Ultrasound-rapidly-synthesized modified graphene super-hydrophobic self-cleaning anticorrosive paint and preparation method thereof

Abstract

The invention discloses a modified graphene super-hydrophobic self-cleaning anticorrosive coating rapidly synthesized by ultrasound and a preparation method thereof, and relates to the technical field of coatings. Adding the modified graphene into a solvent, adding a dispersing agent and a coupling agent into the solvent, and performing ultrasonic stirring to obtain a modified graphene dispersion liquid; adding modified epoxy resin and a filler into the modified graphene dispersion liquid, and performing ultrasonic stirring to obtain a mixed liquid; dropwise adding a curing agent into the mixed solution, and performing ultrasonic stirring treatment to prepare the modified graphene super-hydrophobic self-cleaning anticorrosive coating. By using an ultrasonic rapid synthesis method, the chemical reaction of the modified graphene, the modified epoxy resin with a special structure, the filler and the coupling agent in the same solvent system is promoted, so that the modified graphene, the modified epoxy resin, the filler and the coupling agent are compounded together, and the modified graphene super-hydrophobic self-cleaning anticorrosive coating with excellent performance is further obtained.

Description

Technical Field

[0001] The present application relates to the field of coating technology, and in particular to an ultrasonically rapidly synthesized modified graphene super-hydrophobic self-cleaning anti-corrosion coating and a preparation method thereof. Background Art

[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 and reduces their performance, but may also cause safety hazards and cause huge economic losses. Traditional anti-corrosion coatings such as alkyd paints and epoxy paints can play a protective role to a certain extent, but they have many limitations, especially in terms of hydrophobicity, self-cleaning performance and corrosion resistance.

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

[0004] The Chinese patent application with publication number CN111234696 A discloses a super-hydrophobic conductive anti-corrosion graphene coating and its preparation method. The super-hydrophobic conductive anti-corrosion graphene coating is composed of synthetic resin, modified graphene nanosheets, auxiliary agent, solvent and curing agent. Its preparation method includes: firstly, graphene nanosheets are modified by fluorine-containing silicon compounds; then the modified graphene nanosheets are added to synthetic resin, auxiliary agent and solvent, and after being matched with curing agent, super-hydrophobic conductive anti-corrosion graphene coating is formed. The super-hydrophobic conductive anti-corrosion graphene coating formed by the super-hydrophobic conductive anti-corrosion graphene coating obtained by the invention has good super-hydrophobicity, conductivity, corrosion resistance, and good storage stability, is not easy to sink to the bottom, and large-scale construction can be achieved. However, the super-hydrophobic conductive anti-corrosion graphene coating preparation cycle is long, and other properties still have room for improvement.

[0005] In summary, there is an urgent need to develop modified graphene coatings and preparation methods that can quickly and efficiently prepare superhydrophobic self-cleaning and excellent anti-corrosion properties to meet the needs of modern industry and daily life for high-performance protective materials. Summary of the invention

[0006] In view of the deficiencies of the prior art, the present application provides a modified graphene superhydrophobic self-cleaning and anti-corrosion coating prepared by ultrasonic rapid synthesis and a preparation method thereof. The modified graphene, modified epoxy resin and filler chemically react with a coupling agent under ultrasonic waves, so as to be compounded with each other, and further a modified graphene superhydrophobic self-cleaning and anti-corrosion coating is prepared. The modified graphene superhydrophobic self-cleaning and anti-corrosion coating is rapidly and efficiently synthesized under the action of ultrasonic waves, has excellent performance, and has broad application prospects and market value.

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

[0008] In a first aspect, the present application provides a modified graphene superhydrophobic self-cleaning and anti-corrosion coating prepared by ultrasonic rapid synthesis, comprising modified graphene, modified epoxy resin, solvent, filler, dispersant, coupling agent and curing agent; the structure of the modified epoxy resin includes:

[0009]

[0010] wherein, n is an integer between 1 and 5; the modified graphene, modified epoxy resin and filler chemically react with a coupling agent under ultrasonic waves, so as to be compounded with each other.

[0011] In a second aspect, the present application provides a preparation method of a modified graphene superhydrophobic self-cleaning and anti-corrosion coating prepared by ultrasonic rapid synthesis, comprising:

[0012] First, add the modified graphene into the solvent, and add a dispersant and a coupling agent into the solvent, and perform ultrasonic stirring treatment at a first set frequency for a first set time to obtain a modified graphene dispersion;

[0013] Then, add the modified epoxy resin and the filler into the modified graphene dispersion, and perform ultrasonic stirring treatment at a second set frequency for a second set time to obtain a mixture;

[0014] Finally, drop the curing agent into the mixture, and perform ultrasonic stirring treatment at a third set frequency for a third set time to prepare the modified graphene superhydrophobic self-cleaning and anti-corrosion coating.

[0015] Beneficial technical effects:

[0016] In this application, the modified epoxy resin with a special structure has fluorine-containing groups and epoxy groups. The epoxy groups participate in chemical reactions with modified graphene, fillers, and coupling agents, and the components are compounded and cross-linked with each other, resulting in a significant improvement in anti-corrosion performance, while the fluorine-containing groups are retained. In the modified graphene superhydrophobic self-cleaning anti-corrosion coating obtained after the compounding of each component, the retained fluorine-containing groups have an extremely low surface energy, significantly reducing the surface energy of the coating and achieving a superhydrophobic effect. At the same time, nano-titanium dioxide and nano-zinc oxide in the filler generate superoxide radicals under light irradiation, which can decompose organic pollutants on the surface of the coating and achieve a self-cleaning effect.

[0017] In addition, by utilizing the phenomenon that when ultrasonic waves propagate in a liquid, tiny bubbles are generated, and when the bubbles burst, a huge amount of energy is released, forming a local instantaneous high-temperature and high-impact environment, the chemical reactions of modified graphene, modified epoxy resin with a special structure, fillers, and coupling agents in the same solvent system are promoted, enabling them to be compounded with each other, and finally a modified graphene superhydrophobic self-cleaning anti-corrosion coating with excellent performance is obtained.

[0018] The modified graphene superhydrophobic self-cleaning anti-corrosion coating prepared in this application uses ultrasound throughout the preparation process, the reaction conditions are very mild, the preparation process is very simple, the synthesis process is rapid and efficient, and it has broad application prospects. Description of the Drawings

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

[0020] Figure 2 is a schematic diagram of the process for preparing the modified graphene superhydrophobic self-cleaning anti-corrosion coating. Detailed Embodiments

[0021] In order to make the technical problems, technical solutions, and beneficial effects to be solved by this application clearer and more understandable, the following will further elaborate on this application in combination with embodiments. However, this should not be construed as limiting the scope of this application to the following examples. Without departing from the above-mentioned method concept of this application, all other embodiments obtained by those of ordinary skill in the art without creative efforts fall within the scope of protection of this application.

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

[0023] The singular forms "is", "a", and "the" used in this application are intended to include the plural forms unless the context clearly indicates otherwise.

[0024] In addition, if terms such as "first" and "second" appear, they are for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0025] In a first aspect, the present application provides a modified graphene superhydrophobic self-cleaning and anti-corrosion coating for ultrasonic rapid synthesis, 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 undergo chemical reactions with the coupling agent under ultrasonic waves, and thus are compounded with each other, as Figure 1 shown.

[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-silica; 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-methylpyrrolidone and polyvinylpyrrolidone.

[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; however, the use of the coupling agent is not limited to the types listed above, and other unlisted types of 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 method for preparing a modified graphene superhydrophobic self-cleaning and anti-corrosion coating by ultrasonic rapid synthesis, as Figure 2 shown, including:

[0035] First, add modified graphene to a solvent, and add a dispersant and a coupling agent to the solvent. While ultrasonicating and stirring at a first set frequency for a first set time, a modified graphene dispersion is obtained;

[0036] Then, add a modified epoxy resin and a filler to the modified graphene dispersion. While ultrasonicating and stirring at a second set frequency for a second set time, a mixture is obtained;

[0037] Finally, add a curing agent dropwise to the mixture. While ultrasonicating and stirring at a third set frequency for a third set time, the modified graphene superhydrophobic self-cleaning and anti-corrosion coating is prepared.

[0038] In a possible implementation, the first set frequency is 15 - 20 kHz; the second set frequency is 25 - 30 kHz; 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; the third set time is 10 - 15 min.

[0040] The following will specifically describe a modified graphene superhydrophobic self-cleaning and anti-corrosion coating and a preparation method thereof provided by the present application in combination with different embodiments.

[0041] Example 1:

[0042] As Figure 2 shown, a method for preparing a modified graphene superhydrophobic self-cleaning and anti-corrosion coating by ultrasonic rapid synthesis includes the following steps:

[0043] 1. Preparation of the modified graphene dispersion:

[0044] First, add 5 g of graphene oxide to 45 g of ethanol, and add 1 g of N-methylpyrrolidone and 1 g of silane coupling agent (KH550) to the ethanol; while ultrasonicating and stirring at a frequency of 15 kHz for 20 min, a modified graphene dispersion is obtained.

[0045] 2. Preparation of the mixture:

[0046] Then, add 35 g of modified epoxy resin, 5 g of nano-zinc oxide and 5 g of nano-titanium dioxide to the modified graphene dispersion; while ultrasonicating and stirring at a frequency of 25 kHz for 15 min, a mixture is obtained.

[0047] 3. Preparation of the coating:

[0048] Finally, 3 g of ethylenediamine was added dropwise to the mixed solution, and the mixture was treated with ultrasonic stirring at a frequency of 35 kHz for 10 min to obtain the modified graphene superhydrophobic self-cleaning and anti-corrosion coating.

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

[0050] Example 2:

[0051] As Figure 2 shown, a preparation method of a modified graphene superhydrophobic self-cleaning and anti-corrosion coating by ultrasonic rapid synthesis includes the following steps:

[0052] 1. Preparation of the modified graphene dispersion:

[0053] First, 4 g of reduced graphene oxide was added to 35 g of acetone, and 2 g of polyvinylpyrrolidone and 1 g of titanate coupling agent (TCA-201) were added to the acetone; the mixture was treated with ultrasonic stirring at a frequency of 18 kHz for 25 minutes to obtain the modified graphene dispersion.

[0054] 2. Preparation of the mixed solution:

[0055] Then, 40 g of modified epoxy resin, 7 g of nano-titanium dioxide, and 7 g of nano-silica were added to the modified graphene dispersion; the mixture was treated with ultrasonic stirring at a frequency of 28 kHz for 18 minutes to obtain the mixed solution.

[0056] 3. Preparation of the coating:

[0057] Finally, 4 g of diethylenetriamine was added dropwise to the mixed solution, and the mixture was treated with ultrasonic stirring at a frequency of 38 kHz for 12 min to obtain the modified graphene superhydrophobic self-cleaning and anti-corrosion coating.

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

[0059] Example 3:

[0060] As Figure 2 shown, a preparation method of a modified graphene superhydrophobic self-cleaning and anti-corrosion coating by ultrasonic rapid synthesis includes the following steps:

[0061] 1. Preparation of modified graphene dispersion:

[0062] First, add 2 g of graphene oxide to 35 g of ethyl acetate, and add 1.5 g of N-methylpyrrolidone and 0.5 g of aluminate coupling agent (DL-411) to the ethyl acetate; under the frequency of 20 kHz, perform ultrasonic treatment while stirring for 25 min to obtain the modified graphene dispersion.

[0063] 2. Preparation of the mixed solution:

[0064] Then, add 50 g of modified epoxy resin, 3.5 g of nano-zinc oxide, and 3.5 g of nano-silica to the modified graphene dispersion; under the frequency of 30 kHz, perform ultrasonic treatment while stirring for 16 min to obtain the mixed solution.

[0065] 3. Preparation of the coating:

[0066] Finally, drop 4 g of m-phenylenediamine into the mixed solution, and under the frequency of 40 kHz, perform ultrasonic treatment while stirring for 15 min to prepare the modified graphene superhydrophobic self-cleaning and anti-corrosion coating.

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

[0068] Example 4:

[0069] As Figure 2 shown, a preparation method of a modified graphene superhydrophobic self-cleaning and anti-corrosion coating by ultrasonic rapid synthesis includes the following steps:

[0070] 1. Preparation of modified graphene dispersion:

[0071] First, add 3 g of reduced graphene oxide to 40 g of N,N-dimethylformamide, and add 0.5 g of polyvinylpyrrolidone and 2 g of silane coupling agent (KH560) to the N,N-dimethylformamide; under the frequency of 16 kHz, perform ultrasonic treatment while stirring for 22 min to obtain the modified graphene dispersion.

[0072] 2. Preparation of the mixed solution:

[0073] Then, add 40 g of modified epoxy resin, 6 g of nano-titanium dioxide, and 6 g of nano-silica to the modified graphene dispersion; under the frequency of 25 kHz, perform ultrasonic treatment while stirring for 16 min to obtain the mixed solution.

[0074] 3. Preparation of the coating:

[0075] Finally, 2.5 g of ethylenediamine was added dropwise to the mixed solution, and the mixture was treated with ultrasonic stirring at a frequency of 36 kHz for 12 min to obtain the modified graphene superhydrophobic self-cleaning and anti-corrosion coating.

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

[0077] Example 5:

[0078] As Figure 2 shown, a preparation method of a modified graphene superhydrophobic self-cleaning and anti-corrosion coating by ultrasonic rapid synthesis includes the following steps:

[0079] 1. Preparation of the modified graphene dispersion:

[0080] First, 8 g of reduced graphene oxide was 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) were added to the N,N-dimethylformamide; the mixture was treated with ultrasonic stirring at a frequency of 18 kHz for 25 min to obtain the modified graphene dispersion.

[0081] 2. Preparation of the mixed solution:

[0082] Then, 45 g of modified epoxy resin, 5 g of nano-zinc oxide and 5 g of nano-silica were added to the modified graphene dispersion; the mixture was treated with ultrasonic stirring at a frequency of 28 kHz for 15 min to obtain the mixed solution.

[0083] 3. Preparation of the coating:

[0084] Finally, 4 g of diethylenetriamine was added dropwise to the mixed solution, and the mixture was treated with ultrasonic stirring at a frequency of 40 kHz for 10 min to obtain the modified graphene superhydrophobic self-cleaning and anti-corrosion coating.

[0085] In the above steps 1-3, the mass ratio of reduced graphene oxide, modified epoxy resin, N,N-dimethylformamide, nano-zinc oxide, nano-silica, 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 Figure 2 shown, a preparation method of a modified graphene superhydrophobic self-cleaning and anti-corrosion coating by ultrasonic rapid synthesis includes the following steps:

[0088] 1. Preparation of modified graphene dispersion:

[0089] First, add 7 g of graphene oxide to 40 g of acetone, and add 3 g of polyvinylpyrrolidone and 2 g of aluminate coupling agent (DL-414) to the acetone; under the frequency of 20 kHz, perform ultrasonic treatment while stirring for 30 min to obtain the modified graphene dispersion.

[0090] 2. Preparation of the mixed solution:

[0091] Then, add 30 g of modified epoxy resin, 6.5 g of nano-titanium dioxide, and 6.5 g of nano-silica to the modified graphene dispersion; under the frequency of 26 kHz, perform ultrasonic treatment while stirring for 20 min to obtain the mixed solution.

[0092] 3. Preparation of the coating:

[0093] Finally, add 5 g of m-phenylenediamine dropwise to the mixed solution, and perform ultrasonic treatment while stirring for 15 min under the frequency of 40 kHz to obtain the modified graphene superhydrophobic self-cleaning and anti-corrosion coating.

[0094] In the above steps 1-3, the mass ratio of graphene oxide, modified epoxy resin, acetone, nano-titanium dioxide, nano-silica, 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 superhydrophobic self-cleaning and anti-corrosion coating by ultrasonic rapid synthesis includes the following steps:

[0097] 1. Preparation of modified graphene dispersion:

[0098] First, add 5 g of graphene to 45 g of ethanol, and add 1 g of N-methylpyrrolidone and 1 g of silane coupling agent (KH550) to the ethanol; under the frequency of 15 kHz, perform ultrasonic treatment while stirring for 20 min to obtain the modified graphene dispersion.

[0099] 2. Preparation of the mixed solution:

[0100] Then, add 35 g of modified epoxy resin, 5 g of nano-zinc oxide, and 5 g of nano-titanium dioxide to the modified graphene dispersion; under the frequency of 25 kHz, perform ultrasonic treatment while stirring for 15 min to obtain the mixed solution.

[0101] 3. Preparation of the coating:

[0102] Finally, add 3 g of ethylenediamine dropwise to the mixed solution, and perform ultrasonic treatment while stirring for 10 min under the frequency of 35 kHz to obtain the modified graphene superhydrophobic self-cleaning and anti-corrosion coating.

[0103] In the above steps 1 to 3, the mass ratio of graphene, modified epoxy resin, ethanol, nano-zinc oxide, nano-titanium dioxide, N-methylpyrrolidone, 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 superhydrophobic self-cleaning and anti-corrosion coating by ultrasonic rapid synthesis, comprising the following steps:

[0106] 1. Preparation of a modified graphene dispersion:

[0107] First, add 2 g of graphene oxide to 35 g of ethyl acetate, and add 2.0 g of N-methylpyrrolidone to the ethyl acetate; under the frequency of 20 kHz, perform ultrasonic treatment while stirring for 25 min to obtain a modified graphene dispersion.

[0108] 2. Preparation of a mixed solution:

[0109] Then, add 50 g of modified epoxy resin, 3.5 g of nano-zinc oxide, and 3.5 g of nano-silica to the modified graphene dispersion; under the frequency of 30 kHz, perform ultrasonic treatment while stirring for 16 min to obtain a mixed solution.

[0110] 3. Preparation of the coating:

[0111] Finally, add 4 g of m-phenylenediamine dropwise to the mixed solution, and perform ultrasonic treatment while stirring for 15 min under the frequency of 40 kHz to prepare the modified graphene superhydrophobic self-cleaning and anti-corrosion coating.

[0112] In the above steps 1 to 3, the mass ratio of graphene oxide, modified epoxy resin, ethyl acetate, nano-zinc oxide, nano-silica, N-methylpyrrolidone, 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 superhydrophobic self-cleaning and anti-corrosion coating by ultrasonic rapid synthesis, comprising the following steps:

[0115] 1. Preparation of a modified graphene dispersion:

[0116] First, add 7 g of graphene to 40 g of acetone, and add 5 g of polyvinylpyrrolidone to the acetone; under the frequency of 20 kHz, perform ultrasonic treatment while stirring for 30 min to obtain a modified graphene dispersion.

[0117] 2. Preparation of a mixed solution:

[0118] Then, 30 g of modified epoxy resin, 6.5 g of nano-titanium dioxide and 6.5 g of nano-silica are added to the modified graphene dispersion liquid; ultrasonic stirring treatment is carried out for 20 min at a frequency of 26 kHz to obtain a mixed liquid.

[0119] 3. Preparation of the coating:

[0120] Finally, 5 g of m-phenylenediamine is dropped into the mixed liquid, and ultrasonic stirring treatment is carried out for 15 min at a frequency of 40 kHz to obtain the modified graphene superhydrophobic self-cleaning anti-corrosion coating.

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

[0122] The water contact angle of the modified graphene superhydrophobic self-cleaning anti-corrosion coating prepared in this application is tested, and the corresponding contact angle size is measured to reflect its hydrophobic performance.

[0123] Referring to GB / T 9780-2013, the stain resistance performance of the modified graphene superhydrophobic self-cleaning anti-corrosion coating prepared in this application is tested by the standard state method, and the stain resistance grade of the result is determined to reflect its self-cleaning performance.

[0124] Referring to GB / T 1771-2007, the neutral salt spray resistance performance of the modified graphene superhydrophobic self-cleaning anti-corrosion coating prepared in this application is tested, and the defect situation of the surface of the test sample being corroded is observed to reflect its corrosion resistance performance.

[0125] Table 1 Test results of the modified graphene superhydrophobic self-cleaning anti-corrosion coatings prepared in the examples and comparative examples

[0126] Contact angle (°) Self-cleaning performance level Corrosion resistance Example 1 155 Level 1 No defects after 240h Example 2 154 Level 1 No defects after 240h Example 3 155 Level 1 No defects after 240h Example 4 152 Level 1 No defects after 240h Example 5 153 Level 1 No defects after 240h Example 6 158 Level 1 No defects after 240h Comparative Example 1 135 Level 2 Defects after 168h Comparative Example 2 131 Level 2 Defects after 168h Comparative Example 3 124 Level 3 Defects after 120h

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

[0128] This is because, in Examples 1 to 6, the modified epoxy resin with a special structure has fluorine-containing groups and epoxy groups. The epoxy groups participate in the chemical reactions with modified graphene, fillers and coupling agents, and the components are mutually compounded and cross-linked, so that the anti-corrosion performance is significantly improved, while the fluorine-containing groups are retained. In the modified graphene superhydrophobic self-cleaning anti-corrosion coating obtained after the compounding of each component, the retained fluorine-containing groups have extremely low surface energy, significantly reducing the surface energy of the coating and achieving the superhydrophobic effect. At the same time, nano-titanium dioxide and nano-zinc oxide in the filler generate superoxide radicals under light, which can decompose the organic pollutants on the surface of the coating and achieve the self-cleaning effect.

[0129] In Comparative Example 1, graphene was used instead of modified graphene, and there were almost no active functional groups that could react on the surface of graphene. Therefore, it was difficult to be compounded with other components through chemical reactions. In addition, its non-polar structure also made it difficult to disperse in the whole reaction system, ultimately resulting in slightly worse performance in all aspects. In Comparative Example 2, no coupling agent was contained, which also made it difficult for each component to be compounded together through chemical reactions, and the performance in all aspects was also poor. In Comparative Example 3, neither modified graphene nor coupling agent was used, so the performance in all aspects was the worst.

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

[0131] Those skilled in the art of this industry should understand that the present application is not limited by the above-mentioned embodiments. What is described in the above-mentioned embodiments and the specification only illustrates the principle of the present application. Without departing from the spirit and scope of the present application, the present application will have various changes and improvements, and these changes and improvements all fall within the scope of the present application claimed. The scope of protection claimed by the present application is defined by the equivalents of the appended claims.

Claims

1. A modified graphene super-hydrophobic self-cleaning anti-corrosion coating synthesized by ultrasonic rapid synthesis, characterized in that: The invention comprises 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: Wherein, n is an integer between 1 and 5; the modified graphene, modified epoxy resin and filler are compounded with each other by chemically reacting with a coupling agent under ultrasound.

2. The ultrasonically rapidly synthesized modified graphene super-hydrophobic self-cleaning anti-corrosion coating 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 ultrasonically rapidly synthesized modified graphene super-hydrophobic self-cleaning anti-corrosion coating according to claim 1, characterized in that: The solvent includes at least one of ethanol, acetone, ethyl acetate and N,N-dimethylformamide.

4. The ultrasonically rapidly synthesized modified graphene super-hydrophobic self-cleaning anti-corrosion coating according to claim 1, characterized in that: The filler comprises any two of nano zinc oxide, nano titanium dioxide and nano silicon dioxide.

5. The ultrasonically rapidly synthesized modified graphene super-hydrophobic self-cleaning anti-corrosion coating 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 to 100 nm.

6. The ultrasonically rapidly synthesized modified graphene super-hydrophobic self-cleaning anti-corrosion coating according to claim 1, characterized in that: The dispersant includes at least one of N-methylpyrrolidone and polyvinylpyrrolidone.

7. The ultrasonically rapidly synthesized modified graphene super-hydrophobic self-cleaning anti-corrosion coating according to claim 1, characterized in that: The coupling agent includes at least one of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent.

8. The ultrasonically rapidly synthesized modified graphene super-hydrophobic self-cleaning anti-corrosion coating according to claim 1, characterized in that: The curing agent includes at least one of ethylenediamine, diethylenetriamine and metaphenylenediamine.

9. A method for preparing a modified graphene super-hydrophobic self-cleaning anti-corrosion coating synthesized by ultrasonic rapid synthesis according to any one of claims 1 to 8, characterized in that: The following steps are involved: First, the modified graphene is added to a solvent, and a dispersant and a coupling agent are added to the solvent, and the modified graphene dispersion is obtained by ultrasonically stirring the solvent at a first set frequency for a first set time; Then, the modified epoxy resin and the filler are added to the modified graphene dispersion, and the mixture is subjected to ultrasonic stirring at a second set frequency for a second set time to obtain a mixed solution; Finally, the curing agent is added dropwise to the mixed solution, and the mixed solution is treated with ultrasound and stirring at a third set frequency for a third set time to obtain the modified graphene super-hydrophobic self-cleaning anti-corrosion coating.

10. The method for preparing a modified graphene super-hydrophobic self-cleaning anti-corrosion coating synthesized by ultrasonic rapid synthesis according to claim 9, characterized in that: The first setting frequency is 15 to 20 kHz; the second setting frequency is 25 to 30 kHz; the third setting frequency is 35 to 40 kHz; the first setting time is 20 to 30 minutes; the second setting time is 15 to 20 minutes; the third setting time is 10 to 15 minutes.

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