Anticorrosive and antirust water-based acrylic paint and preparation method thereof

Abstract

This invention belongs to the field of coatings, specifically relating to a water-based anti-corrosion and rust-preventive acrylic paint and its preparation method. It includes a water-based acrylic emulsion, deionized water, film-forming aids, dispersants, defoamers, pigments and fillers, thickeners, and functional composite fillers; the functional composite fillers include the following three components: HNTs@BTA, MoS... 2 @ZIF-8 / BTA and PANI-NF.

Description

A water-based anti-corrosion and anti-rust acrylic paint and its preparation method Technical Field

[0001] This invention belongs to the field of coatings, specifically relating to an anti-corrosion and anti-rust water-based acrylic paint and its preparation method. Background Technology

[0002] With increasingly stringent environmental regulations and heightened public health awareness, the emission of volatile organic compounds (VOCs) is strictly limited, driving the coatings industry towards green and environmentally friendly practices. Waterborne acrylic (WBAC) resin coatings, using water as the dispersion medium, offer advantages such as low VOC content, low odor, good weather resistance, excellent gloss and color retention, and convenient application. They have become widely used in construction, woodworking, container manufacturing, and anti-corrosion engineering, making them an important alternative to traditional solvent-based coatings. However, compared to traditional solvent-based coatings, waterborne acrylic coatings still have significant shortcomings in terms of physical and mechanical properties and protective performance. First, their film density is relatively low, resulting in insufficient hardness, abrasion resistance, and scratch resistance, making it difficult to meet the protective requirements of high-intensity mechanical contact (such as furniture surfaces and construction machinery). Second, waterborne acrylic resins contain a large number of hydrophilic groups (such as carboxyl and hydroxyl groups), which makes the coating less water-resistant and limits its barrier ability against corrosive media (such as water, oxygen, and chloride ions). Especially in complex and harsh service environments (such as inland river terminals and marine atmospheres), hydraulic steel structures are subjected to long-term ultraviolet radiation, alternating wet and dry conditions, and erosion and wear from high-speed water flow and sediment. A single waterborne acrylic coating is prone to blistering, peeling, and wear, failing to provide long-term corrosion protection. To overcome these shortcomings, modifying waterborne acrylic resins with nanomaterials has become a current research hotspot. Nanomaterials, due to their unique surface effects, small size effects, and quantum size effects, can significantly improve the mechanical properties and functional characteristics of polymer matrices. Currently, related research mainly focuses on the following technical routes: Hard nanoparticle reinforcement: Zero-dimensional hard nanoparticles, represented by nano-alumina and nano-silica, are widely used to improve the hardness and wear resistance of coatings. Studies have shown that nano-alumina has extremely high hardness and good chemical stability, effectively enhancing the coating's scratch resistance and wear resistance. However, nanoparticles have a huge specific surface area and high surface energy, making them prone to aggregation in aqueous media, leading to uneven dispersion in the resin matrix. This not only limits their reinforcing effect but may even become a defect in the coating. Therefore, developing efficient dispersion techniques (such as using specific dispersants and ultrasonic treatment) to prepare storage-stable nanodispersions is key to this approach. One-dimensional fiber toughening and framework construction: Utilizing one-dimensional nanomaterials with high aspect ratios (such as sepiolite and carbon nanotubes) as "micro-ribs" to reinforce the coating can effectively improve the cohesive strength and toughness of the coating. Sepiolite is a natural fibrous silicate mineral with abundant porous structures and a large specific surface area. After acid activation or hydrothermal modification, sepiolite fiber bundles can depolymerize and expose more active sites, constructing a three-dimensional network framework within the coating, thereby significantly improving the tensile strength and erosion resistance of the coating.Furthermore, the porous structure of sepiolite can also be used as a carrier to load other functional nanoparticles. Two-dimensional sheet barrier and lubrication: Two-dimensional nanomaterials (such as hexagonal boron nitride (h-BN), graphene, etc.) have shown great application potential in anti-corrosion coatings due to their unique sheet structure. Hexagonal boron nitride (h-BN), known as "white graphite," possesses excellent chemical inertness, electrical insulation, and lubricity. After exfoliation and functionalization, boron nitride nanosheets (BNNSs) can be stacked layer by layer in the coating, forming a dense "labyrinth effect," effectively extending the penetration path of corrosive media. Simultaneously, the interlayer slip properties endow the coating with excellent self-lubricating and anti-friction properties. Multidimensional synergistic modification: Single-dimensional nanomaterials often only improve one aspect of the coating's performance. For example, simply adding particulate fillers may lead to brittle coatings, while simply adding fibrous materials may have limited improvement in surface wear resistance. Therefore, in recent years, a synergistic modification strategy of "one-dimensional reinforcement + two-dimensional lubrication / barrier" has emerged. For example, combining sepiolite fibers with boron nitride nanosheets utilizes sepiolite to enhance coating cohesion and boron nitride to provide surface lubrication and barrier properties, thereby simultaneously improving the coating's erosion resistance and corrosion protection. Despite these advancements, current waterborne acrylic-modified coatings remain insufficient in handling extreme corrosive environments (such as high salt spray and self-healing after coating damage). Existing modification schemes primarily focus on building physical barriers (passive corrosion protection), lacking intelligent response mechanisms for actively inhibiting corrosion (active corrosion protection). Furthermore, the long-term dispersion stability of nanomaterials in waterborne systems and their compatibility with resin interfaces remain key technological bottlenecks hindering the industrial application of high-performance waterborne anti-corrosion coatings. Summary of the Invention

[0003] To address the problems existing in the prior art, this invention provides a corrosion-resistant and rust-proof water-based acrylic paint and its preparation method.

[0004] This invention is achieved through the following technical solution:

[0005] A corrosion-resistant and rust-proof water-based acrylic paint includes a water-based acrylic emulsion, deionized water, film-forming aid, dispersant, defoamer, pigments and fillers, thickener, and functional composite filler; the functional composite filler includes the following three components: HNTs@BTA, MoS2@ZIF-8 / BTA, and PANI-NF.

[0006] Furthermore, the film-forming aid is alcohol ester-12, the dispersant is BYK-190, the defoamer is BYK-024, the pigment / filler is sericite powder, and the thickener is RM-8W.

[0007] Further, the preparation method of the HNTs@BTA includes the following steps: Step S1: Disperse the raw halloysite powder in sulfuric acid solution, stir and react under heating conditions, centrifuge, wash and dry to obtain expanded-pore halloysite; Step S2: Dissolve benzotriazole in anhydrous ethanol, add the expanded-pore halloysite, disperse ultrasonically and place in a vacuum container, and perform multiple "vacuuming-vacuum breaking" cycles; Step S3: Centrifuge to collect the solid, rinse to remove surface residue and then vacuum dry.

[0008] Further, in step S1, the sulfuric acid solution concentration is 1.0 mol / L, the reaction temperature is 60℃, and the reaction time is 6 hours; in step S2, the BTA ethanol solution concentration is 60 mg / mL, the solid-liquid ratio of expanded halloysite to BTA ethanol solution is 1g:10mL, the vacuum pressure is reduced to -0.09 MPa and maintained for 40 minutes, and the operation is repeated 3 times.

[0009] Further, the preparation method of MoS2@ZIF-8 / BTA includes the following steps: Step S1: Disperse blocky molybdenum disulfide in a solvent and perform high-energy ultrasonic exfoliation, centrifuge to remove unexfoliated particles, and collect few-layer MoS2 nanosheets; Step S2: In-situ growth, disperse MoS2 nanosheets in methanol, add zinc salt for adsorption first, and then add 2-methylimidazole solution to react and generate MoS2@ZIF-8; Step S3: Immerse MoS2@ZIF-8 in BTA ethanol solution, adsorb, and then centrifuge and dry.

[0010] Further, in step S1, the solvent is N-methylpyrrolidone, and the ultrasonic peeling time is 10 hours; in step S2, the zinc salt is zinc nitrate hexahydrate, and the reaction time is 4 hours; in step S3, the concentration of the BTA ethanol solution is 40 mg / mL, and the soaking time is 24 hours.

[0011] Furthermore, the preparation method of PANI-NF is as follows: using aniline as a monomer and ammonium persulfate as an oxidant, the reaction is carried out in hydrochloric acid medium by interfacial polymerization or rapid mixing method; the temperature is controlled at 0-5℃ during the reaction, and after the reaction is completed, the solution is filtered, washed until the filtrate is colorless and dried.

[0012] The present invention also provides a method for preparing anti-corrosion and anti-rust water-based acrylic paint, comprising the following steps: Step S1: Add deionized water, dispersant and defoamer to a mixing tank and mix at low speed until uniform;

[0013] Step S2: Add sericite powder, PANI-NF, HNTs@BTA and MoS2@ZIF-8 / BTA in sequence while stirring. After the addition is complete, disperse at 1500 rpm for 30 minutes.

[0014] Step S3: Reduce the rotation speed to 500 rpm, add water-based acrylic emulsion and film-forming aid, stir for 20 minutes, and filter out the material.

[0015] Compared with the prior art, the present invention has the following advantages and beneficial effects:

[0016] This invention combines one-dimensional halloysite nanotubes and polyaniline nanofibers with two-dimensional molybdenum disulfide nanosheets. In the coating matrix, the two-dimensional MoS2 nanosheets act as the primary physical barrier, forcing corrosive media to diffuse around the sheets, significantly extending the diffusion path. Meanwhile, one-dimensional HNTs and PANI-NFs are interspersed between the sheets, filling micropores and preventing the aggregation of MoS2 nanosheets. The ZIF-8 metal-organic framework, grown in situ on the MoS2 surface, possesses a high specific surface area and serves as a secondary BTA reservoir. When the coating is subjected to mechanical damage or local pH changes, the BTA encapsulated in the HNTs and ZIF-8 is released responsively, adsorbing onto the exposed metal surface to form a protective film. Simultaneously, polyaniline, as a conductive polymer, enables the formation of a dense oxide passivation film on the metal surface. This triple mechanism of "physical barrier + corrosion inhibitor release + anodic protection" endows the coating with excellent long-term corrosion resistance and self-healing properties. This invention utilizes an interfacial polymerization / rapid mixing method to prepare PANI in the form of nanofibers (PANI-NF). Compared to traditional granular polyaniline, the fibrous structure more easily establishes a conductive network within the coating, enabling efficient electron transfer with lower addition amounts, thus more effectively exerting its passivation and catalytic effects. Simultaneously, the fibrous structure also provides a toughening and reinforcing effect similar to "micro-reinforcing bars," enhancing the mechanical strength of the coating. In the preparation process of this invention, the acid etching of HNTs, the vacuum loading of BTA, and the in-situ growth of ZIF-8 on MoS2 are carried out under mild reaction conditions, requiring no expensive equipment or harsh high-temperature and high-pressure environments. The preparation processes of each component are relatively independent, ensuring strong quality control and facilitating large-scale preparation and widespread application. Detailed Implementation

[0017] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below with reference to the embodiments. The illustrative embodiments and descriptions of this invention are only used to explain this invention and are not intended to limit this invention.

[0018] The preparation method of HNTs@BTA (modified halloysite nanotubes with supported corrosion inhibitors) in this invention is as follows:

[0019] Step S1: Acid etching to expand pores: Disperse 100g of raw halloysite powder in 1000mL of 1.0mol / L sulfuric acid solution and react with magnetic stirring in a constant temperature water bath at 60℃ for 6 hours. Centrifuge, wash repeatedly with deionized water until neutral, dry under vacuum at 80℃ for 12 hours, and grind to obtain expanded halloysite.

[0020] Step S2: Vacuum Loading: Prepare 200 mL of anhydrous ethanol solution of benzotriazole (BTA) with a concentration of 60 mg / mL. Add 20 g of expanded halloysite to this solution (solid-liquid ratio 1 g: 10 mL) and sonicate for 30 minutes. Place in a vacuum container, evacuate to -0.09 MPa and maintain for 40 minutes, then slowly restore to normal pressure. Repeat the "evacuation-vacuum breaking" operation 3 times.

[0021] Step S3: Post-processing: Centrifuge to collect the solid, rinse once with anhydrous ethanol to remove surface residue, and vacuum dry at 50°C for 12 hours to obtain HNTs@BTA.

[0022] The preparation method of MoS2@ZIF-8 / BTA (MoS2@ZIF-8 heterojunction material with corrosion inhibitor) in this invention is as follows:

[0023] Step S1: Disperse 2.0g of blocky molybdenum disulfide in 200mL of N-methylpyrrolidone (NMP), exfoliate with high-energy ultrasound for 10 hours, remove unexfoliated particles by centrifugation, collect the supernatant, filter, wash and dry to obtain MoS2 nanosheets.

[0024] Step S2: Disperse 100 mg of MoS2 nanosheets in 50 mL of methanol, add 297 mg of zinc nitrate hexahydrate and stir for 30 minutes to adsorb, then add 328 mg of 2-methylimidazolium methanol solution and stir the reaction at room temperature for 4 hours.

[0025] Step S3: After centrifuging the product from step S2, the resulting solid was directly immersed in 50 mL of 40 mg / mL BTA ethanol solution for 24 hours without drying. After centrifugation and drying, the MoS2@ZIF-8 heterojunction material loaded with corrosion inhibitor was obtained.

[0026] The preparation method of PANI-NF (polyaniline nanofibers) in this invention is as follows:

[0027] Step S1: Add 0.93g (10mmol) of aniline monomer to 50mL of 1.0mol / L hydrochloric acid solution and stir until completely dissolved to obtain solution A.

[0028] Step S2: Add 2.28 g (10 mmol) of ammonium persulfate to another 50 mL of 1.0 mol / L hydrochloric acid solution, stir to dissolve, and this is solution B.

[0029] Step S3: Place solutions A and B in an ice-water bath at 0-5°C for 30 minutes to pre-cool.

[0030] Step S4: Quickly pour solution B into solution A all at once, stir vigorously for 30 seconds, then stop stirring and let it stand for 12 hours to react.

[0031] Step S5: After the reaction is complete, the precipitate is collected by filtration and washed with deionized water and anhydrous ethanol until the filtrate is colorless. Finally, it is dried in a vacuum drying oven at 60°C for 24 hours to obtain polyaniline nanofibers (PANI-NF).

[0032] Example 1

[0033] A water-based acrylic paint for corrosion and rust prevention, comprising, by weight: 65 parts water-based acrylic emulsion (48% solid content), 15 parts deionized water, 3 parts film-forming aid (alcohol ester-12), 0.5 parts dispersant (BYK-190), 0.3 parts defoamer (BYK-024), 20 parts pigments and fillers (sericite powder, 1250 mesh), 0.5 parts thickener (RM-8W), 1.0 part HNTs@BTA, 0.8 parts MoS2@ZIF-8, and 0.3 parts PANI-NF.

[0034] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows:

[0035] Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0036] Step S2: While stirring, add sericite powder, PANI-NF, HNTs@BTA, and MoS2@ZIF-8 / BTA sequentially. After addition, disperse at 1500 rpm for 30 minutes. Carefully control the dispersion temperature to not exceed 45℃ to avoid damaging the nanotube structure.

[0037] Step S3: Reduce the rotation speed to 500 rpm, add water-based acrylic emulsion and film-forming aid, stir for 20 minutes, and filter out the material.

[0038] Example 2

[0039] A corrosion- and rust-proof water-based acrylic paint, comprising, by weight: 65 parts water-based acrylic emulsion (48% solid content), 15 parts deionized water, 3 parts film-forming aid (alcohol ester-12), 0.5 parts dispersant (BYK-190), 0.3 parts defoamer (BYK-024), 20 parts pigments and fillers (sericite powder, 1250 mesh), 0.5 parts thickener (RM-8W), 1.5 parts HNTs@BTA, 0.6 parts MoS2@ZIF-8, and 0.3 parts PANI-NF.

[0040] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows:

[0041] Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0042] Step S2: While stirring, add sericite powder, PANI-NF, HNTs@BTA, and MoS2@ZIF-8 / BTA sequentially. After addition, disperse at 1500 rpm for 30 minutes. Carefully control the dispersion temperature to not exceed 45℃ to avoid damaging the nanotube structure.

[0043] Step S3: Reduce the rotation speed to 500 rpm, add water-based acrylic emulsion and film-forming aid, stir for 20 minutes, and filter out the material.

[0044] Example 3

[0045] A water-based acrylic paint for corrosion and rust prevention, comprising, by weight: 65 parts water-based acrylic emulsion (48% solid content), 15 parts deionized water, 3 parts film-forming aid (alcohol ester-12), 0.5 parts dispersant (BYK-190), 0.3 parts defoamer (BYK-024), 20 parts pigments and fillers (sericite powder, 1250 mesh), 0.5 parts thickener (RM-8W), 0.8 parts HNTs@BTA, 1.2 parts MoS2@ZIF-8, and 0.3 parts PANI-NF.

[0046] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows:

[0047] Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0048] Step S2: While stirring, add sericite powder, PANI-NF, HNTs@BTA, and MoS2@ZIF-8 / BTA sequentially. After addition, disperse at 1500 rpm for 30 minutes. Carefully control the dispersion temperature to not exceed 45℃ to avoid damaging the nanotube structure.

[0049] Step S3: Reduce the rotation speed to 500 rpm, add water-based acrylic emulsion and film-forming aid, stir for 20 minutes, and filter out the material.

[0050] Example 4

[0051] A corrosion- and rust-proof water-based acrylic paint, comprising, by weight: 65 parts water-based acrylic emulsion (48% solid content), 15 parts deionized water, 3 parts film-forming aid (alcohol ester-12), 0.5 parts dispersant (BYK-190), 0.3 parts defoamer (BYK-024), 20 parts pigments and fillers (sericite powder, 1250 mesh), 0.5 parts thickener (RM-8W), 1.0 part HNTs@BTA, 0.8 parts MoS2@ZIF-8, and 0.6 parts PANI-NF.

[0052] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows:

[0053] Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0054] Step S2: While stirring, add sericite powder, PANI-NF, HNTs@BTA, and MoS2@ZIF-8 / BTA sequentially. After addition, disperse at 1500 rpm for 30 minutes. Carefully control the dispersion temperature to not exceed 45℃ to avoid damaging the nanotube structure.

[0055] Step S3: Reduce the rotation speed to 500 rpm, add water-based acrylic emulsion and film-forming aid, stir for 20 minutes, and filter out the material.

[0056] Example 5

[0057] A corrosion- and rust-proof water-based acrylic paint, comprising, by weight: 65 parts water-based acrylic emulsion (48% solid content), 15 parts deionized water, 3 parts film-forming aid (alcohol ester-12), 0.5 parts dispersant (BYK-190), 0.3 parts defoamer (BYK-024), 20 parts pigments and fillers (sericite powder, 1250 mesh), 0.5 parts thickener (RM-8W), 0.5 parts HNTs@BTA, 0.4 parts MoS2@ZIF-8, and 0.15 parts PANI-NF.

[0058] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows:

[0059] Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0060] Step S2: While stirring, add sericite powder, PANI-NF, HNTs@BTA, and MoS2@ZIF-8 / BTA sequentially. After addition, disperse at 1500 rpm for 30 minutes. Carefully control the dispersion temperature to not exceed 45℃ to avoid damaging the nanotube structure.

[0061] Step S3: Reduce the rotation speed to 500 rpm, add water-based acrylic emulsion and film-forming aid, stir for 20 minutes, and filter out the material.

[0062] Comparative Example 1

[0063] A corrosion- and rust-proof water-based acrylic paint, comprising, by weight: 65 parts water-based acrylic emulsion (48% solid content), 15 parts deionized water, 3 parts film-forming aid (alcohol ester-12), 0.5 parts dispersant (BYK-190), 0.3 parts defoamer (BYK-024), 22.1 parts pigments and fillers (sericite powder, 1250 mesh), and 0.5 parts thickener (RM-8W).

[0064] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows:

[0065] Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0066] Step S2: Add sericite powder sequentially while stirring. After addition, disperse at 1500 rpm for 30 minutes. Note that the dispersion temperature should not exceed 45℃ to avoid damaging the nanotube structure.

[0067] Step S3: Reduce the rotation speed to 500 rpm, add water-based acrylic emulsion and film-forming aid, stir for 20 minutes, and filter out the material.

[0068] Comparative Example 2

[0069] A corrosion- and rust-proof water-based acrylic paint, comprising, by weight: 65 parts water-based acrylic emulsion (48% solid content), 15 parts deionized water, 3 parts film-forming aid (alcohol ester-12), 0.5 parts dispersant (BYK-190), 0.3 parts defoamer (BYK-024), 20 parts pigments and fillers (sericite powder, 1250 mesh), 0.5 parts thickener (RM-8W), 1.0 part HNTs, 0.2 parts BTA powder, 0.8 parts MoS2@ZIF-8 / BTA, and 0.3 parts PANI-NF.

[0070] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows:

[0071] Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0072] Step S2: While stirring, add sericite powder, PANI-NF, HNTs, BTA, and MoS2@ZIF-8 / BTA sequentially. After addition, disperse at 1500 rpm for 30 minutes. Carefully control the dispersion temperature to not exceed 45℃ to avoid damaging the nanotube structure.

[0073] Step S3: Reduce the rotation speed to 500 rpm, add water-based acrylic emulsion and film-forming aid, stir for 20 minutes, and filter out the material.

[0074] Comparative Example 3

[0075] A corrosion- and rust-proof water-based acrylic paint, comprising, by weight: 65 parts water-based acrylic emulsion (48% solid content), 15 parts deionized water, 3 parts film-forming aid (alcohol ester-12), 0.5 parts dispersant (BYK-190), 0.3 parts defoamer (BYK-024), 20 parts pigments and fillers (sericite powder, 1250 mesh), 0.5 parts thickener (RM-8W), 1.0 part HNTs@BTA, 0.6 parts MoS2, 0.2 parts ZIF-8, and 0.3 parts PANI-NF.

[0076] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows:

[0077] Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0078] Step S2: While stirring, add sericite powder, PANI-NF, HNTs@BTA, MoS2, and ZIF-8 sequentially. After addition, disperse at 1500 rpm for 30 minutes. Carefully control the dispersion temperature to not exceed 45℃ to avoid damaging the nanotube structure.

[0079] Step S3: Reduce the rotation speed to 500 rpm, add water-based acrylic emulsion and film-forming aid, stir for 20 minutes, and filter out the material.

[0080] Comparative Example 4

[0081] A corrosion- and rust-proof water-based acrylic paint, comprising, by weight: 65 parts water-based acrylic emulsion (48% solid content), 15 parts deionized water, 3 parts film-forming aid (alcohol ester-12), 0.5 parts dispersant (BYK-190), 0.3 parts defoamer (BYK-024), 20 parts pigments and fillers (sericite powder, 1250 mesh), 0.5 parts thickener (RM-8W), 1.0 part HNTs@BTA, and 0.8 parts MoS2@ZIF-8 / BTA.

[0082] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows:

[0083] Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0084] Step S2: While stirring, add sericite powder, HNTs@BTA, and MoS2@ZIF-8 / BTA sequentially. After addition, disperse at 1500 rpm for 30 minutes. Carefully control the dispersion temperature to not exceed 45℃ to avoid damaging the nanotube structure.

[0085] Step S3: Reduce the rotation speed to 500 rpm, add water-based acrylic emulsion and film-forming aid, stir for 20 minutes, and filter out the material.

[0086] Comparative Example 5

[0087] A corrosion- and rust-proof water-based acrylic paint, comprising, by weight: 65 parts water-based acrylic emulsion (48% solid content), 15 parts deionized water, 3 parts film-forming aid (alcohol ester-12), 0.5 parts dispersant (BYK-190), 0.3 parts defoamer (BYK-024), 20 parts pigments and fillers (sericite powder, 1250 mesh), 0.5 parts thickener (RM-8W), 1.0 part HNTs, 0.2 parts BTA, 0.6 parts MoS2, 0.2 parts ZIF-8, and 0.3 parts PANI-NF.

[0088] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows:

[0089] Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0090] Step S2: While stirring, add sericite powder, HNTs, BTA, MoS2, ZIF-8, and PANI-NF sequentially. After addition, disperse at 1500 rpm for 30 minutes. Carefully control the dispersion temperature to not exceed 45℃ to avoid damaging the nanotube structure.

[0091] Step S3: Reduce the rotation speed to 500 rpm, add water-based acrylic emulsion and film-forming aid, stir for 20 minutes, and filter out the material.

[0092] Test Example 1

[0093] Adhesion testing was performed according to GB / T9286-1998 "Cross-cut test for paint and varnish films". Water resistance testing was performed according to GB / T1733-1993 "Determination of water resistance of paint films". Neutral salt spray resistance testing was performed according to GB / T1771-2007 "Determination of neutral salt spray resistance of paint and varnish". Simultaneously, unidirectional corrosion propagation at the scratch was determined by peeling off the loose coating at the scratch with tape after 500 hours of neutral salt spray resistance testing, and measuring the maximum width (mm) of rust propagation on one side. The results are shown in Table 1.

[0094] Table 1 Performance Tests.

[0095]

[0096] As shown in Table 1, Example 1 (optimal formulation) exhibits the best overall performance. It achieves an adhesion rating of 0, water resistance exceeding 360 hours, and salt spray resistance reaching 480 hours. This is attributed to the synergistic effect of the active repair of HNTs@BTA, the efficient barrier properties of MoS2@ZIF-8 / BTA, and the passivation effect of PANI. Example 3 (high barrier type): Due to its high MoS2@ZIF-8 / BTA content (1.2 parts), its hydrophobic shielding network is the densest, resulting in the longest water resistance and salt spray resistance times. However, the excessively high amount of lamellar filler may slightly affect the bonding between the resin and the substrate, leading to an adhesion rating of 1. Comparative Example 1 only provides basic physical shielding, allowing water molecules and chloride ions to easily penetrate, resulting in a water resistance of only 48 hours and a salt spray resistance of only 72 hours. Comparative Example 2 (unencapsulated BTA): Compared to Example 1, the salt spray resistance time is significantly reduced (240 hours), and the scratch corrosion spread is wider (3.5 mm). The reason is that the directly added BTA is easily dissolved and lost by water in the early stage of film formation or soaking, and cannot achieve long-term "intelligent release" and lasting protection. Although Comparative Example 5 contains all the components, due to the lack of "in-situ growth" and "encapsulation" structure, the nanomaterials are prone to agglomeration (adhesion drops to level 2), and the MoS2 sheets are severely stacked, losing the "maze effect", resulting in its performance being far inferior to Example 1, and only slightly better than commercially available ordinary products.

Claims

1. A water-based acrylic paint for corrosion and rust prevention, characterized in that, The product includes an aqueous acrylic emulsion, deionized water, film-forming aids, dispersants, defoamers, pigments and fillers, thickeners, and functional composite fillers. The functional composite fillers comprise three components: HNTs@BTA, MoS2@ZIF-8 / BTA, and PANI-NF. The preparation method of HNTs@BTA includes the following steps: Step S1: Disperse raw halloysite powder in a sulfuric acid solution, stir under heating conditions, centrifuge, wash, and dry to obtain expanded-pore halloysite; Step S2: Dissolve benzotriazole in anhydrous ethanol, add the expanded-pore halloysite, ultrasonically disperse, and place in a vacuum container for multiple "vacuuming-vacuum breaking" cycles; Step S3: Collect the solid by centrifugation, and remove impurities by rinsing. Vacuum drying is performed after surface residue removal; the preparation method of MoS2@ZIF-8 / BTA includes the following steps: Step S1: Molybdenum disulfide is dispersed in a solvent and subjected to high-energy ultrasonic exfoliation, and unexfoliated particles are removed by centrifugation to collect few-layer MoS2 nanosheets; Step S2: MoS2 nanosheets are dispersed in methanol, zinc salt is added for adsorption, and then 2-methylimidazole solution is added to react and generate MoS2@ZIF-8; Step S3: MoS2@ZIF-8 is immersed in benzotriazole ethanol solution, adsorbed, and then centrifuged and dried; the preparation method of PANI-NF is as follows: aniline is used as a monomer, ammonium persulfate is used as an oxidant, the temperature is controlled at 0-5℃ during the reaction, and after the reaction is completed, the mixture is filtered, washed until the filtrate is colorless and dried.

2. The anti-corrosion and rust-proof water-based acrylic paint according to claim 1, characterized in that, The film-forming aid is alcohol ester-12, the dispersant is BYK-190, the defoamer is BYK-024, the pigment / filler is sericite powder, and the thickener is RM-8W.

3. The anti-corrosion and rust-proof water-based acrylic paint according to claim 1, characterized in that, In step S1 of the preparation method of HNTs@BTA, the concentration of sulfuric acid solution is 1.0 mol / L, the reaction temperature is 60℃, and the reaction time is 6 hours; in step S2, the concentration of benzotriazole ethanol solution is 60 mg / mL, the solid-liquid ratio of expanded halloysite to benzotriazole ethanol solution is 1 g:10 mL, the vacuum pressure is reduced to -0.09 MPa and maintained for 40 minutes, and the operation is repeated 3 times.

4. The anti-corrosion and rust-proof water-based acrylic paint according to claim 1, characterized in that, In step S1 of the preparation method of MoS2@ZIF-8 / BTA, the solvent is N-methylpyrrolidone and the ultrasonic exfoliation time is 10 hours; in step S2, the zinc salt is zinc nitrate hexahydrate and the reaction time is 4 hours; in step S3, the concentration of benzotriazole ethanol solution is 40 mg / mL and the soaking time is 24 hours.

5. A method for preparing a water-based anti-corrosion and anti-rust acrylic paint as described in any one of claims 1-4, characterized in that, The process includes the following steps: Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous; Step S2: While stirring, add sericite powder, PANI-NF, HNTs@BTA, and MoS2@ZIF-8 / BTA in sequence. After the addition is complete, disperse at 1500 rpm for 30 minutes; Step S3: Reduce the speed to 500 rpm, add aqueous acrylic emulsion and film-forming aid, stir for 20 minutes, and filter out the material.

Images