Anti-corrosion and anti-rust water-based acrylic paint and preparation method thereof

Abstract

The invention belongs to the field of coatings, and particularly relates to an anti-corrosion and anti-rust water-based acrylic paint and a preparation method thereof. Comprising a water-based acrylic emulsion, deionized water, a coalescing agent, a dispersing agent, a defoaming agent, a pigment filler, a thickening agent and a functional composite filler, the functional composite filler is prepared from the following three components: HNTs (at) BTA, MoS2 (at) ZIF-8 / BTA and PANI-NF.

Description

TECHNICAL FIELD

[0001] The present application belongs to the field of coatings, and particularly relates to a kind of anticorrosive and antirust water-based acrylic paint and a preparation method thereof. BACKGROUND

[0002] With the increasingly stringent environmental regulations and the growing public awareness of health, the emission of volatile organic compounds (VOCs) is strictly limited, which promotes the transformation of the coatings industry to green and environmentally friendly direction. Waterborne acrylic (WBAC) resin coatings have been widely used in the fields of construction, wood, container and corrosion protection engineering, etc. due to their low VOCs content, small odor, good weather resistance, excellent gloss and color retention, and convenient construction, etc. They have become an important choice to replace traditional solvent-based coatings. However, compared with traditional solvent-based coatings, WBAC coatings still have obvious shortcomings in physical and mechanical properties and protective performance. Firstly, the compactness of WBAC coatings after film formation is relatively low, which leads to insufficient hardness, wear resistance and scratch resistance of the coating, making it difficult to meet the protection requirements of high-strength mechanical contact (such as furniture surface, engineering machinery). Secondly, WBAC resin contains a large number of hydrophilic groups (such as carboxyl and hydroxyl groups), which makes the water resistance of the coating poor and the barrier ability to corrosive media (such as water, oxygen and chloride ions) limited. Especially in complex and harsh service environments (such as inland wharf and marine atmosphere), the water conservancy steel structure is subjected to ultraviolet radiation, dry-wet alternating and high-speed water flow and sand erosion and wear for a long time. The single WBAC coating is prone to blistering, peeling and wear, and cannot provide long-term corrosion protection. In order to overcome the above defects, the modification of WBAC resin by introducing nanomaterials has become a research hotspot. Due to its unique surface effect, small size effect and quantum size effect, nanomaterials can significantly improve the mechanical properties and functional characteristics of polymer matrix. At present, the related research mainly focuses on the following technical routes: hard nanoparticle reinforcement: zero-dimensional hard nanoparticles such as nano-alumina and nano-silica are widely used to improve the hardness and wear resistance of the coating. Studies have shown that nano-alumina has extremely high hardness and good chemical stability, which can effectively enhance the scratch load and wear resistance of the coating. However, nanoparticles have a large specific surface area and high surface energy, which are prone to agglomeration in aqueous medium, leading to uneven dispersion in the resin matrix, which not only limits its reinforcing effect, but may even become a defect point of the coating. Therefore, the development of efficient dispersion technology (such as the use of special dispersants and ultrasonic treatment) to prepare storage-stable nanodispersion is the key to this route. One-dimensional fiber toughening and skeleton construction: the use of one-dimensional nanomaterials (such as sepiolite and carbon nanotubes) with high aspect ratio 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 pore structure and large specific surface area. After acid activation or hydrothermal modification treatment, the sepiolite fiber bundle can be depolymerized and more active sites can be exposed, thus constructing a three-dimensional network skeleton in the coating, which can significantly improve 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: 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.

[0005] 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.

[0006] 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.

[0007] 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.

[0008] 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.

[0009] 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.

[0010] 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.

[0011] 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; 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. 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.

[0012] Compared with the prior art, the present invention has the following advantages and beneficial effects: 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

[0013] 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.

[0014] The preparation method of HNTs@BTA (modified halloysite nanotubes with supported corrosion inhibitors) in this invention is as follows: 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.

[0015] 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.

[0016] 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.

[0017] The preparation method of MoS2@ZIF-8 / BTA (MoS2@ZIF-8 heterojunction material with corrosion inhibitor) in this invention is as follows: 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.

[0018] 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.

[0019] 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.

[0020] The preparation method of PANI-NF (polyaniline nanofibers) in this invention is as follows: 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.

[0021] 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.

[0022] Step S3: Place solutions A and B in an ice-water bath at 0-5°C for 30 minutes to pre-cool.

[0023] 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.

[0024] 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).

[0025] Example 1 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.

[0026] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows: Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0027] 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.

[0028] 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.

[0029] Example 2 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.

[0030] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows: Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0031] 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.

[0032] 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.

[0033] Example 3 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.

[0034] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows: Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0035] 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.

[0036] 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.

[0037] Example 4 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.

[0038] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows: Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0039] 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.

[0040] 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.

[0041] Example 5 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.

[0042] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows: Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0043] 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.

[0044] 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.

[0045] Comparative Example 1 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).

[0046] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows: Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0047] 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.

[0048] 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.

[0049] Comparative Example 2 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.

[0050] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows: Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0051] 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.

[0052] 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.

[0053] Comparative Example 3 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.

[0054] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows: Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0055] 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.

[0056] 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.

[0057] Comparative Example 4 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.

[0058] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows: Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0059] 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.

[0060] 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.

[0061] Comparative Example 5 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.

[0062] A method for preparing a corrosion- and rust-resistant water-based acrylic paint is as follows: Step S1: Add deionized water, dispersant, and defoamer to a mixing tank and mix at low speed until homogeneous.

[0063] 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.

[0064] 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.

[0065] Test Example 1 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.

[0066] Table 1 Performance Tests.

[0067]

[0068] 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. An anticorrosive antirust water-based acrylic paint, characterized by, The functional composite filler comprises HNTs@BTA, MoS2@ZIF-8 / BTA and PANI-NF.

2. The anticorrosive antirust water-based acrylic paint according to claim 1, characterized by, The film forming aid is alcohol ester-12, the dispersant is BYK-190, the defoaming agent is BYK-024, the pigment and filler is sericite powder, and the thickening agent is RM-8W.

3. The anticorrosive and antirust water-based acrylic paint according to claim 1, characterized by, The preparation method of the HNTs@BTA comprises the following steps: step S1, dispersing raw ore halloysite powder in a sulfuric acid solution, stirring and reacting under heating conditions, centrifuging, washing and drying to obtain expanded halloysite; step S2, dissolving benzotriazole in anhydrous ethanol, adding the expanded halloysite, ultrasonic dispersing and then placing in a vacuum container to perform multiple "vacuum-pumping vacuum" cycle operations; step S3, centrifugally collecting the solid, washing to remove the surface residues and then vacuum drying.

4. The anticorrosive antirust water-based acrylic paint according to claim 3, characterized by, In step S1, the concentration of the sulfuric acid solution is 1.0 mol / L, the reaction temperature is 60 DEG C, and the reaction time is 6 hours; in step S2, the concentration of the BTA ethanol solution is 60 mg / mL, the solid-liquid ratio of the expanded halloysite and the BTA ethanol solution is 1g:10 mL, the vacuum pressure is reduced to-0.09 MPa and maintained for 40 minutes, and the operation is repeated for 3 times.

5. The anticorrosive and antirust water-based acrylic paint according to claim 1, characterized by, The preparation method of the MoS2@ZIF-8 / BTA comprises the following steps: step S1, dispersing blocky molybdenum disulfide in a solvent to perform high-energy ultrasonic peeling, centrifugally removing unpeeled particles and collecting few-layer MoS2 nanosheets; step S2, dispersing the MoS2 nanosheets in methanol, first adding zinc salt for adsorption, then adding 2-methyl imidazole solution to generate MoS2@ZIF-8; step S3, immersing the MoS2@ZIF-8 in a BTA ethanol solution, adsorbing, centrifugally drying and then collecting.

6. The anticorrosive antirust water-based acrylic paint according to claim 5, characterized by, In step S1, the solvent is N-methyl pyrrolidone, 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 immersion time is 24 hours.

7. The anticorrosive and antirust water-based acrylic paint according to claim 1, characterized by, The preparation method of the PANI-NF is as follows: taking aniline as a monomer and ammonium persulfate as an oxidant, controlling the temperature to be 0-5 DEG C during the reaction, filtering and washing the reaction product until the filtrate is colorless and then drying.

8. A process for the preparation of the anticorrosive and antirust waterborne acrylic paint according to any one of claims 1-7, characterized in that, The method comprises the following steps: step S1, adding deionized water, a dispersant and a defoaming agent into a stirring tank and uniformly mixing at a low speed; Step S2, sequentially adding sericite powder, PANI-NF, HNTs@BTA and MoS2@ZIF-8 under stirring, and dispersing for 30 minutes at 1500 rpm after completing the feeding; Step S3, reducing the rotating speed to 500 rpm, adding water-based acrylic emulsion and a film forming aid, stirring for 20 minutes and then filtering and discharging.

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