatly improved, and it can be seen that the corrosion resistance of the oxide-graphene coating material modified with bifunctional groups is greatly improved.
Example 6
A preparation method of bifunctional ligand dispersed graphene for a coating comprises the following steps:
(1) taking 31.25 liters of pure water as a solvent, sequentially adding 10 moles of ferric oxide and 25 moles of p-acetamidobenzoic acid under the condition of magnetic stirring, stirring for 10 minutes by using a magnetic stirrer, and adding 2.5 moles of graphene during the stirring process to obtain a mixed solution, wherein the rotating speed of the magnetic stirrer is 800 revolutions per minute, and the temperature is 40 ℃; the graphene is prepared by an oxidation-reduction method and contains carbon-oxygen bond defects;
(2) stirring the mixed solution obtained in the step (1) for 2 hours, carrying out centrifugal operation at the rotating speed of a magnetic stirrer of 800 revolutions per minute and the temperature of 40 ℃, wherein the centrifugal speed is 5000 revolutions per minute, the centrifugal time is 10 minutes, centrifuging is carried out for three times, washing the obtained iron oxide-graphene by pure water between every two centrifugal operations, and then drying to obtain the iron oxide-graphene, wherein the drying temperature is 110 ℃, and the drying time is 13 hours;
(3) and (3) adding the iron oxide-graphene prepared in the step (2) into a liquid to be used, dispersing by using a high-speed stirrer, wherein the rotating speed of the high-speed stirrer is 2000 rpm, and then adding resin to obtain a coating application system with highly dispersed graphene.
Referring to fig. 6, it can be seen that graphene is uniformly dispersed on the surface of iron oxide, and no bulk agglomeration occurs.
Comparative example
(1) Taking 27 liters of isopropanol as a solvent, adding 10 moles of silicon dioxide under the condition of magnetic stirring, stirring for 10 minutes by using a magnetic stirrer, and adding 4 moles of graphene during the stirring process to obtain a mixed solution, wherein the rotating speed of the magnetic stirrer is 800 revolutions per minute, and the temperature is 25 ℃; the graphene is prepared by a combustion method and contains carbon-oxygen bond defects;
(2) stirring the mixed solution obtained in the step (1) for 2 hours, carrying out centrifugal operation at the rotating speed of a magnetic stirrer of 800 revolutions per minute and the temperature of 25 ℃, wherein the centrifugal speed is 5000 revolutions per minute, the centrifugal time is 10 minutes, centrifuging is carried out for three times, washing the obtained silicon dioxide-graphene with pure water between every two centrifugal operations, and then drying to obtain the silicon dioxide-graphene, wherein the drying temperature is 110 ℃, and the drying time is 13 hours;
(3) 0.5g of the prepared silicon dioxide-graphene composite is dispersed into 10ml of pure water, then 40ml of epoxy acrylic emulsion is added, and a paint film is prepared after high-speed dispersion and stirring at 2000 rpm, so that a graphene modified coating film can be obtained. Referring to fig. 5, which contains a polarization curve of a coating prepared from the silica-graphene prepared in the comparative example, it can be seen that the oxide-graphene coating not modified with bifunctional groups has general corrosion prevention performance. Referring to fig. 7, it can be seen that graphene is delaminated from silica, and by comparing fig. 2, fig. 3 and fig. 7, it can be demonstrated that the introduction of bifunctional ligands improves the dispersion degree of graphene.
According to the invention, a bifunctional ligand is innovatively introduced into a graphene dispersion system, two functional groups in the bifunctional ligand are respectively bonded with an oxide and graphene to form a high-dispersity and high-stability compound, the agglomeration degree of graphene is reduced, and the purpose of improving the dispersion degree of graphene in the oxide is further realized.
The above description is only an embodiment utilizing the technical content of the present disclosure, and any modification and variation made by those skilled in the art can be covered by the claims of the present disclosure, and not limited to the embodiments disclosed.
Claims (2)
1. A preparation method of bifunctional ligand dispersed graphene for coating is characterized by comprising the following steps: comprises the following steps:
(1) mixing the oxide and bifunctional ligand in the pigment or filler used in the coating in a solvent, adding graphene while stirring by a magnetic stirrer to obtain a mixed solution, controlling the rotating speed of the magnetic stirrer to be 500-800 rpm, the temperature to be 10-50 ℃, the stirring time to be 10-30 minutes, the bifunctional ligand is p-aminobenzoic acid or terephthalic acid or lysine, the oxide is any one of silicon dioxide, titanium dioxide, cerium dioxide and ferric oxide, the molar ratio of the oxide to the bifunctional ligand to the graphene is 10:1:0.05-10:50:5, the total molar concentration of the oxide, the bifunctional ligand and the graphene is 0.001-2 mol/L, the graphene is prepared by an oxidation-reduction method or a combustion method and contains carbon-oxygen bond defects;
(2) continuously stirring the mixed solution obtained in the step (1) for 1-3 hours at the rotating speed of 500-;
(3) and (3) adding the oxide-graphene prepared in the step (2) into liquid to be used, dispersing by using a high-speed stirrer, wherein the rotating speed of the high-speed stirrer is 1500-.
2. The method for preparing bifunctional ligand-dispersed graphene for coating according to claim 1, wherein: the solvent is any one of water, ethanol, isopropanol and dimethyl sulfoxide.
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| CN105399987A (en) * | 2015-09-24 | 2016-03-16 | 上海大学 | Surface-modified silica/oxidized graphene nanocomposite and preparation method thereof |
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| CN105385310A (en) * | 2016-01-04 | 2016-03-09 | 沈阳顺风实业集团有限公司 | Steel structure fireproof anticorrosion function integrated coating and preparing method thereof |
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