Heavy-duty anti-corrosion resin and preparation method thereof

Abstract

The invention relates to heavy anti-corrosion resin and a preparation method thereof, and belongs to the technical field of resin preparation. The formula of the heavy anti-corrosion resin comprises the following components in parts by weight: 80-100 parts of epoxy resin, 6-8 parts of liquid nitrile rubber, 3-5 parts of composite cerous phosphate, 1.5-2.5 parts of modified graphene oxide and 1-2 parts of polyethylene glycol. Wherein the cerous phosphate nanorods are large in specific surface area and high in length-diameter ratio, and are stably compounded with uniformly loaded nano zinc oxide to form double anti-corrosion barriers, and the dispersity and compatibility of the cerous phosphate nanorods can be improved by a dopamine coating; the modified graphene oxide is uniformly dispersed to form a labyrinth type shielding layer, and the modified graphene oxide and the composite cerous phosphate are mutually filled to form a multi-layer barrier; the liquid nitrile rubber and the epoxy resin form an interpenetrating network, so that the impact resistance and the adhesive force are enhanced; the polyethylene glycol improves the flexibility of the resin, adjusts the glass transition temperature and reduces the defects of the coating. The resin prepared according to the formula provided by the invention has an excellent anti-corrosion effect.

Description

Technical Field

[0001] The invention belongs to the technical field of resin preparation and relates to a heavy-duty anticorrosive resin and a preparation method thereof. Background Art

[0002] In the industrial field, metal structures and equipment serve as the basic support for various production activities and are constantly facing erosion from complex and harsh environments. Taking the marine environment as an example, the corrosive ions such as chloride ions rich in seawater will undergo strong electrochemical reactions with the metal surface, accelerating the corrosion process of the metal. In the chemical environment, chemical substances such as strong acids and strong bases are extremely chemically active and corrosive, and can cause serious damage to metal materials. These corrosion phenomena are not limited to changes in the appearance of the metal surface, but will penetrate deep into the metal, resulting in reduced strength of metal components and damaged structural integrity. Therefore, the development of heavy-duty anti-corrosion resins with excellent anti-corrosion properties is of great practical significance.

[0003] However, although existing heavy-duty anti-corrosion resins have a certain anti-corrosion effect, they perform poorly in extreme environments. At high temperatures, the molecular chain movement of common heavy-duty anti-corrosion resins such as epoxy resins intensifies, the internal cross-linking structure may be destroyed, and the mechanical properties and anti-corrosion performance are greatly reduced. At the same time, high temperatures accelerate the diffusion of corrosive media, making it easier for them to penetrate the coating and react with the metal substrate, reducing the protective effect. In highly corrosive media, such as strong acid and strong alkali solutions, the resin may undergo hydrolysis, dissolution and other reactions and become ineffective; solutions containing oxidizing substances may also oxidize and destroy the coating, weakening the anti-corrosion ability. This makes existing heavy-duty anti-corrosion resins unable to meet the long-term and high-efficiency anti-corrosion needs in extreme industrial environments. Therefore, there is an urgent need to develop heavy-duty anti-corrosion resins that can maintain excellent anti-corrosion properties in extreme environments to address the limitations of existing technologies in extreme environment applications. Summary of the Invention

[0004] The object of the present invention is to provide a heavy-duty anticorrosive resin and a preparation method thereof, wherein the prepared resin has the characteristics of excellent corrosion resistance.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A heavy-duty anti-corrosion resin, wherein the formula of the heavy-duty anti-corrosion resin is as follows: in parts by weight, 80-100 parts of epoxy resin, 6-8 parts of liquid nitrile rubber, 3-5 parts of composite cerium phosphate, 1.5-2.5 parts of modified graphene oxide, and 1-2 parts of polyethylene glycol; The preparation method of the composite cerium phosphate is as follows: S1-1: 20 parts by weight of a 0.1 M sodium hydrogen phosphate solution was added dropwise to 20 parts by weight of a 0.1 M cerium nitrate solution at 300-400 rpm, and the mixture was stirred for 0.5-1.5 h. The pH of the solution was adjusted with a 50% by mass aqueous orthophosphoric acid solution. The mixture was then stirred in a constant temperature water bath at 88-92°C for 20-24 h, washed with deionized water and anhydrous ethanol, respectively, and then dried in a vacuum oven at 70-80°C for 12 h to obtain powder A. S1-2: 10-20 parts by weight of powder A were added to 80-90 parts by weight of anhydrous ethanol, and ultrasonicated for 1-2 hours. Nano-zinc oxide was then added and ultrasonicated for 2-4 hours. The pH value of the suspension was adjusted to 7-8, and the suspension was allowed to stand for 1-2 hours. The suspension was washed with deionized water and then vacuum dried at 100°C for 12 hours to obtain powder B. S1-3: Prepare a dopamine hydrochloric acid solution and adjust the pH to 8.5-9.5, add powder B to the dopamine hydrochloric acid solution so that the solid-liquid mass ratio is 10 g / L, stir at a speed of 500-600 rpm for 1-2 hours, wash with deionized water until the pH of the eluate is neutral, and freeze-dry at -40°C for 12 hours to obtain the composite cerium phosphate.

[0006] As a preferred technical solution of the present invention, the preparation steps of the modified graphene oxide are as follows: 10 parts by weight of graphene oxide are dispersed in 100 parts by weight of a 50% ethanol solution, 3-aminopropyltriethoxysilane is added, and the mixture is stirred at 60-80°C for 4-6 hours. The mixture is then washed with deionized water and dried at 60°C for 12 hours to obtain the modified graphene oxide.

[0007] As a preferred technical solution of the present invention, the dropping speed of the disodium hydrogen phosphate solution in S1-1 is 2 to 3 mL / min.

[0008] As a preferred technical solution of the present invention, in S1-1, the pH of the solution is adjusted to 1.3-1.5 using an orthophosphoric acid aqueous solution.

[0009] As a preferred technical solution of the present invention, the ultrasonic power in S1-2 is 200-300 W.

[0010] As a preferred technical solution of the present invention, the added amount of nano zinc oxide in S1-2 is 0.4 to 0.6 times the mass of powder A.

[0011] As a preferred technical solution of the present invention, a dopamine hydrochloric acid solution with a mass fraction of 10% to 20% is prepared in S1-3.

[0012] As a preferred technical solution of the present invention, the addition amount of the 3-aminopropyltriethoxysilane is 3% to 5% of the mass of the graphene oxide.

[0013] A method for preparing a heavy-duty anticorrosive resin, wherein the specific steps of the preparation method are as follows: Epoxy resin is added to a reaction vessel according to the formula ratio, stirred at a speed of 250 to 350 rpm for 5 to 10 minutes, liquid nitrile rubber is added, stirring is continued for 10 to 20 minutes, modified graphene oxide is added, ultrasonic stirring is performed for 10 to 20 minutes, and finally, composite cerium phosphate and polyethylene glycol are added, and the speed is adjusted to 150 to 250 rpm to obtain the heavy-duty anticorrosion resin.

[0014] Using an aqueous solution of orthophosphoric acid to adjust the solution's pH influences the activity and charge distribution of ions, guiding crystal growth in specific directions and ultimately forming a nanorod structure. Stirring in a constant-temperature water bath at 88-92°C for 20-24 hours intensifies the molecular thermal motion of the reactants, significantly increasing their activity and leading to more frequent and effective intermolecular collisions, which promotes nucleation and orderly crystal growth. The resulting cerium phosphate nanorod structure possesses a large surface area, meaning more active sites on the nanorod surface, enabling more efficient interactions with the resin matrix and other additives. The cerium phosphate nanorods intertwine within the resin, forming a three-dimensional protective network. This network effectively blocks the penetration of corrosive media, significantly reducing the penetration path and difficulty. The high aspect ratio of the cerium phosphate nanorods allows them to better fill the voids in the resin. During the resin curing process, the nanorods fill the gaps between resin molecules, forming a denser protective layer that blocks the ingress of corrosive media such as oxygen and moisture, further enhancing the resin's corrosion protection.

[0015] After adding nano-zinc oxide, the material is ultrasonically treated. The ultrasound waves generate sufficient energy for the nano-zinc oxide particles to overcome the inter-particle interactions, resulting in uniform loading on the surface of the cerium phosphate nanorods. Furthermore, the pH of the suspension is adjusted to align the surface charge states of the nano-zinc oxide particles with those of the cerium phosphate nanorods, promoting adsorption and enhancing the stability of the composite. The combination of nano-zinc oxide and cerium phosphate complements each other in terms of corrosion resistance, creating a significant synergistic effect. Nano-zinc oxide, which possesses inherent antibacterial and anticorrosive properties, can form a dual anticorrosive barrier with cerium phosphate. By releasing zinc ions, nano-zinc oxide inhibits bacterial growth and reproduction, reducing microbial corrosion of the resin. Cerium phosphate also chemically reacts with the corrosive medium, forming a dense protective film that prevents further penetration. Nano-zinc oxide fills the gaps between the cerium phosphate particles, forming a denser protective layer together with the cerium phosphate nanorods. The close bonding between nano-zinc oxide and cerium phosphate nanorods enhances the stability of the resin. When affected by the external environment, such as temperature and humidity changes, the resin can maintain the stability of its structure and performance and is not prone to decomposition or failure.

[0016] Dopamine hydrochloric acid solution undergoes self-polymerization under alkaline conditions, forming a polydopamine coating on the surface of the cerium phosphate and nano-zinc oxide composite. This polydopamine coating improves the dispersibility of the composite cerium phosphate in the resin. The polydopamine molecules possess both hydrophilic and lipophilic properties, forming a well-dispersed interface within the resin matrix, evenly dispersing the composite cerium phosphate particles and preventing agglomeration. The polydopamine coating also enhances the compatibility of the composite cerium phosphate with the resin. Functional groups such as amino and phenolic hydroxyl groups in the polydopamine molecules chemically react or physically adsorb with the resin molecules, forming chemical or hydrogen bonds, thereby improving the interfacial bonding of the composite and better integrating the composite cerium phosphate with the resin. The polydopamine coating itself exhibits certain anti-corrosion properties, forming a physical barrier to prevent the penetration of corrosive media. Furthermore, the polydopamine coating synergizes with the cerium phosphate and nano-zinc oxide, further enhancing the composite's anti-corrosion effectiveness. For example, the polydopamine coating can repair minor defects in the protective layer of the cerium phosphate and nano-zinc oxide, enhancing the integrity of the protective layer.

[0017] After modification with 3-aminopropyltriethoxysilane, the steric hindrance between the graphene oxide flakes is increased, effectively preventing the flakes from agglomerating, allowing the modified graphene oxide to be evenly dispersed in the heavy-duty anti-corrosion resin. Modified graphene oxide inherits the large specific surface area and two-dimensional lamellar structure of graphene oxide, enabling it to form a maze-like shielding layer in the coating. At the same time, modified graphene oxide has excellent mechanical properties. When the coating is subjected to external forces, the modified graphene oxide can bear part of the stress and improve the mechanical properties of the coating. The active groups on the surface of the modified graphene oxide and its unique lamellar structure allow the modified graphene oxide flakes to rearrange and interact at the cracks when the coating is slightly damaged, restoring the protective properties of the coating.

[0018] The flake structure of the modified graphene oxide and the nanorod structure of the composite cerium phosphate can interpenetrate each other, forming a denser coating structure. The flakes of modified graphene oxide fill the gaps between the composite cerium phosphate particles, while the composite cerium phosphate particles are dispersed between the flakes of modified graphene oxide, reducing porosity and defects in the coating. The synergistic effect of the composite cerium phosphate and modified graphene oxide forms a multi-layered, three-dimensional corrosion barrier, further increasing the difficulty for corrosive media to reach the metal substrate, significantly enhancing the coating's corrosion protection.

[0019] Epoxy resin is inherently brittle and prone to cracking under external impact. Liquid nitrile rubber, however, leverages its flexibility to form an interpenetrating network with epoxy resin. When subjected to external forces, the rubber molecular chains deform to absorb energy, dissipating stress and preventing crack propagation, significantly enhancing the coating's impact resistance. Furthermore, it helps strengthen the adhesion between the resin and the metal substrate. The polar cyanide groups in the nitrile rubber molecules can form chemical or hydrogen bonds with metal atoms, and its good compatibility with epoxy resin allows the coating to adhere firmly to the metal surface, preventing shedding that could compromise its corrosion resistance.

[0020] Polyethylene glycol can improve the resin's flexibility and impact resistance. Its long-chain molecules can insert into the epoxy resin's cross-linked network, acting as a lubricant and plasticizer, reducing the forces between molecular chains, making the resin more deformable, absorbing external energy, and reducing the risk of cracking. It can also regulate the glass transition temperature, allowing the resin to maintain flexibility at low temperatures and adapt to different ambient temperatures. Secondly, polyethylene glycol has good surface activity and good compatibility with ingredients such as epoxy resin and liquid nitrile rubber, helping to form a uniform system and reduce coating defects.

[0021] Beneficial effects of the present invention: The cerium phosphate nanorods prepared by the present invention have a large specific surface area and a high aspect ratio. They are interwoven in the resin to form a three-dimensional protective network, fill the gaps, and effectively block the penetration of corrosive media; nano zinc oxide is evenly loaded on the surface of the nanorods, and the two are composited and stable, complementing each other in terms of anti-corrosion performance to form a double anti-corrosion barrier, and can also enhance the stability of the resin; the polydopamine coating formed by the self-polymerization of the dopamine hydrochloric acid solution can improve the dispersibility of the composite cerium phosphate in the resin, avoid agglomeration, enhance the compatibility with the resin, improve the interfacial bonding force, and further enhance the overall anti-corrosion effect of the composite material.

[0022] Modified graphene oxide is uniformly dispersed in the resin, forming a labyrinthine shielding layer with its large surface area and two-dimensional structure. Its excellent mechanical properties enhance the coating's mechanical strength and possess self-healing potential. Interpenetrating with composite cerium phosphate, it forms a dense structure and a multi-layered anti-corrosion barrier, enhancing its effectiveness. Liquid nitrile rubber and epoxy resin form an interpenetrating network, improving impact resistance, while its polar groups enhance adhesion between the resin and the metal substrate. Polyethylene glycol improves the resin's flexibility and impact resistance, modulates its glass transition temperature, and, through its excellent surface activity and compatibility, reduces coating defects, ensuring stable performance in a variety of environments and significantly improving its anti-corrosion effectiveness. DETAILED DESCRIPTION

[0023] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined purpose of the invention, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0024] In the Examples of the present invention and the Comparative Examples: Epoxy resin: purchased from Jinan Chuangshi Chemical Co., Ltd., model E51; Liquid nitrile rubber: purchased from Wuhan Hongde Yuexin Pharmaceutical Technology Co., Ltd. Sodium hydrogen phosphate: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. Cerium nitrate: purchased from Shandong Zhengxing New Materials Co., Ltd. Nano zinc oxide: purchased from Shanghai Dingfen Chemical Technology Co., Ltd. Dopamine hydrochloric acid solution: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. Graphene oxide: purchased from Anhui Kerun Nanotechnology Co., Ltd. 3-Aminopropyltriethoxysilane: purchased from Jiangxi Hongbai New Materials Co., Ltd. Polyethylene glycol 600: purchased from Shandong Qianfanshun Chemical Co., Ltd.

[0025] Example 1

[0026] A heavy-duty anticorrosion resin, wherein the formula of the heavy-duty anticorrosion resin is as follows: in parts by weight, 90 parts of epoxy resin, 7 parts of liquid nitrile rubber, 4 parts of composite cerium phosphate, 2 parts of modified graphene oxide, and 1.5 parts of polyethylene glycol; The preparation method of the composite cerium phosphate is as follows: S1-1: 20 parts by weight of a 0.1 M sodium hydrogen phosphate solution were added dropwise to 20 parts by weight of a 0.1 M cerium nitrate solution at a rate of 2.5 mL / min at a rotation speed of 350 rpm. The mixture was stirred for 1 h. The pH of the solution was adjusted to 1.4 with a 50% by mass aqueous solution of orthophosphoric acid. The mixture was then stirred in a 90°C constant temperature water bath for 22 h. The mixture was washed with deionized water and anhydrous ethanol, respectively, and then dried in a vacuum oven at 75°C for 12 h to obtain powder A. S1-2: 15 parts by weight of powder A was added to 85 parts by weight of anhydrous ethanol and ultrasonicated for 1.5 h. Subsequently, 0.5 times the mass of nano-zinc oxide of powder A was added and ultrasonicated for 3 h at a power of 250 W. The pH value of the suspension was adjusted to 7.5 and the suspension was allowed to stand for 1.5 h. The suspension was then washed with deionized water and vacuum dried at 100 °C for 12 h to obtain powder B. S1-3: Prepare a 15% mass fraction dopamine hydrochloric acid solution and adjust the pH to 9, add powder B to the dopamine hydrochloric acid solution so that the solid-liquid mass ratio is 10 g / L, stir at 550 rpm for 1.5 hours, wash with deionized water until the pH of the eluate is neutral, and freeze-dry at -40°C for 12 hours to obtain the composite cerium phosphate.

[0027] The modified graphene oxide is prepared by dispersing 10 parts by weight of graphene oxide in 100 parts by weight of a 50% ethanol solution, adding 4% by weight of 3-aminopropyltriethoxysilane based on the mass of the graphene oxide, stirring at 70°C for 5 hours, then washing with deionized water and drying at 60°C for 12 hours to obtain the modified graphene oxide.

[0028] A method for preparing a heavy-duty anticorrosive resin, wherein the specific steps of the preparation method are as follows: Epoxy resin was added to a reaction vessel according to the formula ratio, stirred at 300 rpm for 8 minutes, liquid nitrile rubber was added, and stirring was continued for 15 minutes, modified graphene oxide was added, and ultrasonic stirring was performed for 15 minutes. Finally, composite cerium phosphate and polyethylene glycol were added, and the rotation speed was adjusted to 200 rpm to obtain the heavy-duty anticorrosion resin.

[0029] Example 2

[0030] A heavy-duty anticorrosion resin, wherein the formula of the heavy-duty anticorrosion resin is as follows: in parts by weight, 80 parts of epoxy resin, 6 parts of liquid nitrile rubber, 3 parts of composite cerium phosphate, 1.5 parts of modified graphene oxide, and 1 part of polyethylene glycol; The preparation method of the composite cerium phosphate is as follows: S1-1: 20 parts by weight of a 0.1 M sodium hydrogen phosphate solution were added dropwise to 20 parts by weight of a 0.1 M cerium nitrate solution at a rate of 2 mL / min at a rotation speed of 300 rpm. The mixture was stirred for 0.5 h. The pH of the solution was adjusted to 1.3 with a 50% by mass aqueous solution of orthophosphoric acid. The mixture was then stirred in a constant temperature water bath at 88°C for 20 h. The mixture was washed with deionized water and anhydrous ethanol, respectively, and then dried in a vacuum oven at 70°C for 12 h to obtain powder A. S1-2: 10 parts by weight of powder A was added to 80 parts by weight of anhydrous ethanol and ultrasonicated for 1 h. Subsequently, 0.4 times the mass of nano-zinc oxide of powder A was added and ultrasonicated for 2 h at a power of 200 W. The pH value of the suspension was adjusted to 7 and the suspension was allowed to stand for 1 h. The suspension was then washed with deionized water and dried in a vacuum oven at 100°C for 12 h to obtain powder B. S1-3: Prepare a 10% mass fraction dopamine hydrochloric acid solution and adjust the pH to 8.5, add powder B to the dopamine hydrochloric acid solution so that the solid-liquid mass ratio is 10 g / L, stir at 500 rpm for 1 hour, wash with deionized water until the pH of the eluate is neutral, and freeze-dry at -40°C for 12 hours to obtain the composite cerium phosphate.

[0031] The modified graphene oxide is prepared by dispersing 10 parts by weight of graphene oxide in 100 parts by weight of a 50% ethanol solution, adding 3% 3-aminopropyltriethoxysilane based on the mass of the graphene oxide, stirring at 60°C for 4 hours, then washing with deionized water and drying at 60°C for 12 hours to obtain the modified graphene oxide.

[0032] A method for preparing a heavy-duty anticorrosive resin, wherein the specific steps of the preparation method are as follows: Epoxy resin was added to a reaction vessel according to the formula ratio, stirred at a speed of 250 rpm for 5 minutes, liquid nitrile rubber was added, and stirring was continued for 10 minutes, modified graphene oxide was added, and ultrasonic stirring was performed for 10 minutes. Finally, composite cerium phosphate and polyethylene glycol were added, and the speed was adjusted to 150 rpm to obtain the heavy-duty anticorrosion resin.

[0033] Example 3

[0034] A heavy-duty anticorrosion resin, wherein the formula of the heavy-duty anticorrosion resin is as follows: in parts by weight, 100 parts of epoxy resin, 8 parts of liquid nitrile rubber, 5 parts of composite cerium phosphate, 2.5 parts of modified graphene oxide, and 2 parts of polyethylene glycol; The preparation method of the composite cerium phosphate is as follows: S1-1: 20 parts by weight of a 0.1 M sodium hydrogen phosphate solution were added dropwise to 20 parts by weight of a 0.1 M cerium nitrate solution at a rate of 3 mL / min at 400 rpm. The mixture was stirred for 1.5 h. The pH of the solution was adjusted to 1.5 with a 50% by mass aqueous solution of orthophosphoric acid. The mixture was then stirred in a 92°C water bath for 24 h. The mixture was washed with deionized water and anhydrous ethanol, respectively, and then dried in a vacuum oven at 80°C for 12 h to obtain powder A. S1-2: 20 parts by weight of powder A were added to 90 parts by weight of anhydrous ethanol and ultrasonicated for 2 h. Subsequently, 0.6 times the mass of nano-zinc oxide was added to powder A and ultrasonicated for 4 h at a power of 300 W. The pH value of the suspension was adjusted to 8, and the suspension was allowed to stand for 2 h. The suspension was then washed with deionized water and dried in a vacuum oven at 100°C for 12 h to obtain powder B. S1-3: Prepare a 20% mass fraction dopamine hydrochloric acid solution and adjust the pH to 9.5, add powder B to the dopamine hydrochloric acid solution so that the solid-liquid mass ratio is 10 g / L, stir at 600 rpm for 2 hours, wash with deionized water until the pH of the eluate is neutral, and freeze-dry at -40°C for 12 hours to obtain the composite cerium phosphate.

[0035] The modified graphene oxide is prepared by dispersing 10 parts by weight of graphene oxide in 100 parts by weight of a 50% ethanol solution, adding 3-aminopropyltriethoxysilane at a concentration of 5% by weight of the graphene oxide, stirring at 80°C for 6 hours, then washing with deionized water and drying at 60°C for 12 hours to obtain the modified graphene oxide.

[0036] A method for preparing a heavy-duty anticorrosive resin, wherein the specific steps of the preparation method are as follows: Epoxy resin was added to a reaction vessel according to the formula ratio, stirred at 350 rpm for 10 minutes, liquid nitrile rubber was added, and stirring was continued for 20 minutes, modified graphene oxide was added, and ultrasonic stirring was performed for 20 minutes. Finally, composite cerium phosphate and polyethylene glycol were added, and the rotation speed was adjusted to 250 rpm to obtain the heavy-duty anticorrosion resin.

[0037] Comparative Example 1 The preparation of the composite cerium phosphate does not go through step S1-2, and the remaining steps are consistent with Example 1.

[0038] Comparative Example 2 The preparation of the composite cerium phosphate does not go through steps S1-3, and the remaining steps are consistent with those in Example 1.

[0039] Comparative Example 3 In the preparation of the composite cerium phosphate, commercially available cerium phosphate was used instead of powder A. The commercially available cerium phosphate was purchased from Guangdong Wengjiang Chemical Reagent Co., Ltd., and the remaining steps were the same as those in Example 1.

[0040] Comparative Example 4 The preparation of the composite cerium phosphate does not go through steps S1-2 and S1-3, and the remaining steps are consistent with those in Example 1.

[0041] Comparative Example 5 Without adding composite cerium phosphate, the remaining steps were the same as those in Example 1.

[0042] Comparative Example 6 The graphene oxide was not modified, and the remaining steps were consistent with those in Example 1.

[0043] Comparative Example 7 Without adding modified graphene oxide, the remaining steps were the same as those in Example 1.

[0044] Comparative Example 8 Without adding polyethylene glycol, the remaining steps were the same as those in Example 1.

[0045] Test Example 1 Corrosion resistance test: The heavy-duty anticorrosive resins prepared in the Examples and Comparative Examples were evenly coated on the surfaces of Q235 carbon steel specimens to a coating thickness of 100 μm. The specimens were cured for 7 days at 37°C and 50% humidity. The specimens were then placed in a salt spray chamber and periodically sprayed with a 3.5wt% sodium chloride solution. The specimen surfaces were observed, and the time it took for rust and blistering to appear was recorded. The experimental results are reported in the following table.

[0046]

[0047] It can be seen from the examples and comparative examples that the resin prepared in the present invention has excellent corrosion resistance.

[0048] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as a preferred embodiment as above, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are within the scope of the technical solution of the present invention.

Claims

1. A heavy-duty anticorrosive resin, characterized in that: The formula of the heavy anti-corrosion resin is as follows: in parts by weight, 80-100 parts of epoxy resin, 6-8 parts of liquid nitrile rubber, 3-5 parts of composite cerium phosphate, 1.5-2.5 parts of modified graphene oxide, and 1-2 parts of polyethylene glycol; The preparation method of the composite cerium phosphate is as follows: S1-1: 20 parts by weight of a 0.1 M sodium hydrogen phosphate solution was added dropwise to 20 parts by weight of a 0.1 M cerium nitrate solution at 300-400 rpm, and the mixture was stirred for 0.5-1.5 h. The pH of the solution was adjusted with a 50% by mass aqueous orthophosphoric acid solution. The mixture was then stirred in a constant temperature water bath at 88-92°C for 20-24 h, washed with deionized water and anhydrous ethanol, respectively, and then dried in a vacuum oven at 70-80°C for 12 h to obtain powder A. S1-2: 10-20 parts by weight of powder A were added to 80-90 parts by weight of anhydrous ethanol, and ultrasonicated for 1-2 hours. Nano-zinc oxide was then added and ultrasonicated for 2-4 hours. The pH value of the suspension was adjusted to 7-8, and the suspension was allowed to stand for 1-2 hours. The suspension was washed with deionized water and then vacuum dried at 100°C for 12 hours to obtain powder B. S1-3: Prepare a dopamine hydrochloric acid solution and adjust the pH to 8.5-9.5, add powder B to the dopamine hydrochloric acid solution so that the solid-liquid mass ratio is 10 g / L, stir at a speed of 500-600 rpm for 1-2 hours, wash with deionized water until the pH of the eluate is neutral, and freeze-dry at -40°C for 12 hours to obtain the composite cerium phosphate.

2. A heavy-duty anticorrosive resin according to claim 1, characterized in that: The modified graphene oxide is prepared by dispersing 10 parts by weight of graphene oxide in 100 parts by weight of a 50% ethanol solution, adding 3-aminopropyltriethoxysilane, stirring at 60-80°C for 4-6 hours, then washing with deionized water and drying at 60°C for 12 hours to obtain the modified graphene oxide.

3. A heavy-duty anticorrosive resin according to claim 1, characterized in that: The dropping speed of the sodium hydrogen phosphate solution in S1-1 is 2 to 3 mL / min.

4. A heavy-duty anticorrosive resin according to claim 1, characterized in that: In the S1-1, the pH of the solution is adjusted to 1.3-1.5 using an orthophosphoric acid aqueous solution.

5. The heavy-duty anticorrosive resin according to claim 1, characterized in that: The ultrasonic power in S1-2 is 200-300 W.

6. The heavy-duty anticorrosive resin according to claim 1, characterized in that: The added amount of nano zinc oxide in S1-2 is 0.4 to 0.6 times the mass of powder A.

7. The heavy-duty anticorrosive resin according to claim 1, characterized in that: In the S1-3, a dopamine hydrochloric acid solution with a mass fraction of 10% to 20% is prepared.

8. The heavy-duty anticorrosive resin according to claim 2, characterized in that: The added amount of the 3-aminopropyltriethoxysilane is 3% to 5% of the mass of the graphene oxide.

9. A method for preparing the heavy-duty anticorrosive resin according to any one of claims 1 to 8, characterized in that: The specific steps of the preparation method are as follows: Epoxy resin is added to a reaction vessel according to the formula ratio, stirred at a speed of 250 to 350 rpm for 5 to 10 minutes, liquid nitrile rubber is added, stirring is continued for 10 to 20 minutes, modified graphene oxide is added, ultrasonic stirring is performed for 10 to 20 minutes, and finally, composite cerium phosphate and polyethylene glycol are added, and the speed is adjusted to 150 to 250 rpm to obtain the heavy-duty anticorrosion resin.

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