Waterproof and anticorrosive paint and preparation method thereof

Abstract

The present application relates to a kind of waterproof anticorrosive paint and its preparation method, belong to coating technical field, coating includes component A and component B;Component A includes organic titanium-silicon-POSS hybrid resin, intercalation modified hydrotalcite-boron nitride composite barrier filler etc.;Component B includes nitrogen phosphorus modified amine composite curing agent, interface metal anchoring accelerator etc. Organic titanium-silicon-POSS hybrid resin is prepared by tetraisopropyl titanate and 2,3-dihydroxynaphthalene, methyltrimethoxysilane, KH-792 and octaamino POSS reaction.Intercalation modified hydrotalcite-boron nitride composite barrier filler is stirred by magnesium-aluminum hydrotalcite powder, phytic acid, KH-550 modified boron nitride nanosheet preparation.Nitrogen phosphorus modified amine composite curing agent is prepared by tris (2-aminoethyl) Amine, hydroxymethyl phenyl phosphinic acid, p-toluenesulfonic acid and T-31 epoxy resin curing agent.Interface metal anchoring accelerator is prepared by triethylamine, anhydrous ethanol and 2-aminoethyl phosphonic acid.

Description

Technical Field

[0001] This invention belongs to the field of coating technology, specifically relating to a waterproof and anti-corrosion coating and its preparation method. Background Technology

[0002] Coatings, as the most widely used surface protection and decorative materials in modern industrial and civil fields, have been deeply integrated into many scenarios such as construction engineering, metal equipment, transportation facilities, shipbuilding and marine applications, and home decoration. Their core function is to form a continuous and dense protective layer on the substrate surface through film-forming substances, achieving functions such as blocking external corrosion, extending the service life of the substrate, and beautifying the appearance. Traditional coating systems are mainly solvent-based, and the film-forming substances often use acrylic, epoxy resin, alkyd resin, etc., which can meet general usage requirements in terms of basic protection and workability, providing basic surface protection for various substrates.

[0003] As operating environments become increasingly complex, ordinary coatings are struggling to cope with harsh conditions such as high temperature, high humidity, strong corrosion, and prolonged water immersion. In prolonged humid or aquatic environments, the hydrophilic structure of the coating allows water molecules to penetrate rapidly, damaging the interface between the coating and the substrate, causing blistering, peeling, chalking, and loss of protective capabilities. In corrosive environments, ordinary coatings, after film formation, contain micropores that cannot effectively block the penetration of chloride ions, acids, alkalis, and oxygen, leading to substrate corrosion, aging, and structural damage, directly reducing the safety and lifespan of engineering projects and equipment. In critical scenarios such as building basements, bathrooms, tunnels, bridges, pipelines, and ship decks, the shortcomings of ordinary coatings are particularly pronounced, with frequent problems such as water seepage, corrosion, and coating peeling, resulting in significant maintenance costs and safety hazards. Existing coatings struggle to simultaneously provide excellent waterproof sealing, chemical corrosion resistance, physical adhesion, and environmental tolerance.

[0004] Therefore, it is necessary to continuously improve and develop waterproof and anti-corrosion coatings with high density, high adhesion, excellent water resistance and corrosion resistance to enhance application value and meet market demands. Summary of the Invention

[0005] To address the shortcomings of existing traditional coatings in terms of adhesion, water resistance, and corrosion resistance, which fail to meet the long-term protective requirements of harsh environments, this invention provides a waterproof and anti-corrosion coating and its preparation method. Through multi-dimensional technical means such as resin modification, cross-linking structure optimization, functional filler modification and compounding, and interfacial bonding enhancement, a synergistic improvement in waterproof barrier and anti-corrosion protection is achieved. The specific technical solution is as follows:

[0006] A waterproof and anti-corrosion coating is prepared by mixing component A and component B in a mass ratio of 100:(25-30) and adjusting the viscosity to 4500-6500 mPa·s with a diluent (PMA). Component A comprises the following raw materials in parts by mass: 82-85 parts of organic titanium-silicon-POSS hybrid resin, 18-22 parts of intercalated modified hydrotalcite-boron nitride composite barrier filler, 1-1.2 parts of rheology modifier, 0.5-1.2 parts of low-foaming wetting and dispersing agent, and 6-8 parts of compound diluent. Component B comprises the following raw materials in parts by mass: 85-88 parts of nitrogen-phosphorus modified amine composite curing agent, 2.5-3 parts of interfacial metal anchoring accelerator, and 6-8 parts of diluent. The preparation of the organotitanium-silicon-POSS hybrid resin involves reacting tetraisopropyl titanate with 2,3-dihydroxynaphthalene in PMA to obtain a monochelated titanium monomer solution; dissolving methyltrimethoxysilane, KH-792, and octaaminoPOSS in PMA, and hydrolyzing with deionized water at pH 4.5–5 to obtain a POSS-grafted oligomeric siloxane solution; reacting and maturing the monochelated titanium monomer solution with the POSS-grafted oligomeric siloxane solution, and adjusting the solid content to 45 wt%–50 wt% to obtain the final product. The intercalated modified hydrotalcite-boron nitride composite barrier filler is a solid obtained by dispersing magnesium aluminum hydrotalcite powder, phytic acid, and KH-550 modified boron nitride nanosheets in a mass ratio of (12-15):(1.5-2):(5-7), dispersing magnesium aluminum hydrotalcite powder in a mixture of anhydrous ethanol and deionized water, adjusting the pH to 3.8-4.2, adding phytic acid and KH-550 modified boron nitride nanosheets, and stirring. The nitrogen-phosphorus modified amine composite curing agent is prepared by reacting tris(2-aminoethyl)amine, PMA, hydroxymethylphenylphosphonic acid, p-toluenesulfonic acid, and T-31 epoxy resin curing agent in a mass ratio of (10-13):(8-12):(3-4):(0.1-0.2):(25-30). Tris(2-aminoethyl)amine, hydroxymethylphenylphosphonic acid, and p-toluenesulfonic acid are reacted in PMA, and then T-31 epoxy resin curing agent is added to react. The pH is adjusted to 7.5-8 with triethanolamine. The interface metal anchoring promoter is prepared by stirring triethylamine, anhydrous ethanol, and 2-aminoethylphosphonic acid in a ratio of (0.3-0.5):(10-12):(3.5-4).

[0007] In the above coating, the compound diluent is PMA to Solvesso 100 in a mass ratio of (6.5-7):(3-3.5); the diluent is PMA.

[0008] In the above coatings, the rheology modifier is a polyurea compound type rheology modifier.

[0009] In the above coating, the preparation of the organotitanium-silicon-POSS hybrid resin involves reacting tetraisopropyl titanate, 2,3-dihydroxynaphthalene, methyltrimethoxysilane, KH-792, octaaminoPOSS, and deionized water at a mass ratio of (15-20):(3-3.5):(20-25):(4.5-5):(4-5):(2-2.5) in PMA at 50-60°C to obtain a monochelated titanium monomer solution; dissolving methyltrimethoxysilane, KH-792, and octaaminoPOSS in PMA and hydrolyzing with deionized water at pH 4.5-5 at 45-50°C to obtain a POSS-grafted oligomeric siloxane solution; and reacting and aging the monochelated titanium monomer solution and the POSS-grafted oligomeric siloxane solution at 60-65°C to adjust the solid content to 45wt%-50wt%.

[0010] The preparation method of the organotitanium-silicon-POSS hybrid resin in the above coating, by mass parts, includes the following steps: mixing 15-20 parts of tetraisopropyl titanate and 25-30 parts of PMA, stirring at 30-35°C, adding 3-3.5 parts of 2,3-dihydroxynaphthalene dropwise, reacting at 50-60°C for 50-60 min, recovering isopropanol by vacuum distillation, and adding PMA to the original volume to obtain a monochelated titanium monomer solution; adding 20-25 parts of methyltrimethoxysilane, 4.5-5 parts of KH-792, and 4-5 parts of octaaminoPO After mixing SS, it is dissolved in 20-25 parts of PMA, stirred at 45-50℃, and 2-2.5 parts of deionized water adjusted to pH 4.5-5 with glacial acetic acid is added dropwise. The hydrolysis reaction is carried out for 40-50 min to obtain a POSS-grafted oligomeric siloxane solution. The monochelated titanium monomer solution is added dropwise to the POSS-grafted oligomeric siloxane solution, reacted at 60-65℃ for 3-3.5 h, and matured at 25-30℃ for 2-2.5 h. The solid content is adjusted to 45wt%-50wt%, filtered, and the organotitanium-silicon-POSS hybrid resin is obtained.

[0011] The preparation method of the intercalated modified hydrotalcite-boron nitride composite barrier filler in the above coating, by mass parts, includes the following steps: dispersing 12-15 parts of magnesium aluminum hydrotalcite powder in 40-45 parts of anhydrous ethanol and 5-8 parts of deionized water, adjusting the pH to 3.8-4.2, stirring at 60-65℃, adding 1.5-2 parts of phytic acid, reacting at 80-85℃ for 1.5-2 hours, adding 5-7 parts of KH-550 modified boron nitride nanosheets, stirring at 70-75℃ for 1-1.5 hours; centrifuging, washing the solid, vacuum drying, and grinding to D50 < 3 μm to obtain the intercalated modified hydrotalcite-boron nitride composite barrier filler.

[0012] The preparation method of the nitrogen-phosphorus modified amine composite curing agent in the above coating, by mass parts, includes the following steps: stirring 10-13 parts of tris(2-aminoethyl)amine and 8-12 parts of PMA at 40-45°C, adding 3-4 parts of hydroxymethylphenylphosphonic acid and 0.1-0.2 parts of p-toluenesulfonic acid, reacting at 70-75°C for 2-2.5 hours, adding 25-30 parts of T-31 epoxy resin curing agent at 40-45°C, adjusting the pH to 7.5-8 with triethanolamine, cooling, and filtering to obtain the nitrogen-phosphorus modified amine composite curing agent.

[0013] The preparation method of the interface metal anchoring accelerator in the above coating, by mass parts, includes the following steps: adding 0.3 to 0.5 parts of triethylamine to 10 to 12 parts of anhydrous ethanol, stirring at 25 to 30°C, and then adding 3.5 to 4 parts of 2-aminoethylphosphonic acid to neutralize and stir, thereby obtaining an interface metal anchoring accelerator solution.

[0014] The preparation method of the above-mentioned waterproof and anti-corrosion coating includes the following steps: S1: According to the formulation amount of component A, stir the organic titanium-silicon-POSS hybrid resin, low foaming wetting and dispersing agent, and compound diluent, add the intercalated modified hydrotalcite-boron nitride composite barrier filler and stir, grind to fineness <10μm; add rheology modifier and stir, filter, and obtain component A; S2: According to the formulation amount of component B, stir the nitrogen-phosphorus modified amine composite curing agent, interface metal anchoring accelerator and diluent, filter and obtain component B; S3: Components A and B are stored separately. When using, they are mixed according to the mass ratio, and the viscosity is adjusted to 4500-6500 mPa·s with diluent (PMA). After standing and maturing, the coating is obtained.

[0015] In step S1 of the above preparation method, the grinding is performed to a fineness of <10μm.

[0016] The standing ripening time in step S3 of the above preparation method is 10-15 min.

[0017] The present invention provides a waterproof and anti-corrosion coating and its preparation method, which have the following beneficial effects: I. This invention's waterproof and anti-corrosion coating utilizes multi-dimensional technical means, including resin modification, cross-linking structure optimization, functional filler modification and compounding, and interface bonding enhancement, to construct an integrated protective structure comprising a high-density hybrid film-forming network, a chemical-physical dual barrier system, a chemically bonded interface bonding layer, and a PN synergistic corrosion-inhibiting cross-linking layer. This fundamentally solves the problems of low density, weak interface bonding, poor barrier ability, and insufficient resistance to harsh media found in traditional coatings. It achieves a synergistic improvement in waterproof sealing and chemical corrosion resistance. The coating exhibits strong adhesion to metal and inorganic substrates, excellent physical and mechanical properties, and effectively blocks the penetration of water, oxygen, and corrosive ions, preventing blistering, peeling, and powdering of the coating, thus extending the service life of the substrate.

[0018] II. An organic titanium-silicon-POSS hybrid resin, possessing both organic flexibility and inorganic rigidity, was prepared through the chelation reaction of tetraisopropyl titanate with 2,3-dihydroxynaphthalene, the hydrolysis reaction of silane monomers, and the formation of Ti-O-Si covalent bonds. The introduction of the POSS cage structure significantly reduces the free volume of the coating, the chelated titanium structure improves hydrolysis resistance, and the siloxane skeleton enhances density. The matching of each component with the preparation parameters ensures the integrity and density of the resin hybrid network, providing the core film-forming support and basic protective capability for the coating.

[0019] III. By controlling parameters such as acid modification conditions and temperature, we achieved the intercalation and layer expansion of hydrotalcite with phytic acid and the surface modification of boron nitride nanosheets with KH-550. A composite barrier filler of intercalated modified hydrotalcite-boron nitride was prepared by precisely proportioning magnesium aluminum hydrotalcite, phytic acid, and modified boron nitride. This formed a dual barrier mechanism of chemical adsorption and physical maze. Phytic acid intercalation of hydrotalcite adsorbed corrosive ions to achieve chemical barrier, while the alternating arrangement of modified boron nitride sheets and hydrotalcite extended the medium penetration path to achieve physical barrier. The preparation parameters ensured the dispersibility of the filler and its compatibility with the resin.

[0020] IV. A nitrogen-phosphorus modified amine composite curing agent was obtained by chemically modifying and compounding tris(2-aminoethyl)amine, hydroxymethylphenylphosphonic acid, and T-31. The multi-amino structure provides a high density of crosslinking points, and phosphorus and nitrogen form a PN synergistic system. The preparation parameters ensure the crosslinking activity and corrosion inhibition performance of the curing agent, which not only enhances the chelation between the coating and the metal, but also inhibits the cathodic and anodic corrosion reactions of the substrate, while improving the acid and alkali resistance and hydrolysis stability of the coating.

[0021] V. In the interfacial metal anchoring accelerator, the precise ratio of triethylamine to 2-aminoethylphosphonic acid ensures that the phosphonate group forms a stable coordination active site, while the amino terminus maintains its covalent reactivity with the resin and curing agent. These preparation parameters guarantee the bonding ability of the additive at the coating-substrate interface. The phosphonate group forms strong coordination and ionic bonds with the metal substrate, and the amino terminus is covalently grafted with the resin, constructing a covalent transition layer without weak bonding layers.

[0022] VI. In the preparation of component A, the hybrid resin is first mixed with the wetting and dispersing agent and the compound diluent, then the composite barrier filler is added and stirred and ground. Finally, the rheology modifier is added, stirred, and filtered. This step follows the principle of first mixing the liquid phase, then dispersing the solid phase, and then grinding and refining. The low-foaming wetting and dispersing agent ensures the uniform dispersion of the filler, and the polyurea rheology modifier improves the thixotropy of the system and prevents sagging during construction. All parameters ensure the dispersion stability and film-forming basis of component A. The precise ratio of components A and B is crucial to ensuring the sufficiency of the crosslinking reaction. Viscosity adjustment matches the construction requirements, and short-time curing allows the resin and curing agent to initially form a crosslinked prepolymer, improving the density of the film after formation and avoiding uneven crosslinking caused by direct construction.

[0023] In summary, the components exhibit excellent synergistic performance. The Ti-O-Si covalent bonds in the organotitanium-silicon-POSS hybrid resin form covalent bonds with the organic functional groups on the surface of the modified filler, ensuring uniform dispersion of the filler within the resin matrix. This utilizes both the film-forming properties of the resin to encapsulate the filler and the barrier properties of the filler to enhance the density of the resin coating. Simultaneously, the intercalated modified hydrotalcite-boron nitride composite barrier filler provides stress support for the curing shrinkage of the organotitanium-silicon-POSS hybrid resin, reducing microcracks in the coating. Together, they synergistically construct a dense film-forming barrier layer. The amino and hydroxyl groups in the organotitanium-silicon-POSS hybrid resin form high-density crosslinks with the polyamino groups in the curing agent, anchoring the POSS cage structure within the crosslinking network and further increasing the crosslinking density. The PN synergistic system in the nitrogen-phosphorus modified amine composite curing agent combines with the titanium-silicon structure in the resin, enhancing both the coating's resistance to media and the hydrolysis resistance of the hybrid network. Together, they synergistically construct a stable crosslinked film-forming network. The chemically bonded layer formed by the interface metal anchoring accelerator on the substrate surface not only forms a strong bond with the metal substrate, but also forms a covalent graft with the cross-linking network of the resin-curing agent, so that there are no weak bonding areas between the barrier layer of the coating and the substrate interface, thus preventing the medium from penetrating along the interface; at the same time, the strong bonding effect of the interface fully transfers the physical and mechanical properties and barrier properties of the coating to the substrate, enhancing the overall protective effect.

[0024] In addition, low-foaming wetting and dispersing agents ensure the uniform dispersion of fillers and additives, avoiding performance shortcomings caused by uneven dispersion; polyurea rheology modifiers improve workability without affecting the crosslinking density of the coating; compounded diluents balance solubility and evaporation rate, ensuring the leveling and film density of the coating during construction; and various additives provide guarantees for the performance of the main components. Detailed Implementation

[0025] Some embodiments are given below, but the present invention is not limited to these embodiments.

[0026] Glossary: ​​PMA stands for propylene glycol methyl ether acetate. The diluent is PMA. The compound diluent is a mixture of PMA and Solvesso 100. OctaaminoPOSS stands for octa(aminophenyltrioxosilane).

[0027] Example 1 A waterproof and anti-corrosion coating is prepared by mixing component A and component B at a mass ratio of 100:27 and adjusting the viscosity to 5000 mPa·s with a diluent (PMA). Component A comprises the following raw materials in parts by mass: 83 parts of organotitanium-silicon-POSS hybrid resin, 20 parts of intercalated modified hydrotalcite-boron nitride composite barrier filler, 1.1 parts of polyurea compound rheology modifier, 0.9 parts of low-foaming wetting and dispersing agent, and 7 parts of compound diluent (PMA to Solvesso 100 in a mass ratio of 6.8:3.2). Component B comprises the following raw materials in parts by mass: 86 parts of nitrogen-phosphorus modified amine composite curing agent, 2.8 parts of interfacial metal anchoring accelerator, and 7 parts of diluent (PMA). The polyurea compound rheology modifier used is BYK-410; the low-foaming wetting and dispersing agent used is EFKA-4050.

[0028] The preparation method of the organotitanium-silicon-POSS hybrid resin, by mass parts, includes the following steps: Under nitrogen protection, 18 parts of tetraisopropyl titanate and 27 parts of PMA are mixed, and 3.2 parts of 2,3-dihydroxynaphthalene are added dropwise while stirring at 32℃ and 400 r / min. After the addition is complete, the temperature is raised to 50-60℃, and the mixture is stirred at 400 r / min for 55 min under reflux protection. The by-product isopropanol is recovered by vacuum distillation, and PMA is added to the original volume to obtain a monochelated titanium monomer solution. 23 parts of methyltrimethoxysilane, 4.8 parts of KH-792, and 4.5 parts of octaaminoPOSS are mixed and dissolved in 23 parts of PMA, and the mixture is stirred at 45-50℃. Under stirring at 400 rpm, 2.2 parts of deionized water with pH adjusted to 4.8 using glacial acetic acid were added dropwise. After the addition was complete, the mixture was refluxed for hydrolysis for 45 min to obtain a POSS-grafted oligomeric siloxane solution. Under nitrogen protection, a monochelated titanium monomer solution was added dropwise at 6 mL / min to the POSS-grafted oligomeric siloxane solution. After the addition was complete, the temperature was raised to 60–65 °C, and the mixture was stirred at 400 rpm for 3 h under reflux protection. The temperature was then lowered to 25–30 °C, and the mixture was stirred at 400 rpm for 2 h to mature. The solid content was adjusted to 48 wt% (by vacuum distillation at 50–55 °C or by adding PMA). The mixture was then filtered through a 150-mesh sieve to obtain an organotitanium-silicon-POSS hybrid resin.

[0029] The preparation method of the intercalated modified hydrotalcite-boron nitride composite barrier filler, by mass parts, includes the following steps: Under nitrogen protection, 13 parts of magnesium aluminum hydrotalcite powder are dispersed in 42 parts of anhydrous ethanol and 7 parts of deionized water, the pH is adjusted to 4.0 with dilute nitric acid, stirred at 700 r / min for 35 min at 60-65℃, 1.8 parts of phytic acid are added, and the intercalation reaction is carried out under reflux at 80-85℃ for 1.5 h; 6 parts of KH-550 modified boron nitride nanosheets (pre-dispersed with 9 times anhydrous ethanol) are added, and the mixture is stirred under reflux at 550 r / min for 1 h at 70-75℃; the mixture is centrifuged, the filter cake is washed twice with ethanol, vacuum dried at 70-75℃ to constant weight, and ground to a D50 of 1.2 μm to obtain the intercalated modified hydrotalcite-boron nitride composite barrier filler.

[0030] Preparation of KH-550 modified boron nitride nanosheets: The boron nitride nanosheets and KH-550 were reacted in an 82 vol% ethanol aqueous solution at a mass ratio of 10:1 at 55-65℃ for 1.5 h. The solid was washed twice with ethanol and dried under vacuum at 70-75℃ to constant weight. The solid was then ground until D50 < 1 μm to obtain KH-550 modified boron nitride nanosheets.

[0031] The preparation method of the nitrogen-phosphorus modified amine composite curing agent, by mass parts, includes the following steps: Under nitrogen positive pressure protection, 12 parts of tris(2-aminoethyl)amine and 10 parts of PMA are added to a reaction vessel, and stirred at 450 r / min for 18 min at a temperature of 40-45℃; 3.5 parts of hydroxymethylphenylphosphonic acid and 0.15 parts of p-toluenesulfonic acid are added, and the temperature is raised to 70-75℃ and refluxed for 2 h; the temperature is lowered to 40-45℃, 28 parts of T-31 epoxy resin curing agent are added, and the reaction is stirred for 35 min; the pH is adjusted to 7.8 with triethanolamine; the temperature is lowered to 28℃, and the mixture is filtered through a 150-mesh filter to obtain the nitrogen-phosphorus modified amine composite curing agent.

[0032] The preparation method of the interfacial metal anchoring accelerator, by mass, includes the following steps: 0.4 parts of triethylamine are added to 11 parts of anhydrous ethanol, and under stirring at 400 rpm in a temperature range of 25–30°C, 3.8 parts of 2-aminoethylphosphonic acid are added for neutralization, and stirring is continued for 35 min to obtain the interfacial metal anchoring accelerator solution. The solution is then sealed and refrigerated. If precipitation occurs, it can be used after gentle heating at a temperature range of 38–42°C until clear.

[0033] The preparation method of the above-mentioned waterproof and anti-corrosion coating includes the following steps: S1: According to the formulation amount of component A, add the organotitanium-silicon-POSS hybrid resin, low-foaming wetting and dispersing agent, and compound diluent to the dispersion vessel, stir at 550 r / min for 15 min, add the intercalated modified hydrotalcite-boron nitride composite barrier filler, stir at 700 r / min for 35 min, and grind with a sand mill to a fineness of <10 μm while controlling the temperature of the cooling water below 30℃; add the polyurea compound rheology modifier while stirring at 550 r / min, stir for 15 min, and filter through a 150 mesh to obtain component A; S2: According to the formulation amount of component B, add nitrogen-phosphorus modified amine composite curing agent, interface metal anchoring accelerator and diluent to dispersion vessel, stir at 700 r / min for 18 min, filter with 150 mesh to obtain component B; S3: Components A and B are stored separately. When using, they are mixed at a mass ratio of 320 r / min for 8 min, the viscosity is adjusted to 5000 mPa·s with diluent, and the mixture is allowed to stand for 12 min to mature, thus obtaining the coating.

[0034] Example 2 A waterproof and anti-corrosion coating is prepared by mixing component A and component B at a mass ratio of 100:25 and adjusting the viscosity to 4500 mPa·s with a diluent (PMA). Component A comprises the following raw materials in parts by mass: 82 parts of organotitanium-silicon-POSS hybrid resin, 18 parts of intercalated modified hydrotalcite-boron nitride composite barrier filler, 1 part of polyurea compound rheology modifier, 0.5 parts of low-foaming wetting and dispersing agent, and 6 parts of compound diluent (PMA to Solvesso 100 in a mass ratio of 6.5:3.5). Component B comprises the following raw materials in parts by mass: 85 parts of nitrogen-phosphorus modified amine composite curing agent, 2.5 parts of interfacial metal anchoring accelerator, and 6 parts of diluent (PMA). The polyurea compound rheology modifier used is BYK-410; the low-foaming wetting and dispersing agent used is BYK-163.

[0035] The preparation method of the organotitanium-silicon-POSS hybrid resin, by mass parts, includes the following steps: Under nitrogen protection, 15 parts of tetraisopropyl titanate and 25 parts of PMA are mixed, and 3 parts of 2,3-dihydroxynaphthalene are added dropwise while stirring at 300 r / min at 30℃. After the addition is complete, the temperature is raised to 50-60℃, and the mixture is stirred at 300 r / min for 50 min under reflux protection. The by-product isopropanol is recovered by vacuum distillation, and PMA is added to the original volume to obtain a monochelated titanium monomer solution. 20 parts of methyltrimethoxysilane, 4.5 parts of KH-792, and 4 parts of octaaminoPOSS are mixed and dissolved in 20 parts of PMA, and the mixture is stirred at 45-50℃. Two parts of deionized water, adjusted to pH 4.5 with glacial acetic acid, were added dropwise under stirring at 300 rpm. After the addition was complete, the mixture was refluxed for hydrolysis for 40 min to obtain a POSS-grafted oligomeric siloxane solution. Under nitrogen protection, a monochelated titanium monomer solution was added dropwise at 5 mL / min to the POSS-grafted oligomeric siloxane solution. After the addition was complete, the temperature was raised to 60–65 °C, and the mixture was stirred at 300 rpm for 3 h under reflux protection. The temperature was then lowered to 25–30 °C, and the mixture was stirred at 300 rpm for 2 h to mature. The solid content was adjusted to 45 wt% (by vacuum distillation at 50–55 °C or by adding PMA). The mixture was then filtered through a 150-mesh sieve to obtain the organotitanium-silicon-POSS hybrid resin.

[0036] The preparation method of the intercalated modified hydrotalcite-boron nitride composite barrier filler, by mass parts, includes the following steps: Under nitrogen protection, 12 parts of magnesium aluminum hydrotalcite powder are dispersed in 40 parts of anhydrous ethanol and 5 parts of deionized water, the pH is adjusted to 3.8 with dilute nitric acid, stirred at 600 r / min for 30 min at 60-65℃, 1.5 parts of phytic acid are added, and the intercalation reaction is carried out under reflux at 80-85℃ for 1.5 h; 5 parts of KH-550 modified boron nitride nanosheets (pre-dispersed with 8 times anhydrous ethanol) are added, and the mixture is stirred under reflux at 500 r / min for 1 h at 70-75℃; the mixture is centrifuged, the filter cake is washed twice with ethanol, vacuum dried at 70-75℃ to constant weight, and ground to a D50 of 2.3 μm to obtain the intercalated modified hydrotalcite-boron nitride composite barrier filler.

[0037] Preparation of KH-550 modified boron nitride nanosheets: The boron nitride nanosheets and KH-550 were reacted at a mass ratio of 10:0.8 in 80 vol% ethanol aqueous solution (8 times the total mass) at 55–65 °C for 1.5 h. The solid was washed twice with ethanol, dried under vacuum at 70–75 °C to constant weight, and ground until D50 < 1 μm to obtain KH-550 modified boron nitride nanosheets.

[0038] The preparation method of the nitrogen-phosphorus modified amine composite curing agent, by mass parts, includes the following steps: Under nitrogen positive pressure protection, 10 parts of tris(2-aminoethyl)amine and 8 parts of PMA are added to a reaction vessel, and stirred at 400 r / min for 15 min at a temperature of 40-45℃; 3 parts of hydroxymethylphenylphosphonic acid and 0.1 parts of p-toluenesulfonic acid are added, and the temperature is raised to 70-75℃ and stirred under reflux for 2 h; the temperature is lowered to 40-45℃, 25 parts of T-31 epoxy resin curing agent are added, and the reaction is stirred for 30 min; the pH is adjusted to 7.5 with triethanolamine; the temperature is lowered to 25℃, and the mixture is filtered through a 150-mesh filter to obtain the nitrogen-phosphorus modified amine composite curing agent.

[0039] The preparation method of the interfacial metal anchoring accelerator, by mass, includes the following steps: 0.3 parts of triethylamine are added to 10 parts of anhydrous ethanol, and under stirring at 300 rpm in a temperature range of 25–30°C, 3.5 parts of 2-aminoethylphosphonic acid are added for neutralization, and stirring is continued for 30 min to obtain the interfacial metal anchoring accelerator solution. The solution is then sealed and refrigerated. If precipitation occurs, it can be used after gentle heating at a temperature range of 38–42°C until clear.

[0040] The preparation method of the above-mentioned waterproof and anti-corrosion coating includes the following steps: S1: According to the formulation amount of component A, add the organotitanium-silicon-POSS hybrid resin, low-foaming wetting and dispersing agent, and compound diluent to the dispersion vessel, stir at 500 r / min for 10 min, add the intercalated modified hydrotalcite-boron nitride composite barrier filler, stir at 600 r / min for 30 min, and grind with a sand mill to a fineness of <10 μm while controlling the temperature of the cooling water below 30℃; add the polyurea compound rheology modifier while stirring at 500 r / min, stir for 10 min, and filter through a 150 mesh to obtain component A; S2: According to the formulation amount of component B, add nitrogen-phosphorus modified amine composite curing agent, interface metal anchoring accelerator and diluent to dispersion vessel, stir at 600 r / min for 15 min, filter with 150 mesh to obtain component B; S3: Components A and B are stored separately. When using, they are mixed at a mass ratio of 300 r / min for 5 min, the viscosity is adjusted to 4500 mPa·s with diluent, and the mixture is allowed to stand for 10 min to mature, thus obtaining the coating.

[0041] Example 3 A waterproof and anti-corrosion coating is prepared by mixing component A and component B in a mass ratio of 100:30, and adjusting the viscosity to 6500 mPa·s with a diluent (PMA). Component A comprises the following raw materials in parts by mass: 85 parts of organotitanium-silicon-POSS hybrid resin, 22 parts of intercalated modified hydrotalcite-boron nitride composite barrier filler, 1.2 parts of polyurea compound rheology modifier, 1.2 parts of low-foaming wetting and dispersing agent, and 8 parts of compound diluent (PMA and Solvesso 100 in a mass ratio of 7:3). Component B comprises the following raw materials in parts by mass: 88 parts of nitrogen-phosphorus modified amine composite curing agent, 3 parts of interfacial metal anchoring accelerator, and 8 parts of diluent (PMA). The polyurea compound rheology modifier used is BYK-420; the low-foaming wetting and dispersing agent used is EFKA-4050.

[0042] The preparation method of the organotitanium-silicon-POSS hybrid resin, by mass parts, includes the following steps: Under nitrogen protection, 20 parts of tetraisopropyl titanate and 30 parts of PMA are mixed, and 3.5 parts of 2,3-dihydroxynaphthalene are added dropwise at 30-35℃ and 500 r / min with stirring. After the addition is complete, the temperature is raised to 50-60℃, and the mixture is stirred at 500 r / min for 60 min under reflux protection. The by-product isopropanol is recovered by vacuum distillation, and PMA is added to the original volume to obtain a monochelated titanium monomer solution; 25 parts of methyltrimethoxysilane, 5 parts of KH-792, and 5 parts of octaaminoPOSS are mixed and dissolved in 25 parts of PMA, and the mixture is stirred at 45-50℃. Under stirring at 500 rpm, 2.5 parts of deionized water with pH adjusted to 5 by glacial acetic acid were added dropwise. After the addition was complete, the mixture was refluxed for hydrolysis for 50 min to obtain a POSS-grafted oligomeric siloxane solution. Under nitrogen protection, a monochelated titanium monomer solution was added dropwise to the POSS-grafted oligomeric siloxane solution at 8 mL / min. After the addition was complete, the temperature was raised to 60–65 °C, and the mixture was stirred at 500 rpm for 3.5 h under reflux protection. The temperature was then lowered to 25–30 °C, and the mixture was stirred at 500 rpm for 2.5 h to mature. The solid content was adjusted to 50 wt% (by vacuum distillation or PMA addition at 50–55 °C). The mixture was then filtered through a 200-mesh filter to obtain an organotitanium-silicon-POSS hybrid resin.

[0043] The preparation method of the intercalated modified hydrotalcite-boron nitride composite barrier filler, by mass parts, includes the following steps: Under nitrogen protection, 15 parts of magnesium aluminum hydrotalcite powder are dispersed in 45 parts of anhydrous ethanol and 8 parts of deionized water, the pH is adjusted to 4.2 with dilute nitric acid, stirred at 800 r / min for 40 min at 60-65℃, 2 parts of phytic acid are added, and the intercalation reaction is carried out under reflux at 80-85℃ for 2 h; 7 parts of KH-550 modified boron nitride nanosheets (pre-dispersed with 10 times anhydrous ethanol) are added, and the mixture is stirred under reflux at 600 r / min for 1.5 h at 70-75℃; the mixture is centrifuged, the filter cake is washed 3 times with ethanol, vacuum dried at 70-75℃ to constant weight, and ground to a D50 of 1.8 μm to obtain the intercalated modified hydrotalcite-boron nitride composite barrier filler.

[0044] Preparation of KH-550 modified boron nitride nanosheets: The boron nitride nanosheets and KH-550 were reacted in an 85 vol% ethanol aqueous solution at a mass ratio of 10:1.2 at 55-65°C for 2 hours. The solid was washed three times with ethanol, dried under vacuum at 70-75°C to constant weight, and ground until D50 < 1 μm to obtain KH-550 modified boron nitride nanosheets.

[0045] The preparation method of the nitrogen-phosphorus modified amine composite curing agent, by mass parts, includes the following steps: Under nitrogen positive pressure protection, 13 parts of tris(2-aminoethyl)amine and 12 parts of PMA are added to a reaction vessel, stirred at 500 r / min for 20 min at a temperature of 40-45℃; 4 parts of hydroxymethylphenylphosphonic acid and 0.2 parts of p-toluenesulfonic acid are added, and the temperature is raised to 70-75℃ and refluxed for 2.5 h; the temperature is lowered to 40-45℃, 30 parts of T-31 epoxy resin curing agent are added, and the reaction is stirred for 40 min; the pH is adjusted to 8 with triethanolamine; the temperature is lowered to 30℃, and the mixture is filtered through a 200-mesh filter to obtain the nitrogen-phosphorus modified amine composite curing agent.

[0046] The preparation method of the interfacial metal anchoring accelerator, by mass, includes the following steps: 0.5 parts of triethylamine are added to 12 parts of anhydrous ethanol, and under stirring at 500 rpm in a temperature range of 25–30°C, 4 parts of 2-aminoethylphosphonic acid are added for neutralization, and stirring is continued for 40 min to obtain the interfacial metal anchoring accelerator solution. The solution is then sealed and refrigerated. If precipitation occurs, it can be used after gentle heating at a temperature range of 38–42°C until clear.

[0047] The preparation method of the above-mentioned waterproof and anti-corrosion coating includes the following steps: S1: According to the formulation amount of component A, add the organotitanium-silicon-POSS hybrid resin, low-foaming wetting and dispersing agent, and compound diluent to the dispersion vessel, stir at 600 r / min for 20 min, add the intercalated modified hydrotalcite-boron nitride composite barrier filler, stir at 800 r / min for 40 min, and grind with a sand mill to a fineness of <10 μm while controlling the temperature of the cooling water below 30℃; add the polyurea compound rheology modifier while stirring at 600 r / min, stir for 20 min, and filter through a 200 mesh to obtain component A; S2: According to the formulation amount of component B, add nitrogen-phosphorus modified amine composite curing agent, interface metal anchoring accelerator and diluent to dispersion vessel, stir at 800 r / min for 20 min, filter with 200 mesh to obtain component B; S3: Components A and B are stored separately. When using, they are mixed at a mass ratio of 350 r / min for 10 min, the viscosity is adjusted to 6500 mPa·s with diluent, and the mixture is allowed to stand for 15 min to mature, thus obtaining the coating.

[0048] In the above embodiments, all "parts by mass" mentioned in the organic titanium-silicon-POSS hybrid resin, intercalated modified hydrotalcite-boron nitride composite barrier filler, KH-550 modified boron nitride nanosheets, nitrogen-phosphorus modified amine composite curing agent, and interface metal anchoring accelerator are equivalent to "mass ratios" and only apply to the material addition and reaction process of each component itself. They have no relation or conversion relationship with the mass parts of other components. Each substance independently completes the material addition and reaction operation according to its own part percentage standard.

[0049] The raw materials used in the above embodiments are sourced as follows: EFKA-4050 is Efka EFKA-4050. Solvesso100 is Exxon aromatic hydrocarbon solvent oil Solvesso100. OctaaminoPOSS is octa(aminophenyltrioxosilane), sourced from Hubei Wande Chemical Co., Ltd. Magnesium aluminum hydrotalcite powder is sourced from Suzhou Senfida Chemical Co., Ltd., pulverized to a D50 < 5μm. KH-550 is sourced from Wuhan Lingjiayi Chemical Co., Ltd. Boron nitride nanosheets are sourced from Zhejiang Yamei Nanotechnology Co., Ltd., hexagonal boron nitride nanosheets with an average particle size of 100nm. T-31 epoxy resin curing agent is sourced from Hubei Rishengchang New Material Technology Co., Ltd., with a purity of 98%. KH-792 is γ-aminoethylaminopropyltrimethoxysilane, sourced from Hubei Zhenbo Chemical Co., Ltd. The purity of other substances is above 99%.

[0050] Comparative Example 1 The difference from Example 1 is that in component A, the organic titanium-silicon-POSS hybrid resin was changed to 95 parts, and the intercalated modified hydrotalcite-boron nitride composite barrier filler was changed to 8 parts. The viscosity of the coating was finally adjusted to 5000 mPa·s using PMA.

[0051] Comparative Example 2 The difference from Example 1 is that in component A, the organic titanium-silicon-POSS hybrid resin was changed to 65 parts, and the intercalated modified hydrotalcite-boron nitride composite barrier filler was changed to 38 parts. The viscosity of the coating was finally adjusted to 5000 mPa·s using PMA.

[0052] Comparative Example 3 The difference from Example 1 is that no interfacial metal anchoring promoter is added to component B.

[0053] Comparative Example 4 The difference from Example 1 is that methyltrimethoxysilane is not added in the preparation method of the organotitanium-silicon-POSS hybrid resin.

[0054] Comparative Example 5 The difference from Example 1 is that KH-792 is not added in the preparation method of the organotitanium-silicon-POSS hybrid resin.

[0055] Comparative Example 6 The difference from Example 1 is that the intercalated modified hydrotalcite-boron nitride composite barrier filler is directly replaced by a mixture of magnesium aluminum hydrotalcite powder and boron nitride nanosheets in a mass ratio of 13:6.

[0056] Comparative Example 7 The difference from Example 1 is that the nitrogen-phosphorus modified amine composite curing agent is directly replaced by a mixture of PMA and T-31 epoxy resin curing agent at a mass ratio of 10:28.

[0057] All performance test specimens were prepared using tinplate (120mm×50mm×0.3mm) after degreasing and rust removal, Q235 carbon steel plate (150mm×70mm×1.5mm) with surface treatment to Sa2.5 grade, and cement mortar test plates (70mm×70mm×10mm) after standard curing for 28 days. Coatings were prepared using wire rod coating, with wet or dry film thickness as specified for each project. Curing conditions were 23±2℃ temperature, 50±5% relative humidity, and 7 days under standard conditions. Three parallel specimens were set for each group, and the average value of the test results was taken. For media resistance tests (water resistance, acid resistance, alkali resistance, oil resistance, and salt spray), the back and sides of the specimens were sealed with a 1:1 mass ratio of paraffin wax and rosin melt mixture, with a sealing width ≥3mm.

[0058] I. Adhesion - Cross-cut Test: Performed according to GB / T 9286, using Q235 steel plate to prepare a dry film thickness of 40μm. Using a 6-blade cutting tool with a cutting interval of 1mm, cut vertically to the substrate. After cleaning with a soft brush, apply 3M 600# transparent tape, press firmly, and then quickly peel vertically within 1 minute. Rating according to the standard.

[0059] II. Adhesion - Pull-off test: Conducted in accordance with GB / T 5210. Q235 steel plates are used to prepare a dry film with a thickness of 40 μm. An epoxy adhesive is used to bond a Φ20mm aluminum test post. After curing for 24h, the test is carried out at a tensile rate of 1mm / min. The failure pulling force is recorded, and the adhesion is calculated.

[0060] III. Flexibility: Conducted in accordance with GB / T 1731. Tinplates are used to prepare a dry film with a thickness of 40 μm. The coating is bent 180° on axis rods of different diameters, and the cracking condition of the coating is observed. It is qualified if the minimum diameter of the passed axis rod is ≤1mm.

[0061] IV. Pencil hardness: Conducted in accordance with GB / T 6739. Q235 steel plates are used to prepare a dry film with a thickness of 40 μm. Under a load of 750g, with the pencil at 45° to the plate surface and moving at a constant speed, the maximum pencil hardness without penetrating scratches is recorded.

[0062] V. Water resistance: Conducted in accordance with Method A of GB / T 1733. Tinplates are used to prepare a dry film with a thickness of 40 μm, and the back and side edges are sealed. The test plate is immersed in deionized water at 23±2°C for 720h, taken out, the surface moisture is absorbed with filter paper, and left to stand for recovery for 2h, then the cross-cut adhesion is retested in accordance with GB / T 9286.

[0063] VI. Neutral salt spray test: Conducted in accordance with GB / T 1771. Q235 steel plates are used to prepare a dry film with a thickness of 150 μm. A cross is scratched on the coating through to the substrate, and the back and side edges are sealed. Test conditions: temperature in the test chamber is 35°C, 5% NaCl solution, pH 6.8, salt spray settlement is 1.5±0.5mL / (80cm 2 ·h), continuous spraying for 1000h. After the test is completed, the test plate is taken out, cleaned and dried, and the rust spread at the scribed line is measured.

[0064] VII. Acid and alkali resistance: Conducted in accordance with GB / T 9274. Q235 steel plates are used to prepare a dry film with a thickness of 40 μm, and the back and side edges are sealed. At 23±2°C, the test plates are immersed in 5wt% H₂SO₄ solution, 5wt% HCl solution, 5wt% NaOH solution and saturated Ca(OH)₂ solution for 168h respectively. After being taken out, cleaned and dried, the appearance of the coating (blistering, falling off, discoloration, etc.) is observed.

[0065] VIII. Oil resistance: Conducted in accordance with GB / T 9274. Q235 steel plates are used to prepare a dry film with a thickness of 40 μm, and the back and side edges are sealed. At 23±2°C, the test plate is immersed in No. 93 gasoline for 720h, taken out, the oil stain is wiped dry, and the coating appearance is observed.

[0066] Table 1 Average test results Note: In Example 3, because the filler ratio was at the upper limit, a small amount of filler agglomeration caused a slight decrease in the density of the coating surface, resulting in slight loss of gloss in acid and alkali resistance, but the overall performance remained excellent.

[0067] Table 1 (continued) Average test results Examples 1 to 3 achieve optimal waterproof and corrosion-resistant performance due to the synergistic effect of components such as organic titanium-silicon-POSS hybrid resin, modified composite barrier filler, nitrogen-phosphorus modified amine curing agent, and interface metal anchoring accelerator. This results in a high-performance protective coating constructed from multiple dimensions, including film structure, interfacial bonding, barrier pathways, and crosslinking density. Tetraisopropyl titanate forms a hydrolysis-resistant chelated titanium structure with 2,3-dihydroxynaphthalene, which is then linked to oligomeric siloxane and KH-792 formed by hydrolysis via Ti-O-Si covalent bonds. The inclusion of an octaamino POSS cage structure in the network introduces inorganic rigidity to enhance hardness and density while retaining organic flexibility to ensure toughness. Simultaneously, it significantly reduces the free volume of the coating, minimizing media penetration channels. Phytic acid intercalation expands the interlayer spacing of hydrotalcite, enabling it to form an intercalated nanostructure with polymer segments, adsorbing corrosive ions to achieve chemical barrier. KH-550-modified boron nitride nanosheets are grafted with organic functional groups, forming covalent bonds with the resin. The alternating arrangement of the sheets and hydrotalcite creates a physical barrier, significantly extending the penetration paths of water, oxygen, and corrosive ions, achieving both chemical and physical barrier effects. In the interfacial metal anchoring accelerator, 2-aminoethylphosphonic acid, after neutralization with triethylamine, forms strong coordination and ionic bonds with hydroxyl groups and metal oxides on the metal substrate surface. The amino terminus is covalently grafted with the resin and curing agent, constructing a covalent transition layer between the substrate and coating. This eliminates weak interfacial bonding layers, significantly improving interfacial bonding strength and preventing blistering and peeling caused by media penetration along the interface. The nitrogen-phosphorus modified amine composite curing agent combines tris(2-aminoethyl)amine, hydroxymethylphenylphosphonic acid and T-31. The multi-amino structure provides high-density cross-linking points, forming a dense curing network. After the introduction of phosphorus, it forms a PN synergistic system with nitrogen, which not only enhances the chelation between the coating and the metal, but also has corrosion inhibition properties, inhibiting the anodic and cathodic corrosion reactions of the substrate, while improving the coating's acid and alkali resistance and hydrolysis stability.

[0068] In Comparative Example 1, the proportion of barrier filler was too low: the significant reduction in filler content resulted in an incomplete nano-barrier network, weakened the physical barrier effect, and changed the penetration path of corrosive media from a maze-like pattern to a near-linear pattern. Excessive resin caused the internal stress generated by curing shrinkage to lack filler support, increasing the number of microcracks in the coating. At the same time, the filler could not effectively transfer stress, leading to a deterioration in the protective performance against water, salt spray, acid and alkali media.

[0069] In Comparative Example 2, the proportion of barrier filler was too high: the filler content exceeded the critical volume fraction, and the excessive filler particles agglomerated to form a network, disrupting the continuity of the resin matrix. The resin could not fully wet the filler particles, resulting in a large number of micropores at the interface, which became rapid penetration channels for corrosive media. At the same time, the disruption of the continuous resin phase hindered the cross-linking reaction, and the excessive rigid filler increased the brittleness and deteriorated the flexibility of the coating. The increased internal stress further reduced the interfacial adhesion.

[0070] In Comparative Example 3, without an interfacial metal anchoring accelerator, the bonding between the coating and the metal substrate degenerates from chemical anchoring and physical adsorption to simple physical adsorption and hydrogen bonding. The coordination effect between phosphonate and metal ions disappears, and the interfacial bonding strength drops sharply. Water molecules easily replace hydrogen bonds at the interface, causing interfacial debonding and blistering. Corrosive media rapidly spread laterally along the interface, leading to decreased adhesion after water resistance and accelerated salt spray corrosion, becoming a weak point in the coating protection.

[0071] In Comparative Example 4, the hybrid resin lacked methyltrimethoxysilane: Methyltrimethoxysilane is the core monomer for forming the Si-O-Si siloxane framework. Its absence led to a significant reduction in the inorganic rigid segments in the hybrid network, a significant decrease in crosslinking density, weakened bridging between titanate and POSS, and partial self-polymerization of titanate to form aggregates, resulting in reduced coating density. The increased free volume made it easier for water molecules and corrosive ions to penetrate, while incomplete crosslinking led to a decrease in hardness and a comprehensive deterioration of all media resistance properties.

[0072] In Comparative Example 5, the hybrid resin lacked KH-792: KH-792, as an aminosilane, serves as both a crosslinking point for the hybrid resin and an active site for reaction with the curing agent. Its absence leads to a decrease in the amino content of the resin, a reduction in its reactivity with the curing agent, and insufficient crosslinking density. Simultaneously, the flexibility of the siloxane network changes, the compatibility of the components decreases, and slight phase separation occurs. However, because the basic titanium-silicon structure still exists, the degree of performance degradation is relatively minor.

[0073] In Comparative Example 6, the unmodified fillers were directly physically mixed: The fillers, without phytic acid intercalation and KH-550 modification, relied solely on van der Waals forces for interfacial bonding with the resin matrix, resulting in extremely poor compatibility and the formation of numerous pores and weak boundary layers at the interface. The interlayer spacing of the hydrotalcite was not expanded, preventing the formation of intercalated nanostructures; the boron nitride sheets aggregated, failing to form continuous physical barriers, and the labyrinthine barrier effect was ineffective; dispersibility was also poor. Corrosive media rapidly penetrated to the substrate through interfacial defects, leading to decreased adhesion, coating blistering and peeling, and deterioration of water resistance, salt spray resistance, and oil resistance.

[0074] In Comparative Example 7, the curing agent was a simple physical mixture: the unmodified nitrogen-phosphorus curing agent lacked the phosphorus element introduced by hydroxymethylphenylphosphonic acid, and the PN synergistic corrosion inhibition and interfacial chelation effects disappeared; the absence of tris(2-aminoethyl)amine led to a significant decrease in crosslinking point density, resulting in a loose and porous cured network. The amidation reaction catalyzed by p-toluenesulfonic acid did not occur, and the reaction between the resin and the curing agent was incomplete. Because the amidation reaction between the curing agent and the resin did not occur, only the solvent from the physical mixture evaporated, causing surface drying. The internal crosslinking reaction did not take place, resulting in a pseudo-dry state. The coating cohesion was extremely low, and the hardness and adhesion decreased significantly. The medium easily penetrated, leading to complete coating destruction. This group had the worst performance among all comparative examples.

Claims

1. A waterproof and anti-corrosion coating, characterized in that, The coating is made by mixing component A and component B at a mass ratio of 100:(25-30), and adjusting the viscosity to 4500-6500 mPa·s with a diluent. Component A includes the following raw materials in parts by mass: 82-85 parts of organic titanium-silicon-POSS hybrid resin, 18-22 parts of intercalated modified hydrotalcite-boron nitride composite barrier filler, 1-1.2 parts of rheology modifier, 0.5-1.2 parts of low-foaming wetting and dispersing agent, and 6-8 parts of compound diluent. Component B includes the following raw materials in parts by mass: 85-88 parts of nitrogen-phosphorus modified amine composite curing agent, 2.5-3 parts of interfacial metal anchoring accelerator, and 6-8 parts of diluent. The preparation of the organotitanium-silicon-POSS hybrid resin involves reacting tetraisopropyl titanate with 2,3-dihydroxynaphthalene in PMA to obtain a monochelated titanium monomer solution; dissolving methyltrimethoxysilane, KH-792, and octaaminoPOSS in PMA, and hydrolyzing with deionized water at pH 4.5–5 to obtain a POSS-grafted oligomeric siloxane solution; reacting and maturing the monochelated titanium monomer solution with the POSS-grafted oligomeric siloxane solution, and adjusting the solid content to 45 wt%–50 wt% to obtain the final product. The intercalated modified hydrotalcite-boron nitride composite barrier filler is a solid obtained by dispersing magnesium aluminum hydrotalcite powder, phytic acid, and KH-550 modified boron nitride nanosheets in a mass ratio of (12-15):(1.5-2):(5-7), dispersing magnesium aluminum hydrotalcite powder in a mixture of anhydrous ethanol and deionized water, adjusting the pH to 3.8-4.2, adding phytic acid and KH-550 modified boron nitride nanosheets, and stirring. The nitrogen-phosphorus modified amine composite curing agent is prepared by reacting tris(2-aminoethyl)amine, PMA, hydroxymethylphenylphosphonic acid, p-toluenesulfonic acid, and T-31 epoxy resin curing agent in a mass ratio of (10-13):(8-12):(3-4):(0.1-0.2):(25-30). Tris(2-aminoethyl)amine, hydroxymethylphenylphosphonic acid, and p-toluenesulfonic acid are reacted in PMA, and then T-31 epoxy resin curing agent is added to react. The pH is adjusted to 7.5-8 with triethanolamine. The interface metal anchoring promoter is prepared by stirring triethylamine, anhydrous ethanol, and 2-aminoethylphosphonic acid in a ratio of (0.3-0.5):(10-12):(3.5-4).

2. The waterproof and anti-corrosion coating according to claim 1, characterized in that, The compound diluent is PMA to Solvesso 100 in a mass ratio of (6.5-7):(3-3.5); the diluent is PMA.

3. The waterproof and anti-corrosion coating according to claim 1, characterized in that, The rheology modifier is a polyurea compound type rheology modifier.

4. The waterproof and anti-corrosion coating according to claim 1, characterized in that, The preparation of the organotitanium-silicon-POSS hybrid resin involves reacting tetraisopropyl titanate, 2,3-dihydroxynaphthalene, methyltrimethoxysilane, KH-792, octaaminoPOSS, and deionized water in a mass ratio of (15-20):(3-3.5):(20-25):(4.5-5):(4-5):(2-2.5) in PMA at 50-60°C to obtain a monochelated titanium monomer solution; dissolving methyltrimethoxysilane, KH-792, and octaaminoPOSS in PMA and hydrolyzing with deionized water at pH 4.5-5 at 45-50°C to obtain a POSS-grafted oligomeric siloxane solution; and reacting and aging the monochelated titanium monomer solution and the POSS-grafted oligomeric siloxane solution at 60-65°C, adjusting the solid content to 45wt%-50wt% to obtain the final product.

5. The waterproof and anti-corrosion coating according to claim 1, characterized in that, The preparation method of the organotitanium-silicon-POSS hybrid resin, by mass parts, includes the following steps: mixing 15-20 parts of tetraisopropyl titanate and 25-30 parts of PMA, stirring at 30-35°C, adding 3-3.5 parts of 2,3-dihydroxynaphthalene dropwise, reacting at 50-60°C for 50-60 min, recovering isopropanol by vacuum distillation, and adding PMA to the original volume to obtain a monochelated titanium monomer solution; mixing 20-25 parts of methyltrimethoxysilane, 4.5-5 parts of KH-792, and 4-5 parts of octaaminoPOSS... After mixing, the solution is dissolved in 20-25 parts of PMA, stirred at 45-50℃, and 2-2.5 parts of deionized water adjusted to pH 4.5-5 with glacial acetic acid is added dropwise. The hydrolysis reaction is carried out for 40-50 min to obtain a POSS-grafted oligomeric siloxane solution. The monochelated titanium monomer solution is added dropwise to the POSS-grafted oligomeric siloxane solution, reacted at 60-65℃ for 3-3.5 h, and matured at 25-30℃ for 2-2.5 h. The solid content is adjusted to 45wt%-50wt%, filtered, and the organotitanium-silicon-POSS hybrid resin is obtained.

6. The waterproof and anti-corrosion coating according to claim 1, characterized in that, The preparation method of the intercalated modified hydrotalcite-boron nitride composite barrier filler, by mass parts, includes the following steps: dispersing 12-15 parts of magnesium aluminum hydrotalcite powder in 40-45 parts of anhydrous ethanol and 5-8 parts of deionized water, adjusting the pH to 3.8-4.2, stirring at 60-65℃, adding 1.5-2 parts of phytic acid, reacting at 80-85℃ for 1.5-2 hours, adding 5-7 parts of KH-550 modified boron nitride nanosheets, stirring at 70-75℃ for 1-1.5 hours; centrifuging, washing the solid, vacuum drying, and grinding to D50 < 3 μm to obtain the intercalated modified hydrotalcite-boron nitride composite barrier filler.

7. The waterproof and anti-corrosion coating according to claim 1, characterized in that, The preparation method of the nitrogen-phosphorus modified amine composite curing agent, by mass parts, includes the following steps: stirring 10-13 parts of tris(2-aminoethyl)amine and 8-12 parts of PMA at 40-45℃, adding 3-4 parts of hydroxymethylphenylphosphonic acid and 0.1-0.2 parts of p-toluenesulfonic acid, reacting at 70-75℃ for 2-2.5h, adding 25-30 parts of T-31 epoxy resin curing agent at 40-45℃, adjusting the pH to 7.5-8 with triethanolamine, cooling, and filtering to obtain the nitrogen-phosphorus modified amine composite curing agent.

8. The waterproof and anti-corrosion coating according to claim 1, characterized in that, The preparation method of the interface metal anchoring promoter, by mass parts, includes the following steps: adding 0.3 to 0.5 parts of triethylamine to 10 to 12 parts of anhydrous ethanol, stirring at 25 to 30°C, and then adding 3.5 to 4 parts of 2-aminoethylphosphonic acid to neutralize and stir, thereby obtaining an interface metal anchoring promoter solution.

9. The method for preparing a waterproof and anti-corrosion coating according to claim 1, characterized in that, Includes the following steps: S1: According to the formulation amount of component A, stir the organic titanium-silicon-POSS hybrid resin, low foaming wetting and dispersing agent, and compound diluent, add the intercalated modified hydrotalcite-boron nitride composite barrier filler and stir, grind to fineness <10μm; add rheology modifier and stir, filter, and obtain component A; S2: According to the formulation amount of component B, stir the nitrogen-phosphorus modified amine composite curing agent, interface metal anchoring accelerator and diluent, filter and obtain component B; S3: Components A and B are stored separately. When using, they are mixed according to the mass ratio, and the viscosity is adjusted to 4500-6500 mPa·s with diluent. After standing and maturing, the coating is obtained.

10. The method for preparing a waterproof and anti-corrosion coating according to claim 9, characterized in that, In S1, the grinding is carried out to a fineness of <10μm; in S3, the standing and ripening time is 10-15min.

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