A modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared by ultrasonic rapid synthesis and a preparation method thereof

Abstract

The application discloses a modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared through ultrasonic rapid synthesis and a preparation method thereof, and relates to the technical field of coatings. Modified graphene is added into a solvent, a dispersing agent and a coupling agent are added into the solvent, and the modified graphene dispersion is obtained through ultrasonic stirring; modified epoxy resin and fillers are added into the modified graphene dispersion, and the mixed solution is obtained through ultrasonic stirring; the curing agent is added dropwise into the mixed solution, and the modified graphene super-hydrophobic self-cleaning anticorrosive coating is prepared through ultrasonic stirring treatment. Through the method of ultrasonic rapid synthesis, the chemical reaction of the modified graphene, the modified epoxy resin with a special structure and the fillers and the coupling agent in the same solvent system is promoted, so that they are compounded together, and the modified graphene super-hydrophobic self-cleaning anticorrosive coating with excellent performance is obtained.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of coatings, in particular to a modified graphene super-hydrophobic self-cleaning anti-corrosion coating prepared by ultrasonic rapid synthesis and a preparation method thereof. BACKGROUND

[0002] With the rapid development of modern industry, various metal structures, building facilities and outdoor equipment are facing increasingly severe corrosion problems. Corrosion not only shortens the service life of materials and equipment, reduces their performance, but also may cause safety hazards and cause huge economic losses. Traditional anti-corrosion coatings such as alkyd paint and epoxy paint can protect to some extent, but they have many limitations, especially in terms of hydrophobicity, self-cleaning performance and corrosion resistance.

[0003] Graphene, as a new type of two-dimensional carbon nanomaterial, has excellent mechanical properties, high electrical conductivity, good chemical stability and many other advantages, which brings new opportunities for the improvement of coating performance. However, unmodified graphene has poor dispersibility in coatings and tends to agglomerate, which not only limits its own performance, but also affects the uniformity and stability of the overall coating. In addition, the conventional preparation method of graphene coating is often complex and time-consuming, which is difficult to meet the needs of large-scale industrial production.

[0004] Chinese patent application with publication number CN111234696 A discloses a super-hydrophobic conductive anti-corrosion graphene coating and a preparation method thereof. The super-hydrophobic conductive anti-corrosion graphene coating is composed of synthetic resin, modified graphene nanosheet, additives, solvent and curing agent, etc. The preparation method comprises: first, modifying the graphene nanosheet with a fluorine-containing silicon compound; then adding the modified graphene nanosheet to the synthetic resin, additives and solvent, and cooperating with the curing agent to form the super-hydrophobic conductive anti-corrosion graphene coating. The super-hydrophobic conductive anti-corrosion graphene coating prepared by the invention has good super-hydrophobicity, conductivity, corrosion resistance and storage stability, and is not prone to sinking, which can realize large-area construction. However, the preparation period of the super-hydrophobic conductive anti-corrosion graphene coating is long, and other properties still have room for improvement.

[0005] In summary, there is an urgent need to develop a modified graphene coating with super-hydrophobic self-cleaning and excellent anti-corrosion performance prepared quickly and efficiently, and a preparation method thereof, to meet the needs of modern industry and daily life for high-performance protective materials. SUMMARY

[0006] In view of the deficiencies of the prior art, the application provides a modified graphene super-hydrophobic self-cleaning anticorrosive coating rapidly synthesized by ultrasonic waves and a preparation method thereof.Modified graphene, modified epoxy resin and fillers are chemically reacted with a coupling agent under ultrasonic waves to be compounded together, so that the modified graphene super-hydrophobic self-cleaning anticorrosive coating is further prepared.The modified graphene super-hydrophobic self-cleaning anticorrosive coating is rapidly and efficiently synthesized under ultrasonic waves, has excellent performance, and has wide application prospect and market value.

[0007] To achieve the above object, the application adopts the following technical solutions:

[0008] In a first aspect, the application provides a modified graphene super-hydrophobic self-cleaning anticorrosive coating rapidly synthesized by ultrasonic waves, which comprises modified graphene, modified epoxy resin, a solvent, fillers, a dispersing agent, a coupling agent and a curing agent.

[0009]

[0010] wherein n is an integer between 1 and 5; the modified graphene, the modified epoxy resin and the fillers are chemically reacted with the coupling agent under ultrasonic waves to be compounded together.

[0011] In a second aspect, the application provides a preparation method of the modified graphene super-hydrophobic self-cleaning anticorrosive coating rapidly synthesized by ultrasonic waves, which comprises the following steps:

[0012] Firstly, the modified graphene is added into the solvent, and the dispersing agent and the coupling agent are added into the solvent, and the mixture is treated by ultrasonic waves and stirring at a first set frequency for a first set time to obtain a modified graphene dispersion liquid;

[0013] Then, the modified epoxy resin and the fillers are added into the modified graphene dispersion liquid, and the mixture is treated by ultrasonic waves and stirring at a second set frequency for a second set time to obtain a mixed liquid;

[0014] Finally, the curing agent is added dropwise into the mixed liquid, and the mixture is treated by ultrasonic waves and stirring at a third set frequency for a third set time, so that the modified graphene super-hydrophobic self-cleaning anticorrosive coating is prepared.

[0015] Beneficial technical effects:

[0016] In the present application, the modified epoxy resin with special structure has fluorine-containing groups and epoxy groups, the epoxy groups participate in the chemical reaction between the modified graphene, fillers and coupling agents, and each component is compounded and crosslinked with each other, so that the corrosion resistance is significantly improved, and the fluorine-containing groups are reserved. In the modified graphene super-hydrophobic self-cleaning anti-corrosion coating obtained after compounding of each component, the reserved fluorine-containing groups have very low surface energy, which significantly reduces the surface energy of the coating and achieves the super-hydrophobic effect. At the same time, the nano-titanium dioxide and nano-zinc oxide in the fillers generate superoxide radicals under light, which can decompose organic pollutants on the surface of the coating to achieve self-cleaning effect.

[0017] In addition, by utilizing the phenomenon that ultrasonic waves produce micro-bubbles when propagating in a liquid, and the bubbles release a huge amount of energy when breaking, forming a local transient high-temperature and high-impact environment, the chemical reaction of the modified graphene, the modified epoxy resin with special structure and the fillers and the coupling agents in the same solvent system is promoted, so that they are compounded together, and finally the modified graphene super-hydrophobic self-cleaning anti-corrosion coating with excellent performance is obtained.

[0018] The modified graphene super-hydrophobic self-cleaning anti-corrosion coating prepared in the present application uses ultrasonic waves in the whole preparation process, the reaction conditions are very mild, the preparation process is very simple, the synthesis process is rapid and efficient, and has a broad application prospect. BRIEF DESCRIPTION OF DRAWINGS

[0019] Figure 1 is a chemical reaction schematic diagram for preparing the modified graphene super-hydrophobic self-cleaning anti-corrosion coating.

[0020] Figure 2 is a flowchart schematic diagram for preparing the modified graphene super-hydrophobic self-cleaning anti-corrosion coating. DETAILED DESCRIPTION

[0021] In order to make the technical problems, technical solutions and beneficial effects of the present application more clear and explicit, the present application will be further described in detail below in conjunction with the embodiments. However, this should not be understood as limiting the scope of the present application to the following examples. Without departing from the method idea of the present application, all other embodiments obtained by those skilled in the art without making creative efforts, fall within the scope of protection of the present application.

[0022] In the present application, the terms used in the present application are merely for the purpose of describing specific embodiments, and are not intended to limit the present application.

[0023] In the present application, the singular forms "is", "a" and "the" are intended to include the plural forms, unless the context clearly indicates otherwise.

[0024] In addition, if the terms "first", "second" appear, they are used only for descriptive purposes and cannot be understood as indicating or implying relative importance.

[0025] In a first aspect, the application provides a modified graphene ultrasonic rapid synthesis super-hydrophobic self-cleaning anti-corrosion coating, comprising modified graphene, modified epoxy resin, solvent, filler, dispersant, coupling agent and curing agent; the modified graphene comprises at least one of graphene oxide and reduced graphene oxide; the structure of the modified epoxy resin comprises:

[0026]

[0027] Wherein, n is an integer between 1 and 5; the modified graphene, modified epoxy resin and filler are chemically reacted with the coupling agent under ultrasonic to be compounded together, as shown in Figure 1 .

[0028] In a possible implementation, the mass ratio of the modified graphene, modified epoxy resin, solvent, filler, dispersant, coupling agent and curing agent is (2-8):(30-50):(30-50):(5-15):(0.5-3):(0.5-2):(2-5).

[0029] In a possible implementation, the solvent comprises at least one of ethanol, acetone, ethyl acetate and N,N-dimethylformamide.

[0030] In a possible implementation, the filler comprises any two of nano-zinc oxide, nano-titanium dioxide and nano-silicon dioxide; the mass ratio of the any two fillers is 50:50; the particle size range of the filler is 10-100 nm.

[0031] In a possible implementation, the dispersant comprises at least one of N-methyl pyrrolidone and polyvinyl pyrrolidone.

[0032] In a possible implementation, the coupling agent comprises at least one of silane coupling agent, titanate coupling agent and aluminate coupling agent; further, the silane coupling agent comprises at least one of KH550 and KH560; the titanate coupling agent comprises at least one of TCA-201 and TCA-44; the aluminate coupling agent comprises at least one of DL-411 and DL-414; but the use of coupling agent is not limited to the above-mentioned kinds, other kinds of coupling agents not listed in silane coupling agent, titanate coupling agent and aluminate coupling agent are also applicable.

[0033] In a possible implementation, the curing agent comprises at least one of ethylenediamine, diethylenetriamine and m-phenylenediamine.

[0034] In a second aspect, the present application provides a preparation method of a modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared by ultrasonic rapid synthesis, as shown in the following formula (II): Figure 2 The preparation method comprises the following steps:

[0035] Firstly, the modified graphene is added into a solvent, and a dispersing agent and a coupling agent are added into the solvent, and the mixture is treated by ultrasonic and stirring at a first set frequency for a first set time to obtain a modified graphene dispersion liquid;

[0036] Then, a modified epoxy resin and a filler are added into the modified graphene dispersion liquid, and the mixture is treated by ultrasonic and stirring at a second set frequency for a second set time to obtain a mixed liquid;

[0037] Finally, a curing agent is added dropwise into the mixed liquid, and the mixture is treated by ultrasonic and stirring at a third set frequency for a third set time, thereby obtaining the modified graphene super-hydrophobic self-cleaning anticorrosive coating.

[0038] In a possible implementation, the first set frequency is 15-20 kHz, the second set frequency is 25-30 kHz, and the third set frequency is 35-40 kHz.

[0039] In a possible implementation, the first set time is 20-30 min, the second set time is 15-20 min, and the third set time is 10-15 min.

[0040] The following will specifically describe the modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared by ultrasonic rapid synthesis and the preparation method thereof according to different embodiments.

[0041] Embodiment 1

[0042] As shown in the following formula (II), a preparation method of a modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared by ultrasonic rapid synthesis comprises the following steps: Figure 2

[0043] 1. Preparation of modified graphene dispersion liquid

[0044] Firstly, 5 g of graphene oxide is added into 45 g of ethanol, and 1 g of N-methyl pyrrolidone and 1 g of silane coupling agent (KH550) are added into the ethanol; the mixture is treated by ultrasonic and stirring at a frequency of 15 kHz for 20 min to obtain a modified graphene dispersion liquid.

[0045] 2. Preparation of mixed liquid

[0046] Then, 35 g of modified epoxy resin, 5 g of nano zinc oxide and 5 g of nano titanium dioxide are added into the modified graphene dispersion liquid; the mixture is treated by ultrasonic and stirring at a frequency of 25 kHz for 15 min to obtain a mixed liquid. ​

[0047] 3. Preparation of the coating:

[0048] Finally, 3 g of ethylenediamine is added dropwise to the mixed solution, and the modified graphene super-hydrophobic self-cleaning anticorrosive coating is prepared by ultrasonic treatment and stirring at a frequency of 35 kHz for 10 min.

[0049] In the above steps 1-3, the mass ratio of graphene oxide, modified epoxy resin, ethanol, nano-zinc oxide and nano-titanium dioxide, N-methyl pyrrolidone, silane coupling agent (KH550) and ethylenediamine is 5:35:45:10:1:1:3.

[0050] Example 2:

[0051] As shown in Figure 2 , a preparation method of a modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared by ultrasonic rapid synthesis includes the following steps:

[0052] 1. Preparation of modified graphene dispersion:

[0053] First, 4 g of reduced graphene oxide is added to 35 g of acetone, and 2 g of polyvinylpyrrolidone and 1 g of titanate coupling agent (TCA-201) are added to the acetone; the modified graphene dispersion is obtained by ultrasonic treatment and stirring at a frequency of 18 kHz for 25 minutes.

[0054] 2. Preparation of the mixed solution:

[0055] Then, 40 g of modified epoxy resin and 7 g of nano-titanium dioxide and 7 g of nano-silicon dioxide are added to the modified graphene dispersion; the mixed solution is obtained by ultrasonic treatment and stirring at a frequency of 28 kHz for 18 minutes.

[0056] 3. Preparation of the coating:

[0057] Finally, 4 g of diethylenetriamine is added dropwise to the mixed solution, and the modified graphene super-hydrophobic self-cleaning anticorrosive coating is prepared by ultrasonic treatment and stirring at a frequency of 38 kHz for 12 min.

[0058] In the above steps 1-3, the mass ratio of reduced graphene oxide, modified epoxy resin, acetone, nano-titanium dioxide and nano-silicon dioxide, polyvinylpyrrolidone, titanate coupling agent (TCA-201) and diethylenetriamine is 4:40:35:14:2:1:4.

[0059] Example 3:

[0060] As shown in Figure 2 , a preparation method of a modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared by ultrasonic rapid synthesis includes the following steps:

[0061] 1. Preparation of modified graphene dispersion liquid:

[0062] First, 2 g of graphene oxide was added to 35 g of ethyl acetate, and 1.5 g of N-methyl pyrrolidone and 0.5 g of aluminate coupling agent (DL-411) were added to the ethyl acetate; under the frequency of 20 kHz, the mixture was treated by ultrasonic stirring for 25 min to obtain a modified graphene dispersion liquid.

[0063] 2. Preparation of mixed liquid:

[0064] Then, 50 g of modified epoxy resin and 3.5 g of nano zinc oxide and 3.5 g of nano silicon dioxide were added to the modified graphene dispersion liquid; under the frequency of 30 kHz, the mixture was treated by ultrasonic stirring for 16 min to obtain a mixed liquid.

[0065] 3. Preparation of coating:

[0066] Finally, 4 g of m-phenylenediamine was added dropwise to the mixed liquid, and the mixture was treated by ultrasonic stirring for 15 min under the frequency of 40 kHz to obtain a modified graphene super-hydrophobic self-cleaning anticorrosive coating.

[0067] In the above steps 1-3, the mass ratio of graphene oxide, modified epoxy resin, ethyl acetate, nano zinc oxide and nano silicon dioxide, N-methyl pyrrolidone, aluminate coupling agent (DL-411) and m-phenylenediamine is 2:50:35:7:1.5:0.5:4.

[0068] Example 4:

[0069] As shown in Figure 2 A method for preparing a modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared by ultrasonic rapid synthesis, comprising the following steps:

[0070] 1. Preparation of modified graphene dispersion liquid:

[0071] First, 3 g of reduced graphene oxide was added to 40 g of N,N-dimethylformamide, and 0.5 g of polyvinylpyrrolidone and 2 g of silane coupling agent (KH560) were added to the N,N-dimethylformamide; under the frequency of 16 kHz, the mixture was treated by ultrasonic stirring for 22 min to obtain a modified graphene dispersion liquid.

[0072] 2. Preparation of mixed liquid:

[0073] Then, 40 g of modified epoxy resin and 6 g of nano titanium dioxide and 6 g of nano silicon dioxide were added to the modified graphene dispersion liquid; under the frequency of 25 kHz, the mixture was treated by ultrasonic stirring for 16 min to obtain a mixed liquid.

[0074] 3. Preparation of coating:

[0075] Finally, 2.5 g of ethylenediamine is added dropwise to the mixed solution, and the modified graphene super-hydrophobic self-cleaning anticorrosive coating is prepared by ultrasonic treatment and stirring at a frequency of 36 kHz for 12 min.

[0076] In the above steps 1-3, the mass ratio of reduced graphene oxide, modified epoxy resin, N,N-dimethylformamide, nano-titanium dioxide and nano-silicon dioxide, polyvinylpyrrolidone, silane coupling agent (KH560) and ethylenediamine is 3:40:40:12:0.5:2:2.5.

[0077] Example 5:

[0078] As shown in Figure 2 , a preparation method of a modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared by ultrasonic rapid synthesis includes the following steps:

[0079] 1. Preparation of modified graphene dispersion:

[0080] First, 8 g of reduced graphene oxide is added to 30 g of N,N-dimethylformamide, and 1.5 g of N-methylpyrrolidone and 1.5 g of titanate coupling agent (TCA-44) are added to the N,N-dimethylformamide; ultrasonic treatment and stirring are performed at a frequency of 18 kHz for 25 min to obtain a modified graphene dispersion.

[0081] 2. Preparation of mixed solution:

[0082] Then, 45 g of modified epoxy resin, 5 g of nano-zinc oxide and 5 g of nano-silicon dioxide are added to the modified graphene dispersion; ultrasonic treatment and stirring are performed at a frequency of 28 kHz for 15 min to obtain a mixed solution.

[0083] 3. Preparation of coating:

[0084] Finally, 4 g of diethylenetriamine is added dropwise to the mixed solution, and the modified graphene super-hydrophobic self-cleaning anticorrosive coating is prepared by ultrasonic treatment and stirring at a frequency of 40 kHz for 10 min.

[0085] In the above steps 1-3, the mass ratio of reduced graphene oxide, modified epoxy resin, N,N-dimethylformamide, nano-zinc oxide and nano-silicon dioxide, N-methylpyrrolidone, titanate coupling agent (TCA-44) and curing agent is 8:45:30:10:1.5:1.5:4.

[0086] Example 6:

[0087] As shown in Figure 2 , a preparation method of a modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared by ultrasonic rapid synthesis includes the following steps:

[0088] 1. Preparation of modified graphene dispersion liquid:

[0089] First, 7 g of graphene oxide was added to 40 g of acetone, and 3 g of polyvinylpyrrolidone and 2 g of aluminate coupling agent (DL-414) were added to the acetone; under the frequency of 20 kHz, the mixture was treated by ultrasonic stirring for 30 min to obtain a modified graphene dispersion liquid.

[0090] 2. Preparation of mixed liquid:

[0091] Then, 30 g of modified epoxy resin and 6.5 g of nano-titanium dioxide and 6.5 g of nano-silicon dioxide were added to the modified graphene dispersion liquid; under the frequency of 26 kHz, the mixture was treated by ultrasonic stirring for 20 min to obtain a mixed liquid.

[0092] 3. Preparation of paint:

[0093] Finally, 5 g of m-phenylenediamine was added dropwise to the mixed liquid, and the mixture was treated by ultrasonic stirring for 15 min under the frequency of 40 kHz to obtain a modified graphene super-hydrophobic self-cleaning anticorrosive paint.

[0094] In the above steps 1-3, the mass ratio of graphene oxide, modified epoxy resin, acetone, nano-titanium dioxide and nano-silicon dioxide, polyvinylpyrrolidone, aluminate coupling agent (DL-414) and m-phenylenediamine is 7:30:40:13:3:2:5.

[0095] Comparative Example 1:

[0096] A preparation method of a modified graphene super-hydrophobic self-cleaning anticorrosive paint synthesized by ultrasonic rapid synthesis, comprising the following steps:

[0097] 1. Preparation of modified graphene dispersion liquid:

[0098] First, 5 g of graphene was added to 45 g of ethanol, and 1 g of N-methylpyrrolidone and 1 g of silane coupling agent (KH550) were added to the ethanol; under the frequency of 15 kHz, the mixture was treated by ultrasonic stirring for 20 min to obtain a modified graphene dispersion liquid.

[0099] 2. Preparation of mixed liquid:

[0100] Then, 35 g of modified epoxy resin and 5 g of nano-zinc oxide and 5 g of nano-titanium dioxide were added to the modified graphene dispersion liquid; under the frequency of 25 kHz, the mixture was treated by ultrasonic stirring for 15 min to obtain a mixed liquid.

[0101] 3. Preparation of paint:

[0102] Finally, 3 g of ethylenediamine was added dropwise to the mixed liquid, and the mixture was treated by ultrasonic stirring for 10 min under the frequency of 35 kHz to obtain a modified graphene super-hydrophobic self-cleaning anticorrosive paint.

[0103] In the above steps 1-3, the mass ratio of graphene, modified epoxy resin, ethanol, nano zinc oxide and nano titanium dioxide, N-methyl pyrrolidone, silane coupling agent (KH550) and ethylenediamine is 5:35:45:10:1:1:3.

[0104] Comparative Example 2:

[0105] A preparation method of a modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared by ultrasonic rapid synthesis, comprising the following steps:

[0106] 1. Preparation of modified graphene dispersion:

[0107] First, 2g of graphene oxide is added to 35g of ethyl acetate, and 2.0g of N-methyl pyrrolidone is added to the ethyl acetate; under the frequency of 20kHz, the mixture is treated by ultrasonic stirring for 25min to obtain a modified graphene dispersion.

[0108] 2. Preparation of the mixed solution:

[0109] Then, 50g of modified epoxy resin and 3.5g of nano zinc oxide and 3.5g of nano silicon dioxide are added to the modified graphene dispersion; under the frequency of 30kHz, the mixture is treated by ultrasonic stirring for 16min to obtain a mixed solution.

[0110] 3. Preparation of the coating:

[0111] Finally, 4g of m-phenylenediamine is added dropwise to the mixed solution, and the mixture is treated by ultrasonic stirring for 15min under the frequency of 40kHz to obtain a modified graphene super-hydrophobic self-cleaning anticorrosive coating.

[0112] In the above steps 1-3, the mass ratio of graphene oxide, modified epoxy resin, ethyl acetate, nano zinc oxide and nano silicon dioxide, N-methyl pyrrolidone, aluminate coupling agent (DL-411) and m-phenylenediamine is 2:50:35:7:2:4.

[0113] Comparative Example 3:

[0114] A preparation method of a modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared by ultrasonic rapid synthesis, comprising the following steps:

[0115] 1. Preparation of modified graphene dispersion:

[0116] First, 7g of graphene is added to 40g of acetone, and 5g of polyvinylpyrrolidone is added to the acetone; under the frequency of 20kHz, the mixture is treated by ultrasonic stirring for 30min to obtain a modified graphene dispersion.

[0117] 2. Preparation of the mixed solution:

[0118] Then 30g modified epoxy resin and 6.5g nano-titanium dioxide and 6.5g nano-silicon dioxide were added to the modified graphene dispersion liquid; the mixture was treated under ultrasonic and stirring at a frequency of 26 kHz for 20 min to obtain a mixed solution.

[0119] 3. Preparation of the coating:

[0120] Finally, 5g m-phenylenediamine was added dropwise to the mixed solution, and the mixture was treated under ultrasonic and stirring at a frequency of 40 kHz for 15 min to obtain the modified graphene super-hydrophobic self-cleaning anticorrosive coating.

[0121] In the above steps 1-3, the mass ratio of graphene, modified epoxy resin, acetone, nano-titanium dioxide and nano-silicon dioxide, polyvinylpyrrolidone and m-phenylenediamine was 7:30:40:13:5:5.

[0122] The modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared in the present application was tested for water contact angle, and the corresponding contact angle was measured to reflect its hydrophobicity.

[0123] According to GB / T 9780-2013, the modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared in the present application was tested for stain resistance by standard state method, and the results were determined for stain resistance grade to reflect its self-cleaning performance.

[0124] According to GB / T 1771-2007, the modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared in the present application was tested for neutral salt spray resistance, and the corrosion defects on the surface of the test sample were observed to reflect its corrosion resistance.

[0125] Table 1 Test results of the modified graphene super-hydrophobic self-cleaning anticorrosive coating prepared in the examples and comparative examples

[0126] Contact angle (°) Self-cleaning performance rating Corrosion resistance performance Example 1 155 1st 240h no defects Example 2 154 1st 240h no defects Example 3 155 1st 240h no defects Example 4 152 1st 240h no defects Example 5 153 1st 240h no defects Example 6 158 1st 240h no defects Comparative Example 1 135 2nd 168h with defects Comparative Example 2 131 2nd 168h with defects Comparative Example 3 124 3rd 120h with defects

[0127] As can be seen from Table 1, the data of Examples 1-6 are overall better than those of Comparative Examples 1-3.

[0128] This is because, in Examples 1-6, the modified epoxy resin with special structure has fluorine-containing groups and epoxy groups, the epoxy groups participate in the chemical reaction between the modified graphene, the filler and the coupling agent, and the components are compounded and crosslinked with each other, so that the corrosion resistance is significantly improved, and the fluorine-containing groups remain. In the modified graphene super-hydrophobic self-cleaning anticorrosive coating obtained after the compounding of the components, the remaining fluorine-containing groups have very low surface energy, which significantly reduces the surface energy of the coating and achieves super-hydrophobic effect. At the same time, the nano-titanium dioxide and nano-zinc oxide in the filler generate superoxide radicals under light, which can decompose organic pollutants on the surface of the coating to achieve self-cleaning effect.

[0129] In Comparative Example 1, graphene instead of modified graphene is used, and the graphene surface has almost no active functional groups that can react, so it is more difficult to be compounded with other components through chemical reaction. In addition, its non-polar structure also makes it more difficult to disperse in the whole reaction system, ultimately resulting in poorer performance. In Comparative Example 2, no coupling agent is used, so it is more difficult for the components to be compounded together through chemical reaction, and the performance is also poorer. In Comparative Example 3, neither modified graphene nor a coupling agent is used, so the performance is the worst.

[0130] The above results show and describe the basic principles and main features of the present application and the advantages of the present application.

[0131] Those skilled in the art should understand that the present application is not limited to the above examples, and the above examples and descriptions in the specification are only to illustrate the principles of the present application. Without departing from the spirit and scope of the present application, various changes and improvements can be made to the present application, and these changes and improvements all fall within the scope of the claimed present application. The scope of protection claimed by the present application is defined by the equivalents of the appended claims.

Claims

1. A modified graphene superhydrophobic self-cleaning anticorrosive coating synthesized rapidly by ultrasound, characterized in that, The mixture includes modified graphene, modified epoxy resin, solvent, filler, dispersant, coupling agent, and curing agent; the modified graphene includes at least one of graphene oxide and reduced graphene oxide; the modified epoxy resin has the following structure: Wherein, n is an integer between 1 and 5; the modified graphene, modified epoxy resin and filler are chemically reacted with the coupling agent under ultrasound, thereby becoming composite together.

2. The modified graphene superhydrophobic self-cleaning anticorrosive coating synthesized by ultrasonic rapid synthesis according to claim 1, characterized in that, The mass ratio of the modified graphene, modified epoxy resin, solvent, filler, dispersant, coupling agent and curing agent is (2-8):(30-50):(30-50):(5-15):(0.5-3):(0.5-2):(2-5).

3. The modified graphene superhydrophobic self-cleaning anticorrosive coating synthesized by ultrasonic rapid synthesis according to claim 1, characterized in that, The solvent includes at least one of ethanol, acetone, ethyl acetate, and N,N-dimethylformamide.

4. The modified graphene superhydrophobic self-cleaning anticorrosive coating synthesized by ultrasonic rapid synthesis according to claim 1, characterized in that, The filler includes any two of nano zinc oxide, nano titanium dioxide, and nano silicon dioxide.

5. The modified graphene superhydrophobic self-cleaning anticorrosive coating synthesized by ultrasonic rapid synthesis according to claim 4, characterized in that, The mass ratio of any two fillers is 50:50; the particle size range of the fillers is 10–100 nm.

6. The modified graphene superhydrophobic self-cleaning anticorrosive coating synthesized by ultrasonic rapid synthesis according to claim 1, characterized in that, The dispersant includes at least one of N-methylpyrrolidone and polyvinylpyrrolidone.

7. The modified graphene superhydrophobic self-cleaning anticorrosive coating synthesized by ultrasonic rapid synthesis according to claim 1, characterized in that, The coupling agent includes at least one of silane coupling agents, titanate coupling agents, and aluminate coupling agents.

8. The modified graphene superhydrophobic self-cleaning anticorrosive coating synthesized by ultrasonic rapid synthesis according to claim 1, characterized in that, The curing agent includes at least one of ethylenediamine, diethylenetriamine, and m-phenylenediamine.

9. A method for preparing a modified graphene superhydrophobic self-cleaning anticorrosive coating rapidly synthesized by ultrasound according to any one of claims 1-8, characterized in that, Includes the following steps: First, the modified graphene is added to the solvent, and a dispersant and a coupling agent are added to the solvent. The mixture is then ultrasonically stirred at a first set frequency for a first set time to obtain a modified graphene dispersion. Then, modified epoxy resin and filler are added to the modified graphene dispersion, and the mixture is ultrasonically stirred at a second set frequency for a second set time to obtain a mixture. Finally, the curing agent is added dropwise to the mixture, and the mixture is ultrasonically stirred at a third set frequency for a third set time to obtain the modified graphene superhydrophobic self-cleaning anti-corrosion coating.

10. The method for preparing a modified graphene superhydrophobic self-cleaning anticorrosive coating rapidly synthesized by ultrasound according to claim 9, characterized in that, The first set frequency is 15-20kHz; the second set frequency is 25-30kHz; the third set frequency is 35-40kHz; the first set time is 20-30min; the second set time is 15-20min; and the third set time is 10-15min.

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