Intelligent response type marine antirust agent composition as well as preparation method and application thereof

Abstract

The invention discloses an intelligent response type marine antirust agent composition as well as a preparation method and application thereof. The intelligent response type marine antirust agent composition comprises a solvent and the following components in parts by mass: 6-8 parts of ion response microcapsules, 6-8 parts of photo-thermal response microcapsules, 6-9 parts of benzotriazole covalent grafting modified functionalized graphene oxide and 34-38 parts of film-forming resin, a capsule core of the ion response microcapsule is a corrosion inhibitor; the capsule wall is a polyelectrolyte composite membrane formed by self-assembling cationic polyelectrolyte and anionic polyelectrolyte layer by layer, and the outer surface of the capsule wall further comprises an inorganic nanoparticle layer formed by biomimetic mineralization; the cationic polyelectrolyte is poly (diallyldimethylammonium chloride), the anionic polyelectrolyte is sodium polystyrenesulfonate, and the inorganic nanoparticles are calcium carbonate; the photo-thermal response microcapsule comprises a capsule core which is a mixture of CsPbBr and n-octacosane, and a capsule wall which is polyurea formaldehyde.

Description

Technical Field

[0001] This application relates to marine environmental corrosion prevention measures, and in particular to intelligent responsive marine rust inhibitor compositions, preparation methods and applications. Background Technology

[0002] Marine and coastal environments are affected by salt spray, which causes rapid corrosion of metal equipment surfaces. Therefore, it is necessary to apply anti-rust compositions to form films or coatings for rust prevention.

[0003] Existing film-forming rust inhibitors isolate corrosive media by forming a physical barrier on the metal surface. However, their high humidity and direct sunlight characteristics significantly accelerate the aging of anti-corrosion coatings on coastal lifting equipment, cargo ship decks, and the exterior of containers. The aged coating is affected by thermal expansion due to diurnal temperature differences, but its protective effect is passive. Once the coating is damaged, the anti-rust effect is significantly weakened or directly fails.

[0004] Therefore, there is an urgent need in the field for a rust-preventive composition that can accurately respond to the marine environment and provide long-lasting protection. Summary of the Invention

[0005] Given the complex corrosive factors in marine environments, existing rust-preventive compositions are unable to maintain long-term protective effects. This paper presents a smart responsive marine rust inhibitor composition, its preparation method, and its application.

[0006] The first inventive objective of this invention is achieved through the following technical solution: A smart responsive marine rust inhibitor composition comprising a solvent and the following components in parts by weight: 6-8 portions of ion-responsive microcapsules 6-8 portions of photothermal responsive microcapsules 6-9 parts of benzotriazole covalently grafted modified functionalized graphene oxide 34-38 parts of film-forming resin; The core of the ion-responsive microcapsule is a rust inhibitor; The capsule wall is a polyelectrolyte composite membrane composed of cationic and anionic polyelectrolytes through layer-by-layer self-assembly, and the outer surface of the capsule wall also contains a layer of inorganic nanoparticles formed by biomimetic mineralization. The cationic polyelectrolyte is polydiallyldimethylammonium chloride, the anionic polyelectrolyte is sodium polystyrene sulfonate, and the inorganic nanoparticles are calcium carbonate; The photothermal responsive microcapsule comprises a core of a mixture of CsPbBr3 and n-octacosan, and a capsule wall of polyurea formaldehyde.

[0007] By adopting the above technical solution, a synergistic anti-rust system is constructed from ion-responsive microcapsules, photothermal-responsive microcapsules, and benzotriazole covalently grafted functionalized graphene oxide. Its ion-responsive microcapsules have a dual response mechanism: when the Cl⁻ concentration in the environment increases in the early stage of corrosion, its polyelectrolyte composite membrane swells through ion exchange, triggering the early warning release of the rust inhibitor; when local corrosion causes the pH value to drop, the outer biomimetic mineralization layer (calcium carbonate) dissolves, exposing the polyelectrolyte membrane, thereby accelerating the targeted repair release of the rust inhibitor and achieving corrosion blocking. Photothermal responsive microcapsules primarily function as physical regulators: CsPbBr3 efficiently converts ambient light energy into heat energy, prompting a solid-liquid phase transition in the core n-octacosane. During the n-octacosane phase transition, a large amount of latent heat is absorbed or released, creating a "thermal buffer" effect on the coating microenvironment. This effectively mitigates temperature fluctuations, significantly reduces coating thermal stress, and inhibits the generation and propagation of microcracks. Simultaneously, the volume change accompanying the phase transition also helps induce the physical self-healing of microcracks, thereby enhancing the physical integrity and durability of the coating. The use of benzotriazole (BTA) covalently grafted graphene oxide is limited. When the coating is damaged or corrosive media penetrates to the metal interface, the benzotriazole molecules covalently grafted onto the graphene oxide sheets do not easily fall off. Instead, relying on the huge specific surface area of ​​graphene oxide, they are transported to the defect area as a highly efficient "corrosion inhibitor reservoir" and react with the metal surface to form a dense and stable chemical adsorption film, inhibiting the anodic dissolution reaction of the metal. When the marine rust inhibitor composition is applied, the influence of benzotriazole molecules on the benzotriazole molecules in the graphene oxide, as a carrier, allows for directional alignment on the metal surface to exert its excellent physical barrier effect. This ensures that the corrosion inhibitor is evenly dispersed and not easily lost, ensuring the durability and targeting of the repair behavior. It also enhances the actual isolation effect of graphene oxide, effectively delaying the penetration of water, oxygen and corrosive ions, and buying critical time for the intelligent response mechanism. Its sheet structure can also spatially fill the two types of microcapsules, further optimizing the density of the coating. In summary, the synergistic effect of chemical repair by ion-responsive microcapsules and physical regulation by photothermal-responsive microcapsules, combined with the barrier-enhancing effect of graphene oxide, constructs an intelligent protection system that combines passive defense, active repair, and environmental adaptability, which can significantly improve rust prevention performance and coating life in complex marine environments.

[0008] Optionally, the rust inhibitor is a compound of sodium benzoate and cyclohexylamine.

[0009] By adopting the above technical solution, cyclohexylamine, with its high volatility, can rapidly vaporize and diffuse, preferentially adsorbing onto the metal surface to form a hydrophobic film. Sodium benzoate, on the other hand, dissolves and migrates to the metal interface under the influence of moisture. Between the two, the adsorption of cyclohexylamine provides directional anchoring sites for benzoate ions, while the complex protective film formed by benzoate and metal cations fills the possible defects in the cyclohexylamine molecular film, thereby constructing a more dense and stable composite protective layer. This forms a synergistic mechanism of gas phase transport and interfacial film formation, improving corrosion inhibition efficiency.

[0010] Optional: also includes a pH buffer, wherein the pH buffer is zinc dihydrogen phosphate, comprising 1.5-2.2 wt%.

[0011] By adopting the above technical solution, during the metal corrosion process, H⁺ is generated in the anodic region, causing the pH value to decrease, while OH⁻ is generated in the cathode region, causing the pH value to increase. Zinc dihydrogen phosphate is introduced as a pH buffer. The slightly soluble nature of zinc dihydrogen phosphate allows it to continuously and slowly release Zn²⁺, H₂PO₄⁻ and other ions. It can not only directly neutralize H⁺ or OH⁻, but also effectively buffer the drastic fluctuations in pH value, providing a stable interfacial microenvironment for the intelligent response system. This reduces the possibility of the intelligent microcapsules becoming inaccurate in the drastically fluctuating corrosive electrochemical environment. On the other hand, the hydrolysis products of zinc dihydrogen phosphate can form an insoluble zinc phosphate composite protective film at active sites on the metal surface (such as scratches and defects), thus possessing the dual functions of buffering pH and film repair.

[0012] Optional: The film-forming resin is zinc polyacrylate resin.

[0013] By adopting the above technical solution and introducing zinc polyacrylate resin, the working mode and lifespan mechanism of the marine rust inhibitor composition in forming the coating have been changed, transforming it from a "static barrier that gradually fails" into a "dynamic, self-renewing intelligent system." When in contact with seawater, the zinc acrylate chains in the resin undergo ion exchange with sodium ions in the seawater, causing the polymer chains to hydrolyze and dissolve in the seawater at a controlled and extremely slow rate. This continuously smooths the coating surface, effectively preventing marine organisms from adhering, thus providing antifouling functionality. The continuous dissolution of the surface is like "peeling an onion," constantly exposing the unconsumed intelligent microcapsules and functionalized graphene oxide in the inner layer, ensuring that the coating surface always has fresh and highly efficient anti-rust activity. This solves the problem of limited protection cycles caused by aging, contamination, and failure of active ingredients in traditional protective coatings.

[0014] Optional: also includes a stabilizer, wherein the stabilizer is a polyether-modified polysiloxane, comprising 3-5 wt%.

[0015] By adopting the above technical solution, the dispersion stability of graphene oxide and ion-responsive microcapsules in marine rust inhibitor compositions is improved, making the marine rust inhibitor compositions easier to use and store.

[0016] The second objective of this invention is achieved through the following technical solution: A method for preparing a smart responsive marine rust inhibitor composition includes the following steps: S1: Ion-responsive microcapsules, photothermal-responsive microcapsules and graphene oxide are pre-dispersed in a partially environmentally friendly solvent by ultrasound to obtain the first dispersion; S2: Add the remaining environmentally friendly solvent and other remaining components to the first dispersion and mix them evenly under stirring to obtain the second dispersion; S3: Filter the second dispersion to obtain the smart responsive marine rust inhibitor composition.

[0017] By employing the above-mentioned technical solution and a step-by-step mixing process, the preparation involves an initial ultrasonic pre-dispersion step. This involves applying intense but short-duration local energy through the high-frequency cavitation effect generated by ultrasound to highly agglomerated graphene oxide and intricately structured microcapsules in a partially dissolved solvent. This effectively opens the stacked structure of the graphene oxide and allows the microcapsules to initially disperse, while avoiding shear damage to the microcapsule walls that might be caused by mechanical stirring. In the second step, the mixture is gently mechanically stirred with other raw materials to achieve macroscopic homogeneity without requiring high-intensity shear forces. This protects the integrity of the initially dispersed nanomaterials and microcapsules, ensuring that the functional components in the final product exist uniformly and stably, thus achieving the intended intelligent protective effect and preventing the easy agglomeration of graphene oxide and the easy breakage of microcapsules in the intelligent anti-rust composition.

[0018] The third inventive objective of this invention is achieved through the following technical solution: Application of responsive marine rust inhibitor compositions in corrosion protection of marine engineering concrete structures, ship cabins, or enclosed metal components on offshore platforms.

[0019] By adopting the above technical solution, the intelligent responsive marine rust inhibitor composition can effectively diffuse and adsorb onto the metal surface of the entire complex structure in harsh enclosed or semi-enclosed spaces such as marine engineering concrete structures and ship cabins, forming an initial protective film. At the same time, the intelligent microcapsules and functionalized graphene oxide in the composite coating work together to provide a dual guarantee of "targeted repair" and "long-term barrier" for specific parts that are difficult to maintain frequently and have harsh corrosive environments, which cannot be achieved by traditional protection methods.

[0020] In summary, this application has at least the following beneficial effects: 1. By constructing microcapsules with a dual response mechanism of "polyelectrolyte membrane-Cl⁻ response" and "biomimetic mineralization layer-pH response", the rust-preventive composition changes from passive isolation to active adaptation, senses changes in marine environmental corrosion factors, and releases rust inhibitors in a targeted and on-demand manner, significantly improving protection efficiency and component utilization. 2. Functionalized graphene oxide provides a physical barrier; smart microcapsules are responsible for the active repair of damaged areas; self-polishing resin ensures continuous surface renewal and activity; pH ​​buffer stabilizes the interfacial microenvironment; and the synergistic effect between the core components constructs a comprehensive protective network, providing a comprehensive protective effect far exceeding that of single-function technologies. 3. By introducing zinc polyacrylate resin and a stable nanocomposite system, the failure mode of the coating is changed, and the coating surface can continuously self-renew, maintaining the protective activity for a long time. At the same time, the excellent storage stability ensures the consistency of product performance, thereby significantly extending the protection cycle and reducing maintenance costs. Detailed Implementation

[0021] raw material Sodium benzoate, Sinopharm Chemical Reagent Co., Ltd., analytical grade (AR); Cyclohexylamine, a commercially available product from Aladdin Biochemical Technology, analytical grade (AR); Polydiallyldimethylammonium chloride, a commercially available product from Sigma-Aldrich, with an average Mw of 200,000, is available in a 20 wt% aqueous solution. Sodium polystyrene sulfonate, a commercially available product from Sigma-Aldrich, with an average Mw of 70,000; DMF, N,N-dimethylformamide, a commercially available product from Shanghai Titan Technology Co., Ltd., chromatographically pure; Benzotriazole, a commercially available product from TCI (Tokyo Chemical Industry Co., Ltd.), analytical grade (AR); EDC·HCl, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride, a commercially available product from Aladdin Biochemical Technology Co., Ltd., biotechnology grade, 98.8% purity; NHS, N-hydroxysuccinimide, a commercially available product from Aladdin Biochemical Technology Co., Ltd., is biotechnology grade with a purity of 99.5%. Zinc polyacrylate resin, Jiangsu Sanmu Group's commercially available product HPA-Zn50, has a zinc content of 12wt% and a solid content of 50wt%. Polyether-modified polysiloxane, BYK-3490 (commercially available from BYK Chemicals), with 98.5 wt% active ingredient; Propylene glycol methyl ether, Dow Chemical Dowanol™ PM, 99.8% purity; Epoxy resin (E-44 type), commercially available product, epoxy value 0.46 eq / 100g, viscosity at 25℃ 13.6 Pa·s; Graphene oxide powder, a commercially available product from Changzhou Sixth Element Materials Technology Co., Ltd., has a sheet diameter distribution range of 4±1μm, 1-2 layers, and an oxygen content of 45±2%. Silica powder, commercially available product, with a particle size of 5μm; CaCl2, Na2CO3, anhydrous ethanol, and sodium bicarbonate are all commercially available products from Sinopharm Chemical Reagent Co., Ltd., and are of analytical grade. Zinc dihydrogen phosphate is produced by reacting zinc oxide (analytical grade, purchased from Sinopharm Group) and phosphoric acid (85 wt%, analytical grade, purchased from Sinopharm Group) in a molar ratio of 1:2; the actual mass of zinc dihydrogen phosphate shall be used. Cs2CO3, oleic acid (OA), octadecene (ODE), PbBr2, oleylamine (OAm), n-octadecane, urea, and formaldehyde are commercially available analytical grade products.

[0022] Preparation Example 1 The ion-responsive microcapsule has a core of a rust inhibitor and a capsule wall composed of a polyelectrolyte composite membrane formed by the self-assembly of cationic and anionic polyelectrolytes layer by layer. The outer surface of the capsule wall also contains a layer of inorganic nanoparticles formed by biomimetic mineralization.

[0023] The rust inhibitor was obtained by compounding.

[0024] The cationic polyelectrolyte is polydiallyldimethylammonium chloride, the anionic polyelectrolyte is sodium polystyrene sulfonate, and the inorganic nanoparticles are calcium carbonate.

[0025] The specific preparation process is as follows.

[0026] Sodium benzoate was thoroughly ground and screened to obtain sodium benzoate powder with a particle size of 5μm. 5g of sodium benzoate powder and 5g of cyclohexylamine liquid were mixed evenly in a 40℃ water bath to obtain a liquid compound rust inhibitor core. Add 0.1 g of sodium dodecyl sulfate as an emulsifier to 100 mL of polydiallyl dimethyl ammonium chloride (0.5 wt%) aqueous solution and stir at 500 rpm to obtain polydiallyl dimethyl ammonium chloride solution; The above-mentioned 10g of compound rust inhibitor capsule core was slowly added dropwise to the polydiallyldimethylammonium chloride solution, and then emulsified for 5 minutes at 10,000 rpm using a high-speed shear emulsifier to form a stable oil / water (O / W) emulsion. Adsorbed PSS layer: Transfer the oil / water (O / W) emulsion to a beaker with magnetic stirring, slowly add 100 mL of sodium polystyrene sulfonate (0.5 wt%) aqueous solution, react at 300 rpm and room temperature for 15 min. After the reaction is complete, let stand, remove the supernatant, and wash twice with deionized water by centrifugation to remove unadsorbed polyelectrolytes. Adsorbed PDDA layer: Add 100 mL of 0.5 wt% aqueous solution of polydiallyl dimethyl ammonium chloride to the above particle dispersion and react for 15 min under the same conditions; The PSS layer and PDDA layer were repeatedly adsorbed, and a total of 5 cycles of layer-by-layer self-assembly (polydiallyldimethylammonium chloride / sodium polystyrene sulfonate) were carried out to build a 10-layer polyelectrolyte composite membrane preform on the surface of the rust inhibitor droplets. Wash again with deionized water, disperse and dilute to 200 mL to obtain a dispersion of polyelectrolyte microcapsules with positively charged surfaces; The polyelectrolyte microcapsule dispersion was placed in a constant temperature water bath and stirred at 25°C and 200 rpm. 20 mL of CaCl2 solution (0.1 mol / L) and 20 mL of Na2CO3 solution (0.1 mol / L) were simultaneously added dropwise to the microcapsule dispersion at a rate of 1 mL / min. After the addition was complete, the aging reaction was continued for 1 hour. After the reaction was completed, the microcapsules were collected by vacuum filtration and washed repeatedly with deionized water and anhydrous ethanol to remove impurities. The obtained wet microcapsules were placed in a freeze dryer and freeze-dried at -50℃ and <10Pa for 24 hours to obtain powdered ion-responsive microcapsules.

[0027] Preparation Example 2 The ion-responsive microcapsule has a core of a rust inhibitor and a capsule wall of a polyelectrolyte composite membrane composed of cationic and anionic polyelectrolytes assembled layer by layer.

[0028] The cationic polyelectrolyte is polydiallyldimethylammonium chloride, and the anionic polyelectrolyte is sodium polystyrene sulfonate.

[0029] The specific preparation process is as follows.

[0030] Sodium benzoate was thoroughly ground and screened to obtain sodium benzoate powder with a particle size of 5μm. 5g of sodium benzoate powder and 5g of cyclohexylamine liquid were mixed evenly in a 40℃ water bath to obtain a liquid compound rust inhibitor core. Add 0.1 g of sodium dodecyl sulfate as an emulsifier to 100 mL of polydiallyl dimethyl ammonium chloride (0.5 wt%) aqueous solution and stir at 500 rpm to obtain polydiallyl dimethyl ammonium chloride solution; The above-mentioned 10g of compound rust inhibitor capsule core was slowly added dropwise to the polydiallyldimethylammonium chloride solution, and then emulsified for 5 minutes at 10,000 rpm using a high-speed shear emulsifier to form a stable oil / water (O / W) emulsion. Adsorbed PSS layer: Transfer the oil / water (O / W) emulsion to a beaker with magnetic stirring, slowly add 100 mL of sodium polystyrene sulfonate (0.5 wt%) aqueous solution, react at 300 rpm and room temperature for 15 min. After the reaction is complete, let stand, remove the supernatant, and wash twice with deionized water by centrifugation to remove unadsorbed polyelectrolytes. Adsorbed PDDA layer: Add 100 mL of 0.5 wt% aqueous solution of polydiallyl dimethyl ammonium chloride to the above particle dispersion and react for 15 min under the same conditions; The PSS layer and PDDA layer were repeatedly adsorbed, and a total of 5 cycles of layer-by-layer self-assembly (polydiallyldimethylammonium chloride / sodium polystyrene sulfonate) were carried out to build a 10-layer polyelectrolyte composite membrane preform on the surface of the rust inhibitor droplets. The microcapsules were washed again with deionized water and diluted to 200 mL to obtain a dispersion of positively charged polyelectrolyte microcapsules. The microcapsules were collected by vacuum filtration and washed repeatedly with deionized water and anhydrous ethanol to remove impurities. The obtained wet microcapsules were placed in a freeze dryer and freeze-dried at -50 °C and <10 Pa for 24 h to obtain powdered ion-responsive microcapsules.

[0031] Preparation Example 3 The ion-responsive microcapsules differ from those in Preparation Example 1 in that the core is replaced with 100% sodium benzoate (particle size of 5 μm), while the remaining components and preparation process are the same as in Example 1.

[0032] Preparation Example 4 The ion-responsive microcapsules differ from those in Preparation Example 1 in that the core is replaced with 100% cyclohexylamine, while the remaining components and preparation process are the same as in Example 1.

[0033] Preparation Example 5 Functionalized graphene oxide was obtained by covalent grafting modification with benzotriazole.

[0034] The preparation process is as follows: Take 2 mg of graphene oxide powder and add it to 1 LDM solvent to obtain a mixture; The mixture was placed in an ultrasonic cell disruptor and ultrasonically treated at 500W power for 1 hour under ice-water bath conditions to obtain a uniform, dark brown graphene oxide / DMF dispersion.

[0035] Weigh 5g of benzotriazole (BTA), add 200ml of DMF, heat to 30℃ and stir until completely dissolved to obtain a BTA / DMF solution; The graphene oxide / DMF dispersion was heated to 60°C and stirred at 200 rpm. 1.9 g EDC·HCl and 1.15 g NHS were added to the dispersion in sequence, and the reaction was continued for 2 h. After the reaction, BTA / DMF solution was added dropwise over a period of 30 minutes. After the addition was complete, the reaction temperature was raised to 80°C and the reaction was continued under reflux for 24 hours. After the reaction was completed, the reaction system was cooled to room temperature. The product was washed three times with anhydrous DMF (10,000 rpm, 10 min) at eight times the volume of the precipitate. Then it was washed twice with an ethanol / water (ethanol and water volume ratio 1:1) mixture at eight times the volume of the precipitate. Finally, it was washed once with deionized water at eight times the volume of the precipitate. The washed product can be placed in a vacuum drying oven and dried at 50°C for 24 hours to obtain a black, fluffy functionalized graphene oxide (BTA-GO) solid powder.

[0036] Preparation Example 6 Photothermal responsive microcapsules, comprising a core of a mixture of CsPbBr3 and n-octacosan. The capsule wall is made of polyurea-formaldehyde.

[0037] The preparation process of photothermal responsive microcapsules is as follows: 2.61 g of Cs2CO3, 25 mL of oleic acid (OA), and 125 mL of octadecene (ODE) were mixed and dehydrated and deoxygenated at 120 °C for 1 h under nitrogen protection to obtain a Cs-OA precursor solution. 1.38 g PbBr2, 187.5 mL octadecene (ODE), 25 mL oleic acid (OA), and 25 mL oleylamine (OAm) were mixed and stirred under vacuum at 120 °C for 1 h to obtain a PbBr2 solution. The PbBr2 solution was heated to 160℃ (heating rate 10℃ / min), and 10mL of Cs-OA precursor was rapidly injected using a syringe (completed within 10 seconds at 160℃). The reaction was quenched to room temperature in an ice-water bath after 10 seconds to obtain the reaction material. Add 250 mL of toluene to the reactants for dilution, then add 500 mL of ethanol for precipitation. Centrifuge at 8000 rpm for 5 min, discard the supernatant, repeat the precipitate washing twice, and finally redisperse the quantum dots in 500 mL of toluene. Concentrate to 500 mL by rotary evaporation to obtain a CsPbBr3 quantum dot stock solution with a concentration of 10 mg / mL. Take 15.0 g of n-octacosane and place it in a 1000 mL beaker. Melt it in a water bath at 65 °C. Slowly add 1500 mL of quantum dot stock solution (1 mL / min) while stirring (500 rpm). Continue stirring at 70 °C for 2 h to form a homogeneous oil phase. Toluene was removed by rotary evaporation (40℃, -0.08MPa) to obtain a quantum dot-octadecane composite core material; Add 1500mL of water, 0.75g of sodium dodecyl sulfate, and 7.5g of urea to a reaction vessel, stir and dissolve at 60℃, adjust the pH to 8.5 with NaOH, then slowly add 9.0mL of formaldehyde, prepolymerize at 60℃ for 1h to obtain the aqueous reaction phase; Quantum dot-octadecane composite core material (60℃) was added to the aqueous reaction phase, and emulsified at high speed of 12000rpm for 15min. The pH was adjusted to 3.2-3.5, and the polymerization reaction was carried out at 60℃ for 4h. Then, the pH was neutralized to 7.0 with NaOH and cooled to room temperature. The filtrate was filtered and washed until the conductivity of the filtrate was <50 μS / cm, then dried under vacuum at 40℃ for 24 h, and passed through a 100-mesh sieve to obtain a light yellow microcapsule powder.

[0038] Example 1 A smart responsive marine rust inhibitor composition, comprising the following components: Ion-responsive microcapsules 7.5 wt%. Photothermal responsive microcapsules 7.0 wt%. Functionalized graphene oxide 8wt%, Film-forming resin 35wt%, pH buffer 2wt%, 4 wt% polyether-modified polysiloxane The environmentally friendly solvent was replenished to 100 wt%.

[0039] The ion-responsive microcapsules were prepared as described in Preparation Example 1.

[0040] The photothermal responsive microcapsules were prepared in Preparation Example 6.

[0041] Functionalized graphene oxide was prepared in Preparation Example 5.

[0042] The film-forming resin is zinc polyacrylate resin.

[0043] The pH buffer is zinc dihydrogen phosphate.

[0044] The stabilizer is a polyether-modified polysiloxane.

[0045] The environmentally friendly solvent is a mixture of deionized water and propylene glycol methyl ether in a mass ratio of 7:3.

[0046] The preparation method is as follows: Weigh out the following components according to the specified mass ratio: ion-responsive microcapsules, photothermal-responsive microcapsules, pH buffer, zinc polyacrylate resin, polyether-modified polysiloxane, and environmentally friendly solvent. Weigh out a portion of the environmentally friendly solvent (60% of the weighed amount) into an ultrasonic disperser, add functionalized graphene oxide, photothermal responsive microcapsules, and ion responsive microcapsules, and ultrasonically treat for 30 minutes at a power of 600W and a temperature of 10±5℃ to obtain a uniform and stable first dispersion. The first dispersion was transferred to a high-speed mixer, and the remaining environmentally friendly solvent (40% of the weighed amount), pH buffer, film-forming resin and stabilizer were added in sequence. The mixture was stirred at 500 rpm for 60 min to obtain the second dispersion, thus obtaining the smart responsive marine rust inhibitor composition.

[0047] Comparative Example 1 A smart responsive marine rust inhibitor composition, which differs from Example 1 in that it uses the same mass of the ion-responsive microcapsules prepared in Preparation Example 2 instead of the ion-responsive microcapsules prepared in Preparation Example 1, otherwise the same.

[0048] Comparative Example 2 A smart responsive marine rust inhibitor composition differs from Example 1 in that the rust inhibitor is replaced by an equal mass of the ion-responsive microcapsules prepared in Example 1, and the rust inhibitor is obtained by mixing 5 μm sodium benzoate and cyclohexylamine at a mass ratio of 1:1 at 40°C.

[0049] Comparative Example 3 A smart responsive marine rust inhibitor composition differs from Example 1 in that it uses silica powder with a particle size of 5 μm to replace functionalized graphene oxide by mass.

[0050] Comparative Example 4 A smart responsive marine rust inhibitor composition, which differs from Example 1 in that the amount of photothermal responsive microcapsules is 0.

[0051] Example 2 A smart responsive marine rust inhibitor composition, comprising the following components: Ion-responsive microcapsules 7.5 wt%. Photothermal responsive microcapsules 7.0 wt%. 8 wt% graphene oxide Benzotriazole 0.8 wt%. Film-forming resin 35wt%, pH buffer 2wt%, 4 wt% polyether-modified polysiloxane The environmentally friendly solvent was replenished to 100 wt%.

[0052] The ion-responsive microcapsules were prepared as described in Preparation Example 1.

[0053] The photothermal responsive microcapsules were prepared in Preparation Example 6.

[0054] Functionalized graphene oxide was prepared in Preparation Example 5.

[0055] The film-forming resin is zinc polyacrylate resin.

[0056] The pH buffer is zinc dihydrogen phosphate.

[0057] The stabilizer is a polyether-modified polysiloxane.

[0058] The environmentally friendly solvent is a mixture of deionized water and propylene glycol methyl ether in a mass ratio of 7:3.

[0059] The preparation method is as follows: Weigh out the following components according to the specified mass ratio: ion-responsive microcapsules, photothermal-responsive microcapsules, pH buffer, zinc polyacrylate resin, polyether-modified polysiloxane, and environmentally friendly solvent. Weigh out a portion of the environmentally friendly solvent (60% of the weighed amount) into an ultrasonic disperser, add functionalized graphene oxide, photothermal responsive microcapsules, and ion responsive microcapsules, and ultrasonically treat for 30 minutes at a power of 600W and a temperature of 25±5℃ to obtain a uniform and stable first dispersion. The first dispersion was transferred to a high-speed mixer, and the remaining environmentally friendly solvent (40% of the weighed amount), benzotriazole, pH buffer, film-forming resin and stabilizer were added in sequence. The mixture was stirred at 500 rpm for 60 min to obtain a smart responsive marine rust inhibitor composition.

[0060] Example 3 A smart responsive marine rust inhibitor composition differs from Example 1 in that the ion-responsive microcapsules were prepared in Preparation Example 3.

[0061] Example 4 A smart responsive marine rust inhibitor composition differs from Example 1 in that the ion-responsive microcapsules were prepared in Preparation Example 4.

[0062] Example 5 A smart responsive marine rust inhibitor composition, which differs from Example 1 in that it does not contain a pH buffer, and the original pH buffer is replaced by an environmentally friendly solvent.

[0063] Example 6 A smart responsive marine rust inhibitor composition, which differs from Example 1 in that the pH buffer is sodium bicarbonate.

[0064] Example 7 A smart responsive marine rust inhibitor composition, which differs from Example 1 in that an epoxy resin (E-44 type) is used as the film-forming resin instead of zinc polyacrylate resin by mass.

[0065] Example 8 A smart responsive marine rust inhibitor composition, which differs from Example 1 in that it does not contain a stabilizer, and the original stabilizer is replaced by an environmentally friendly solvent.

[0066] Example 9 A smart responsive marine rust inhibitor composition, with the same formulation as in Example 1, but prepared differently, is as follows.

[0067] Weigh out the following components according to the specified mass ratio: ion-responsive microcapsules, photothermal-responsive microcapsules, pH buffer, zinc polyacrylate resin, polyether-modified polysiloxane, and environmentally friendly solvent. An environmentally friendly solvent was added to a high-speed mixer, followed by the addition of functionalized graphene oxide, ion-responsive microcapsules, photothermal-responsive microcapsules, pH buffer, film-forming resin, and stabilizer. The mixture was stirred at 500 rpm for 90 minutes to obtain a smart responsive marine rust inhibitor composition.

[0068] Example 10 A smart-responsive marine rust inhibitor composition, with a different formulation than that of Example 1, is as follows: Ion-responsive microcapsules 6wt%, Photothermal responsive microcapsules 6wt%, Functionalized graphene oxide 6wt%, Film-forming resin 34 wt%, pH buffer 1.5 wt%, 3wt% polyether-modified polysiloxane The environmentally friendly solvent was replenished to 100 wt%.

[0069] Example 11 A smart-responsive marine rust inhibitor composition, with a different formulation than that of Example 1, is as follows: Ion-responsive microcapsules 8wt%, Photothermal responsive microcapsules 8wt%, Functionalized graphene oxide 9wt%, Film-forming resin 38wt%, pH buffer 2.2 wt%, 5wt% polyether-modified polysiloxane The environmentally friendly solvent was replenished to 100 wt%.

[0070] The smart responsive marine rust inhibitor compositions of Examples 1-11 and Comparative Examples 1-4 were tested as follows.

[0071] Neutral salt spray test: Testing was conducted according to GB / T 1771-2007; The tested intelligent responsive marine rust inhibitor composition was uniformly coated onto a standard-sized (150mm × 70mm) sandblasted steel plate, and the dry film thickness was controlled to be 50μm using a wire bar coater. After curing for 7 days under standard conditions of 23℃ and 50% relative humidity, it was used for testing. The sample was placed in the salt spray chamber at a 20° angle to the vertical. The temperature inside the chamber was kept constant at 35°C, and a 5wt% sodium chloride solution was continuously sprayed. After the specified test cycle, the sample was removed, rinsed with clean water and dried. According to GB / T 1740-2007 "Test Method for Damp Heat Resistance of Paint Film", the blistering, rusting, peeling and other phenomena on the sample surface were rated, and the time of the first rust spot was recorded.

[0072] Scratch repair capability: Similar to the neutral salt spray test, a steel plate sample coated with the composition to be tested was prepared; Using a sharp tool (scratch cutter blade), create a standardized scratch on the coating that runs through to the metal substrate, with a length of at least 60 mm. Immerse the scratched sample in a 3.5 wt% sodium chloride solution, maintaining the temperature at 25°C. Regularly observe and record; at 168 hours after soaking, observe whether corrosion products (rust) are generated at the scratch and the extent of their spread.

[0073] Dynamic seawater immersion life: This test was conducted in a laboratory simulation of dynamic seawater. The temperature of the seawater medium (artificial seawater formulation conforming to ASTM D1141-98 standard) was maintained at 25°C and the salinity was between 3.4±0.1%. The seawater was continuously flowed over the sample surface at a flow rate of 0.2 m / s by a circulating pump or agitator to simulate dynamic marine environments such as tides and currents. Samples were prepared using the same method as those for neutral salt spray testing. The samples were then completely immersed in the aforementioned dynamic seawater. Take out the sample every 15 days, rinse it gently with clean water, and check the coating condition; The coating is considered to have failed when any of the following conditions are met, and the total immersion time is recorded as the effective protective life: 1. The sample surface shows corrosion of the base metal covering more than 5% of the area (rated according to GB / T 1766-2008 "Evaluation Method for Aging of Paint and Varnish Coatings"). 2. The coating exhibits severe blistering and peeling (grade ≥ 3); 3. Monitoring by electrochemical methods (such as EIS) showed that the low-frequency impedance modulus |Z| of the coating decreased by more than two orders of magnitude (e.g., from 10^9 Ω·cm² to below 10^7 Ω·cm²).

[0074] Thermal cycling / UV aging coupled test The diurnal cycle is set according to ASTM D5894. A complete cycle is 12 hours. The cycle diagram and conditions are as follows: High temperature / UV irradiation (60℃, 8h)] - [Rapid conversion] - [Low temperature / high humidity (20℃, 4h)] According to GB / T 9754-2007 "Determination of 20°, 60° and 85° specular gloss of paint films without metallic pigments", two sets of samples were prepared. One set served as an initial control and the initial gloss value was measured. The other set was tested for gloss value after aging after 1000 hours of the above-mentioned day-night cycle. The gloss retention rate (%) was calculated as (gloss value after aging / initial gloss value) × 100%.

[0075] Two sets of samples were prepared according to ISO 4624 "Paints and varnishes - test for adhesion by pull-out method". One set was used as an initial control, and the other set was used to obtain an aged sample after 1000 hours of cycling in the above day and night cycle. The initial adhesion and the adhesion after aging were tested according to the test method in the standard. The adhesion retention rate (%) was calculated as (adhesion after aging / initial adhesion) × 100%.

[0076] Samples were prepared according to ASTM B117 "Standard Practice for Neutral Salt Spray Testing". After 1000 hours of cycling in the above-mentioned day-night cycle, aged samples were obtained. The aged samples were then subjected to repeated neutral salt spray tests to obtain the salt spray resistance time after aging.

[0077] The test results are shown in the table below.

[0078] Table 1. Detection results of Examples 1-11 and Comparative Examples 1-4 Neutral salt spray test (time to first rust spot, h) Scratch repair capability (corrosion width at the scratch site after 168 hours, mm) Dynamic seawater immersion life (coating failure time, in months) Example 1 2200 0.1 14 Comparative Example 1 1000 1.5 7 Comparative Example 2 400 3 3 Comparative Example 3 800 2 5 Comparative Example 4 1500 1.8 8 Example 2 1500 0.8 9 Example 3 1300 1 8 Example 4 1250 1.3 7.5 Example 5 1800 0.5 11 Example 6 1600 1.2 10 Example 7 1400 1.1 8 Example 8 2000 0.3 12 Example 9 900 1.6 6 Example 10 1900 0.2 11 Example 11 2100 0.08 13 Table 2. Detection results of Examples 1-11 and Comparative Examples 1-4 Gloss retention rate after thermal cycling / UV aging (%) Adhesion retention rate after thermal cycling / UV aging (%) Residual salt spray resistance time (h) after thermal cycling / UV aging Example 1 70 80 800 Comparative Example 1 45 58 250 Comparative Example 2 30 40 100 Comparative Example 3 35 38 150 Comparative Example 4 40 55 300 Example 2 60 70 500 Example 3 65 72 450 Example 4 62 70 420 Example 5 68 78 700 Example 6 65 75 600 Example 7 50 60 350 Example 8 68 76 720 Example 9 42 53 220 Example 10 67 78 750 Example 11 72 82 850 Based on Table 1, comparing Example 1 and Comparative Examples 1-4, the time to the first rust spot in the intermediate salt spray test of Example 1 was significantly longer than that of Comparative Examples 1-3, the corrosion width at the scratch in Example 1 was significantly smaller than that in Comparative Examples 1-3, and the dynamic seawater immersion life of Example 1 was significantly longer than that of Comparative Examples 1-3. Meanwhile, in Table 2, the performance retention rate and performance of Example 1 after thermal cycling / UV aging were significantly better than those of Comparative Examples 1-4.

[0079] Therefore, this application constructs a synergistic anti-rust system by using ion-responsive microcapsules, photothermal-responsive microcapsules, and benzotriazole covalently grafted functionalized graphene oxide. Its ion-responsive microcapsules have a dual response mechanism: when the Cl⁻ concentration in the environment increases in the early stage of corrosion, its polyelectrolyte composite membrane swells through ion exchange, triggering the early warning release of the rust inhibitor; when local corrosion causes the pH value to drop, the outer biomimetic mineralization layer (calcium carbonate) dissolves, exposing the polyelectrolyte membrane, thereby accelerating the targeted repair release of the rust inhibitor and achieving corrosion blocking. Photothermal responsive microcapsules primarily function as physical regulators: CsPbBr3 efficiently converts ambient light energy into heat energy, prompting a solid-liquid phase transition in the core n-octacosane. During the n-octacosane phase transition, a large amount of latent heat is absorbed or released, creating a "thermal buffer" effect on the coating microenvironment. This effectively mitigates temperature fluctuations, significantly reduces coating thermal stress, and inhibits the generation and propagation of microcracks. Simultaneously, the volume change accompanying the phase transition also helps induce the physical self-healing of microcracks, thereby enhancing the physical integrity and durability of the coating. Benzotriazole covalently grafted functionalized graphene oxide is interwoven in the coating to form a dense physical barrier, effectively delaying the penetration of water, oxygen and corrosive ions, and buying critical time for the intelligent response mechanism. Its layered structure can also fill the space between the two microcapsules, further optimizing the density of the coating. In summary, the synergistic effect of chemical repair by ion-responsive microcapsules and physical regulation by photothermal-responsive microcapsules, combined with the barrier-enhancing effect of graphene oxide, constructs an intelligent protection system that combines passive defense, active repair, and environmental adaptability, which can significantly improve rust prevention performance and coating life in complex marine environments.

[0080] Comparing Example 1 and Example 2, it can be seen that the difference between Example 2 and Example 1 is that the graphene oxide used in Example 2 is unmodified, while the graphene oxide surface in Example 1 is grafted with benzotriazole through covalent bonds; the time to the first rust spot in the intermediate salt spray test of Example 1 is longer than that of Example 2, the corrosion width at the scratch in Example 1 is smaller than that in Example 2, and the dynamic seawater immersion life of Example 1 is greater than that of Example 2. Therefore, the anti-corrosion and anti-rust performance of Example 1 is better than that of Example 2.

[0081] The reason for this is that Example 1 specifies the use of benzotriazole (BTA) covalently grafted modified graphene oxide, which obtains a new hybrid material through covalent bonding. When the coating is damaged or the corrosive medium penetrates to the metal interface, the benzotriazole molecules covalently grafted onto the graphene oxide sheets do not easily fall off. Instead, relying on the huge specific surface area of ​​graphene oxide, they are transported to the defect area as a highly efficient "corrosion inhibitor reservoir" and react with the metal surface to form a dense and stable chemical adsorption film, inhibiting the anodic dissolution reaction of the metal. When the marine rust inhibitor composition is applied, the influence of benzotriazole molecules on the graphene oxide carrier causes it to oriented on the metal surface to exert its excellent physical barrier effect, thereby making the corrosion inhibitor evenly dispersed and not easily lost, ensuring the durability and targeting of the repair behavior, and enhancing the actual isolation effect of graphene oxide.

[0082] Comparing Example 1 and Examples 3-4, the difference lies in the different rust inhibitors, with Example 1 using a compound rust inhibitor. In the test results, the time it took for the first rust spot to appear in the intermediate salt spray test of Example 1 was longer than that of Example 3-4, the corrosion width at the scratch in Example 1 was smaller than that in Example 3-4, and the dynamic seawater immersion life of Example 1 was greater than that of Example 3-4. Therefore, the anti-corrosion and anti-rust performance of Example 1 is better than that of Example 3-4.

[0083] This verification shows that the corrosion inhibition efficiency is improved when the rust inhibitor is a compound of sodium benzoate and cyclohexylamine. This is because cyclohexylamine is highly volatile, rapidly vaporizing and diffusing, preferentially adsorbing onto the metal surface to form a hydrophobic film; sodium benzoate, on the other hand, dissolves and migrates to the metal interface under moisture. Between the two, the adsorption of cyclohexylamine provides directional anchoring sites for benzoate ions, while the complex protective film formed by benzoate and metal cations fills the potential defects in the cyclohexylamine molecular film, thus constructing a more dense and stable composite protective layer, forming a synergistic mechanism of gas-phase transport and interfacial film formation.

[0084] Comparing Example 1 and Examples 5-6, Example 1 added zinc dihydrogen phosphate as a pH buffer, Example 2 did not add a pH buffer, and Example 3 added sodium bicarbonate as a pH buffer.

[0085] The test results show: The time it took for the first rust spot to appear in the intermediate salt spray test of Example 6 was longer than that of Example 5; the corrosion width at the scratch in Example 6 was smaller than that in Example 5; and the dynamic seawater immersion life of Example 6 was greater than that of Example 5. Therefore, the anti-corrosion and anti-rust performance of Example 6 is better than that of Example 5. The time it took for the first rust spot to appear in the intermediate salt spray test of Example 1 was longer than that of Example 6. The corrosion width at the scratch in Example 1 was smaller than that in Example 6. The dynamic seawater immersion life of Example 1 was greater than that of Example 6. Therefore, the anti-corrosion and anti-rust performance of Example 1 is better than that of Example 6.

[0086] During metal corrosion, H⁺ is generated in the anodic region, causing a decrease in pH, while OH⁻ is generated in the cathodic region, causing an increase in pH. The pH buffer added in this application buffers the pH, providing a stable interfacial microenvironment and reducing the possibility of the intelligent microcapsules malfunctioning in the drastically fluctuating electrochemical environment of corrosion. When zinc dihydrogen phosphate is selected as the pH buffer, it not only effectively buffers drastic pH fluctuations, but its hydrolysis products can also form an insoluble zinc phosphate composite protective film at active sites on the metal surface (such as scratches and defects), thus possessing the dual functions of pH buffering and film repair.

[0087] Comparing Example 1 and Example 7: The film-forming resin used in Example 1 is zinc polyacrylate resin. When in contact with seawater, the zinc acrylate chains in the zinc polyacrylate resin will undergo ion exchange with sodium ions in the seawater, resulting in hydrolysis of the polymer chains and dissolution in the seawater at a controllable and extremely slow rate. The resin used in Example 7 is epoxy resin, which does not possess this property; In the test results, the time it took for the first rust spot to appear in the intermediate salt spray test of Example 1 was longer than that of Example 7, the corrosion width at the scratch in Example 1 was smaller than that in Example 7, and the dynamic seawater immersion life of Example 1 was greater than that of Example 7. Therefore, the anti-corrosion and anti-rust performance of Example 1 is better than that of Example 7.

[0088] Therefore, it can be seen that the use of zinc polyacrylate resin as the film-forming resin in this application changes the working mode and lifespan mechanism of the marine rust inhibitor composition in forming the coating film, transforming it from a "static barrier that gradually fails" to a "dynamic, self-renewing intelligent system," making the coating surface continuously smooth and effectively preventing the attachment of marine organisms, i.e., possessing antifouling function; the continuous dissolution of the surface is like "peeling an onion," which can continuously expose the unconsumed intelligent microcapsules and functionalized graphene oxide in the inner layer, ensuring that the coating surface always has fresh and efficient anti-rust activity, thereby solving the problem of limited protection cycle caused by aging, contamination and failure of active ingredients in traditional protective coatings.

[0089] Comparing Example 1 and Example 8, Example 8 did not contain any stabilizer compared to Example 1. In the test results, the time it took for the first rust spot to appear in the intermediate salt spray test of Example 1 was longer than that of Example 8, the corrosion width at the scratch in Example 1 was smaller than that in Example 8, and the dynamic seawater immersion life of Example 1 was greater than that of Example 8. Therefore, the anti-corrosion and anti-rust performance of Example 1 is better than that of Example 8.

[0090] Therefore, it can be seen that the addition of stabilizers to the intelligent responsive marine rust inhibitor composition of this application can improve the dispersion stability of graphene oxide and ion-responsive microcapsules in the marine rust inhibitor composition, making the marine rust inhibitor composition easier to use and store, and ensuring the rust prevention effect.

[0091] Comparing Examples 1 and 9, it can be seen that the difference between Examples 1 and 9 lies in the different raw material mixing steps during preparation. In the test results, the time for the first rust spot to appear in the intermediate salt spray test of Example 1 is longer than that of Example 9, the corrosion width at the scratch of Example 1 is smaller than that of Example 9, and the dynamic seawater immersion life of Example 1 is greater than that of Example 9. Therefore, the anti-corrosion and anti-rust performance of Example 1 is better than that of Example 9.

[0092] Therefore, it is preferable to use a step-by-step preparation method when preparing the intelligent responsive marine rust inhibitor composition of this application. First, through an ultrasonic pre-dispersion step, the easily agglomerated graphene oxide and the finely structured microcapsules are placed in a partial solvent and subjected to the high-frequency cavitation effect generated by ultrasound. The intense but short-lived local energy effectively opens the stacked structure of graphene oxide and allows the microcapsules to be initially dispersed. At the same time, it avoids the shear damage to the microcapsule walls that may be caused by mechanical stirring. In the second step, it is mixed with other raw materials by gentle mechanical stirring to achieve macroscopic homogeneity. High-intensity shear force is no longer required, thus protecting the integrity of the initially dispersed nanomaterials and microcapsules. This ensures that the functional components in the final product can exist uniformly and stably, thereby achieving its preset intelligent protective effect and avoiding the phenomenon of easy agglomeration of graphene oxide and easy breakage of microcapsules in the intelligent rust inhibitor composition.

[0093] Combining Examples 1 and 10-11, the time it took for the first rust spot to appear in the intermediate salt spray test of Example 10-11 was significantly longer than that of Comparative Examples 1-3, the corrosion width at the scratch in Example 10-11 was significantly smaller than that in Comparative Examples 1-3, and the dynamic seawater immersion life of Example 10-11 was significantly longer than that of Comparative Examples 1-3. Therefore, the anti-corrosion and anti-rust performance of Example 10-11 is significantly better than that of Comparative Examples 1-3.

[0094] Therefore, by controlling the component amounts of the intelligent responsive marine rust inhibitor composition of this application to 6-8 parts of ion-responsive microcapsules, 6-8 parts of photothermal-responsive microcapsules, 6-9 parts of benzotriazole covalently grafted functionalized graphene oxide, and 34-38 parts of film-forming resin, excellent intelligent protective effects can be obtained.

[0095] This specific embodiment is merely an explanation of the present invention and is not intended to limit the present invention. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but as long as they are within the scope of protection claimed by the present invention, they are protected by patent law.

Claims

1. A smart responsive marine rust inhibitor composition, characterized in that, Its composition includes a solvent and the following components in parts by mass: 6-8 portions of ion-responsive microcapsules 6-8 portions of photothermal responsive microcapsules 6-9 parts of benzotriazole covalently grafted modified functionalized graphene oxide 34-38 parts of film-forming resin; The core of the ion-responsive microcapsule is a rust inhibitor; The capsule wall is a polyelectrolyte composite membrane composed of cationic and anionic polyelectrolytes through layer-by-layer self-assembly, and the outer surface of the capsule wall also contains a layer of inorganic nanoparticles formed by biomimetic mineralization. The cationic polyelectrolyte is polydiallyldimethylammonium chloride, the anionic polyelectrolyte is sodium polystyrene sulfonate, and the inorganic nanoparticles are calcium carbonate; The photothermal responsive microcapsule comprises a core of a mixture of CsPbBr3 and n-octacosan, and a capsule wall of polyurea formaldehyde.

2. The smart responsive marine rust inhibitor composition according to claim 1, characterized in that, The rust inhibitor is a compound of sodium benzoate and cyclohexylamine.

3. The smart responsive marine rust inhibitor composition according to claim 1, characterized in that, It also includes zinc dihydrogen phosphate, accounting for 1.5-2.2 parts.

4. The smart responsive marine rust inhibitor composition according to claim 1, characterized in that, The film-forming resin is zinc polyacrylate resin.

5. The smart responsive marine rust inhibitor composition according to claim 1, characterized in that, It also includes polyether-modified polysiloxane, accounting for 3-5 parts.

6. A method for preparing the smart responsive marine rust inhibitor composition according to any one of claims 1-5, characterized in that, Includes the following steps: S1: Ion-responsive microcapsules, photothermal-responsive microcapsules and graphene oxide are pre-dispersed in a partially environmentally friendly solvent by ultrasound to obtain the first dispersion; S2: Add the remaining environmentally friendly solvent and other remaining components to the first dispersion and mix them evenly under stirring to obtain the second dispersion; S3: Filter the second dispersion to obtain the smart responsive marine rust inhibitor composition.

7. The use of the smart responsive marine rust inhibitor composition according to any one of claims 1-5 in the corrosion protection of components of marine engineering equipment, ship decks or offshore platforms.