Modified graphene oxide epoxy zinc-containing primer and preparation method thereof

Abstract

The invention relates to a modified graphene oxide epoxy zinc-containing primer and a preparation method thereof.The preparation method comprises the following steps that S1, graphene oxide and KH560 are blended and stirred for a reaction, and an intermediate product 1 is obtained; s2, blending the intermediate product 1, 2-hydroxyethyl acrylate and a catalyst, and carrying out heating and stirring reaction to obtain an intermediate product 2; s3, blending silicon dioxide and KH570, heating, stirring and reacting to obtain silicon dioxide containing double bonds; s4, in an inert atmosphere, blending the intermediate product 2, silicon dioxide containing double bonds and an initiator, and performing heating and stirring reaction to obtain modified graphene oxide; and S5, blending the modified graphene oxide with other components, and uniformly stirring to obtain the modified graphene oxide epoxy zinc-containing primer. Acrylate groups and silicon dioxide are introduced into the modified graphene oxide, so that the compatibility of all the components is improved, and the coating has good performance.

Description

Technical Field

[0001] This invention relates to the field of coating technology, and in particular to a modified graphene oxide epoxy zinc-containing primer and its preparation method. Background Technology

[0002] Atmospheric corrosion is the result of the interaction between materials and the surrounding atmospheric environment. It is the most common and destructive type of corrosion among metals. Although metal equipment cannot completely avoid metal corrosion, the corrosion rate can be slowed down through certain methods. Epoxy zinc-rich anti-corrosion primer is a high-performance anti-corrosion material that combines physical barrier and cathodic protection functions.

[0003] Currently, facing the shortage of zinc resources, the pressure of environmental protection, and the higher requirements for anti-corrosion performance, the contradiction between "traditional epoxy zinc-rich primers" and industry development is becoming increasingly prominent. Therefore, based on the consideration of environmental protection, energy conservation and consumption reduction, it is of great significance to develop anti-corrosion primers with low zinc content and long-lasting anti-corrosion performance.

[0004] Because existing zinc-rich primers have excessively high zinc powder content (generally 55% to 82%), they have certain drawbacks, such as poor film density, low strength, and poor compatibility with topcoats. Zinc oxide fumes and zinc vapors generated during welding, cutting, and other hot processing can harm human health and easily lead to "zinc fever," resulting in significant safety hazards for zinc-rich primers and coatings, especially during production and use. Furthermore, to ensure long-term corrosion resistance, the method of increasing film thickness is usually adopted to extend the corrosion protection period; for example, the dry film thickness of marine primers is generally designed to be above 300µm. This not only increases material consumption and wastes resources but also leads to problems such as easy cracking of the film.

[0005] Currently, although new epoxy zinc-containing primers have solved the above problems to some extent, they still have shortcomings, such as: insufficient compatibility of the components, which makes the components easy to aggregate and leads to a decline in coating performance; and insufficient anti-corrosion performance of the coating, which leads to a significant deterioration of the coating appearance in corrosive environments.

[0006] In conclusion, it is necessary to develop a new technical solution to address the shortcomings of existing technologies. Summary of the Invention

[0007] This invention provides a modified graphene oxide epoxy zinc-containing primer and its preparation method. It is prepared using epoxy resin, modified graphene oxide, zinc powder, etc., as raw materials. The modified graphene oxide is obtained by reacting graphene oxide with KH560, grafting 2-hydroxyethyl acrylate onto it, and then polymerizing it with silica containing double bonds. By introducing acrylate groups and silica, the modified graphene oxide improves the compatibility of the components, giving the coating excellent performance and promising application prospects.

[0008] The purpose of this invention is to provide a modified graphene oxide epoxy zinc-containing primer, wherein the modified graphene oxide epoxy zinc-containing primer comprises the following components in parts by weight: 10-18 parts epoxy resin 15-21 parts mica powder 5-10 parts of barium sulfate 6-9 parts of anti-rust pigment 2-10 parts zinc powder 1-2 parts of modified graphene oxide 15-22 parts solvent 3-8 parts of auxiliary agent 5-11 parts of curing agent; The modified graphene oxide is obtained by reacting graphene oxide with KH560, grafting 2-hydroxyethyl acrylate onto it, and then polymerizing it with silica containing double bonds.

[0009] Furthermore, the solvent is selected from one or more of dimethylformamide, dioxydimethyl ether acetate, xylene, and n-butanol.

[0010] Furthermore, the additive is selected from one or more of dispersants, leveling agents, defoamers, emulsifiers, and film-forming aids.

[0011] Furthermore, the fineness of the barium sulfate, rust-preventive pigment, and mica powder is ≤80µm.

[0012] Another object of the present invention is to provide a method for preparing the above-mentioned modified graphene oxide epoxy zinc-containing primer, wherein the method for preparing the modified graphene oxide epoxy zinc-containing primer includes the following steps: S1. Graphene oxide and KH560 are mixed and stirred to obtain intermediate product 1. S2. The intermediate product 1, 2-hydroxyethyl acrylate, and catalyst are blended and heated and stirred to obtain intermediate product 2. S3. Silica and KH570 are mixed and heated and stirred to react, yielding silica containing double bonds; S4. Under an inert atmosphere, the intermediate product 2, silicon dioxide containing double bonds, and an initiator are blended, heated, and stirred to react and obtain modified graphene oxide. S5. The modified graphene oxide is mixed with the remaining components and stirred evenly to obtain the modified graphene oxide epoxy zinc-containing primer.

[0013] Further, in step S1, the mass ratio of graphene oxide to KH560 is 1:(0.5-0.7).

[0014] Further, in step S2, the mass ratio of the intermediate product 1-hydroxyethyl acrylate to 2-hydroxyethyl acrylate is 1:(4-6).

[0015] Furthermore, in step S2, the temperature of the heating and stirring reaction is 50-70°C.

[0016] Further, in step S3, the mass ratio of silicon dioxide to KH570 is 1:(1.4-1.6).

[0017] Further, in step S4, the mass ratio of the intermediate product 2 to the double-bonded silicon dioxide is 1:(1-3).

[0018] The present invention has the following beneficial effects: The modified graphene oxide epoxy zinc-containing primer of the present invention is prepared from epoxy resin, modified graphene oxide, zinc powder, etc. The modified graphene oxide is obtained by reacting graphene oxide with KH560, grafting 2-hydroxyethyl acrylate onto it, and then polymerizing it with silica containing double bonds. In this invention, the modified graphene oxide is first introduced with epoxy groups through the reaction of graphene oxide with KH560, then the epoxy groups react with the hydroxyl groups of 2-hydroxyethyl acrylate to introduce acrylate groups, and finally, the double bonds on the acrylate groups are used to polymerize with silica containing double bonds. The modified graphene oxide incorporates acrylate groups, which interpenetrate with other components, enhancing compatibility and promoting uniform distribution and preventing aggregation. The addition of silica increases the interlayer spacing of the graphene oxide, reducing its agglomeration tendency and improving dispersibility. This allows the modified graphene oxide to be uniformly distributed in the coating and also acts as a physical barrier, enhancing its corrosion resistance. Furthermore, silica itself exhibits excellent chemical stability, resisting acids, alkalis, and oxidation, further improving the coating's corrosion resistance. The synergistic effect of all components enhances the overall performance of the coating. Attached Figure Description

[0019] Figure 1 The image shows the effect of the modified graphene oxide epoxy zinc-containing primer prepared in Example 1 after a neutral salt spray test.

[0020] Figure 2 The results of the primer prepared in the comparative example underwent a neutral salt spray resistance test are shown in the figure. Detailed Implementation

[0021] To more clearly illustrate the technical solution of the present invention, the following embodiments are provided. Unless otherwise stated, the raw materials, reactions, and post-processing methods appearing in the embodiments are all commercially available raw materials and technical methods well known to those skilled in the art.

[0022] The terms "preferred," "more preferably," and "more suitable" used in this invention refer to embodiments of the invention that provide certain beneficial effects under certain circumstances. However, other embodiments may also be preferred under the same or other circumstances. Furthermore, the description of one or more preferred embodiments does not imply that other embodiments are unavailable, nor is it intended to exclude other embodiments from the scope of this invention.

[0023] It should be understood that, except in any operational instance or otherwise indicated, the amounts or all figures representing ingredients used, for example, in the specification and claims, should be understood to be modified by the term "about" in all cases. Therefore, unless otherwise stated, the numerical parameters set forth in the following specification and appended claims are approximate values ​​varying according to the desired performance to be obtained according to the invention.

[0024] The embodiments of the present invention use the following raw materials: The epoxy resin is E44 bisphenol A epoxy resin, purchased from Guangzhou Rongsheng Chemical Co., Ltd. The mica powder was purchased from Lingshou County Yongqi Mineral Products Co., Ltd. The anti-rust pigment, brand name SHIELDEX® C303, was purchased from Grace Company, USA. Zinc powder, purchased from Yangzhou Huali Zinc Industry Co., Ltd. The graphene oxide, grade GRF-FLGOD-04, was purchased from Suzhou Greifong Nanotechnology Co., Ltd. Sodium hydroxide is used as a catalyst; Ammonium persulfate was used as the initiator; The solvent is dimethylformamide, dioxydimethyl ether acetate, xylene, and n-butanol in a mass ratio of 1:1:6:3; The additives are dispersants, leveling agents, and defoamers in a mass ratio of 2:1:1; The dispersant was Better BD8104, purchased from Foshan Better Chemical Co., Ltd. The leveling agent was BYK-350, purchased from BYK Chemical (Tongling) Co., Ltd. The defoamer was BYK066N, purchased from BYK Chemical (Tongling) Co., Ltd. Silica, grade DL-805, purchased from Shandong Delan Chemical Co., Ltd. The curing agent, brand name BST-32L, was purchased from Jiangxi Baisheng Fine Chemicals Co., Ltd.

[0025] Example 1 A modified graphene oxide epoxy zinc-containing primer, wherein the modified graphene oxide epoxy zinc-containing primer comprises the following components in parts by weight: 18 parts epoxy resin 21 portions of mica powder 10 parts of barium sulfate 9 parts of anti-rust pigment 10 parts zinc powder 2 parts of modified graphene oxide 22 parts of solvent 8 parts of auxiliary agent 11 parts curing agent; The preparation method of the modified graphene oxide epoxy zinc-containing primer includes the following steps: S1. Graphene oxide and deionized water were mixed at a mass ratio of 1:1000 and ultrasonically dispersed for 20 min. KH560 (the mass ratio of graphene oxide to KH560 was 1:0.6) was added. The pH was adjusted to 4 with acetic acid and stirred for 5 h. The mixture was then vacuum filtered, washed, and dried to obtain intermediate product 1. S2. Using deionized water as a solvent, intermediate product 1 and 2-hydroxyethyl acrylate were blended at a mass ratio of 1:5. A 10wt% sodium hydroxide solution was added to adjust the pH to 11. The mixture was heated to 60°C and stirred for 4 hours. After centrifugation, washing, and drying, intermediate product 2 was obtained. S3. Using ethanol and deionized water in a volume ratio of 1:1 as solvents, silica and KH570 were mixed in a mass ratio of 1:1.5, heated to 50°C and stirred for 24 hours. After filtration, washing and drying, silica containing double bonds was obtained. S4. Under a nitrogen atmosphere, using deionized water as a solvent, the intermediate product 2, double-bonded silicon dioxide, and ammonium persulfate were mixed in a mass ratio of 1:2:0.05, heated to 80°C and stirred for 6 hours. After centrifugation, washing, and drying, modified graphene oxide was obtained. S5. According to the above-mentioned mass proportions, the modified graphene oxide is mixed with the remaining components and stirred evenly to obtain the modified graphene oxide epoxy zinc-containing primer.

[0026] Example 2 A modified graphene oxide epoxy zinc-containing primer, wherein the modified graphene oxide epoxy zinc-containing primer comprises the following components in parts by weight: 14 parts epoxy resin 18 portions of mica powder 7 parts barium sulfate 8 parts of anti-rust pigment 6 parts zinc powder 2 parts of modified graphene oxide 18 parts of solvent 6 parts of auxiliary agent 7 parts curing agent; The preparation method of the modified graphene oxide epoxy zinc-containing primer includes the following steps: S1. Graphene oxide and deionized water were mixed at a mass ratio of 1:1000 and ultrasonically dispersed for 20 min. KH560 (the mass ratio of graphene oxide to KH560 was 1:0.7) was added. The pH was adjusted to 4 with acetic acid and stirred for 5 h. The mixture was then vacuum filtered, washed, and dried to obtain intermediate product 1. S2. Using deionized water as a solvent, intermediate product 1 and 2-hydroxyethyl acrylate were blended at a mass ratio of 1:5. A 10wt% sodium hydroxide solution was added to adjust the pH to 11. The mixture was heated to 60°C and stirred for 4 hours. After centrifugation, washing, and drying, intermediate product 2 was obtained. S3. Using ethanol and deionized water in a volume ratio of 1:1 as solvents, silica and KH570 were mixed in a mass ratio of 1:1.5, heated to 50°C and stirred for 24 hours. After filtration, washing and drying, silica containing double bonds was obtained. S4. Under a nitrogen atmosphere, using deionized water as a solvent, the intermediate product 2, double-bonded silicon dioxide, and ammonium persulfate were mixed in a mass ratio of 1:2:0.05, heated to 80°C and stirred for 6 hours. After centrifugation, washing, and drying, modified graphene oxide was obtained. S5. According to the above-mentioned mass proportions, the modified graphene oxide is mixed with the remaining components and stirred evenly to obtain the modified graphene oxide epoxy zinc-containing primer.

[0027] Example 3 A modified graphene oxide epoxy zinc-containing primer, wherein the modified graphene oxide epoxy zinc-containing primer comprises the following components in parts by weight: 10 parts epoxy resin 15 parts mica powder 5 parts barium sulfate 6 parts of anti-rust pigment 2 parts zinc powder 1 part modified graphene oxide 15 parts solvent 3 parts of auxiliary agent 5 parts curing agent; The preparation method of the modified graphene oxide epoxy zinc-containing primer includes the following steps: S1. Graphene oxide and deionized water were mixed at a mass ratio of 1:1000 and ultrasonically dispersed for 20 min. KH560 (the mass ratio of graphene oxide to KH560 was 1:0.6) was added. The pH was adjusted to 4 with acetic acid and stirred for 5 h. The mixture was then vacuum filtered, washed, and dried to obtain intermediate product 1. S2. Using deionized water as solvent, intermediate product 1 and 2-hydroxyethyl acrylate were blended at a mass ratio of 1:6. A 10wt% sodium hydroxide solution was added to adjust the pH to 11. The mixture was heated to 60°C and stirred for 4 hours. After centrifugation, washing, and drying, intermediate product 2 was obtained. S3. Using ethanol and deionized water in a volume ratio of 1:1 as solvents, silica and KH570 were mixed in a mass ratio of 1:1.5, heated to 50°C and stirred for 24 hours. After filtration, washing and drying, silica containing double bonds was obtained. S4. Under a nitrogen atmosphere, using deionized water as a solvent, the intermediate product 2, double-bonded silicon dioxide, and ammonium persulfate were mixed in a mass ratio of 1:2:0.05, heated to 80°C and stirred for 6 hours. After centrifugation, washing, and drying, modified graphene oxide was obtained. S5. According to the above-mentioned mass proportions, the modified graphene oxide is mixed with the remaining components and stirred evenly to obtain the modified graphene oxide epoxy zinc-containing primer.

[0028] Comparative Example The difference between the comparative example and Example 1 is that steps S3 and S4 are deleted, intermediate product 2 is used instead of modified graphene oxide, and the remaining components and preparation methods are the same as in Example 1.

[0029] Test case The performance of the primers prepared in Examples 1-3 and the comparative examples was tested.

[0030] Coating preparation method: Select a sandblasted steel plate with a surface cleanliness of Sa2.5 grade as specified in GB / T 8923.1-2011 and a surface roughness of "Medium (G)" grade as specified in GB / T 13288.1-2008. The substrate size is 150×70×5mm. Apply two coats of primer to the sample. The dry film thickness is 130-140µm. Then, cure it for seven days under the conditions specified in GB / T 9278 and seal the edges for testing.

[0031] Test method: Adhesion: Tested in accordance with GB / T 9286 standard.

[0032] Resistance to neutral salt spray: Tested according to GB / T 1771 standard.

[0033] Storage stability (settling properties): Tested in accordance with GB / T 6753.3-1986 standard.

[0034] Acid resistance: The coated samples were immersed in 10wt% HCl for acid corrosion resistance testing.

[0035] Alkali resistance: The coated samples were immersed in 10wt% NaOH for alkali corrosion resistance test.

[0036] The test results are shown in Table 1. Figure 1 , Figure 2 As shown.

[0037] Figure 1 The image shows the effect of the modified graphene oxide epoxy zinc-containing primer prepared in Example 1 after a neutral salt spray test.

[0038] Figure 2 The results of the primer prepared in the comparative example underwent a neutral salt spray resistance test are shown in the figure.

[0039] Table 1. Test results of primer performance From Table 1, Figure 1 , Figure 2 As can be seen, the performance of Examples 1-3 is better than that of the comparative example. This is because the comparative example did not introduce silica, which reduced the compatibility of intermediate product 2 with the other components, making it difficult to disperse evenly and prone to aggregation. This reduced the barrier effect against corrosive substances, resulting in a decline in the performance of the coating.

[0040] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, it is intended that all variations falling within the meaning and scope of equivalents of the claims be included within the present invention.

[0041] Furthermore, it should be understood that although this specification describes embodiments, not every embodiment contains only one independent technical solution. This narrative style is merely for clarity. Those skilled in the art should consider the specification as a whole, and the technical solutions in each embodiment can also be appropriately combined to form other embodiments that can be understood by those skilled in the art.

Claims

1. A modified graphene oxide epoxy zinc-containing primer, characterized in that, The modified graphene oxide epoxy zinc-containing primer comprises the following components in parts by weight: 10-18 parts epoxy resin 15-21 parts mica powder 5-10 parts of barium sulfate 6-9 parts of anti-rust pigment 2-10 parts zinc powder 1-2 parts of modified graphene oxide 15-22 parts solvent 3-8 parts of auxiliary agent 5-11 parts of curing agent; The modified graphene oxide is obtained by reacting graphene oxide with KH560, grafting 2-hydroxyethyl acrylate onto it, and then polymerizing it with silica containing double bonds.

2. The modified graphene oxide epoxy zinc-containing primer according to claim 1, characterized in that, The solvent is selected from one or more of dimethylformamide, dioxydimethyl ether acetate, xylene, and n-butanol.

3. The modified graphene oxide epoxy zinc-containing primer according to claim 1, characterized in that, The additives are selected from one or more of dispersants, leveling agents, defoamers, emulsifiers, and film-forming aids.

4. The method for preparing the modified graphene oxide epoxy zinc-containing primer according to any one of claims 1-3, characterized in that, The preparation method of the modified graphene oxide epoxy zinc-containing primer includes the following steps: S1. Graphene oxide and KH560 are mixed and stirred to obtain intermediate product 1. S2. The intermediate product 1, 2-hydroxyethyl acrylate, and catalyst are blended and heated and stirred to obtain intermediate product 2. S3. Silica and KH570 are mixed and heated and stirred to react, yielding silica containing double bonds; S4. Under an inert atmosphere, the intermediate product 2, silicon dioxide containing double bonds, and an initiator are blended, heated, and stirred to react and obtain modified graphene oxide. S5. The modified graphene oxide is mixed with the remaining components and stirred evenly to obtain the modified graphene oxide epoxy zinc-containing primer.

5. The preparation method of the modified graphene oxide epoxy zinc-containing primer according to claim 4, characterized in that, In step S1, the mass ratio of graphene oxide to KH560 is 1:(0.5-0.7).

6. The preparation method of the modified graphene oxide epoxy zinc-containing primer according to claim 4, characterized in that, In step S2, the mass ratio of the intermediate product 1-hydroxyethyl acrylate to 2-hydroxyethyl acrylate is 1:(4-6).

7. The preparation method of the modified graphene oxide epoxy zinc-containing primer according to claim 4, characterized in that, In step S2, the temperature of the heating and stirring reaction is 50-70℃.

8. The preparation method of the modified graphene oxide epoxy zinc-containing primer according to claim 4, characterized in that, In step S3, the mass ratio of silicon dioxide to KH570 is 1:(1.4-1.6).

9. The preparation method of the modified graphene oxide epoxy zinc-containing primer according to claim 4, characterized in that, In step S4, the mass ratio of intermediate product 2 to silicon dioxide containing double bonds is 1:(1-3).

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