Corrosion-resistant, fireproof and explosion-proof material, preparation method thereof and application of corrosion-resistant, fireproof and explosion-proof material in electric power tunnel
By coating the surface of the fireproof and explosion-proof substrate with a corrosion-resistant and fireproof coating, the problem of easy corrosion of fireproof board materials in power tunnels has been solved, achieving excellent corrosion resistance, fireproof and explosion-proof performance, and improving the safety of power tunnels.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- NANCHANG TAISHIDA ELECTRIC CO LTD
- Filing Date
- 2026-03-09
- Publication Date
- 2026-05-19
AI Technical Summary
The fireproof board materials used in existing power tunnels are prone to rust and corrosion, and their fireproof and explosion-proof effects are poor, resulting in short service life and insufficient safety.
A method for preparing corrosion-resistant, fire-resistant, and explosion-proof materials is adopted, in which a multifunctional modifier is generated by reacting an epoxidized phosphosilicate compound with a tripyridine compound, and then combined with a loaded modified composite nanomaterial to form a corrosion-resistant and fire-resistant coating, which is then coated on the surface of a fire-resistant and explosion-proof substrate.
It improves the corrosion resistance, fire resistance, and explosion-proof properties of the material, extends its service life, reduces the risk of explosion and fire, and enhances the safety of power tunnels.
Smart Images
Figure CN122060375A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of high-performance coatings and their application technology, and in particular to a corrosion-resistant, fire-resistant and explosion-proof material, its preparation method, and its application in power tunnels. Background Technology
[0002] With urban development, the development and utilization of urban underground space has become increasingly important, and the construction of power tunnels has become an effective way for cities to solve the problem of insufficient power line corridors. As a closed underground facility, the potential dangers of tunnels are far greater than those of surface buildings. Once an explosion or fire occurs in a tunnel, the difficulty of personnel escape and firefighting is far greater than that of surface buildings, and the resulting losses are also enormous. Power tunnels are also places with dense power lines, and the risk of explosion and fire is far greater than that of general underground facilities.
[0003] Installing fireproof boards is a common method to improve the fire resistance of tunnel structures. Currently, there are many types of fireproof boards on the market, with varying fire and explosion-proof effects. Furthermore, since the environment in power tunnels is often darker and more humid, fireproof boards containing metal materials are prone to rust and corrosion, thus shortening their service life. Therefore, developing a fireproof board material that combines corrosion resistance, fire resistance, and explosion-proof properties for use in power tunnels is crucial for improving the safety of power tunnels. Summary of the Invention
[0004] To address the aforementioned technical problems, this invention provides a method for preparing a corrosion-resistant, fire-resistant, and explosion-proof material, comprising the following steps: Step 1: Hydroquinone and diphenyldichlorosilane are reacted to obtain a silicon-containing compound; the silicon-containing compound is then reacted with phosphorus oxychloride, epichlorohydrin, and sodium hydroxide to obtain an epoxidized phosphorus silicon compound. Step 2: p-Nitrobenzaldehyde reacts with 2-acetylpyridine to obtain an intermediate; the intermediate is reduced by hydrazine hydrate to obtain a tripyridyl compound; the epoxidized phosphosilicate compound reacts with the tripyridyl compound to obtain a multifunctional modifier; Step 3: Disperse epoxy resin and loaded modified composite nanomaterials in a mixed solvent to obtain mixture A; disperse multifunctional modifier in a mixed solvent to obtain mixture B; mix mixture A and mixture B, add additives and curing agent to obtain corrosion-resistant and fire-retardant coating; Step 3: Spray the corrosion-resistant and fire-retardant coating onto the upper and lower surfaces of the fireproof and explosion-proof substrate, and cure it to form a corrosion-resistant and fire-retardant coating, thereby obtaining a corrosion-resistant, fireproof, and explosion-proof material.
[0005] Preferably, in step one, the method for preparing the epoxidized phosphorus silicon compound is as follows: Hydroquinone was added to tetrahydrofuran and stirred. Then triethylamine was added. Under a nitrogen atmosphere, diphenyldichlorosilane was added at 0°C. After the addition was complete, the reaction was continued at 38-42°C for 3-5 hours. After purification, a silicon-containing compound was obtained. The mass ratio of hydroquinone, tetrahydrofuran, triethylamine, and diphenyldichlorosilane was (11.01-22.02):(150-250):(11.13-22.26):(5.06-10.12). A silicon-containing compound was added to ethanol and stirred. Then phosphorus oxychloride was added, and the mixture was stirred and reacted at 38-42°C for 40-50 hours. Epichlorohydrin was then added, and the mixture was reacted at 65-75°C for 20-30 hours. The mixture was cooled to 48-52°C, and then 50wt% sodium hydroxide aqueous solution was added. The mixture was stirred for 5-7 hours and purified to obtain an epoxidized phosphorus silicon compound. The mass ratio of the silicon-containing compound, ethanol, phosphorus oxychloride, epichlorohydrin, and 50wt% sodium hydroxide aqueous solution was (7.83-15.66):(120-150):(1-2):(1.8-3.6):(1.56-3.12). In the above process, the phenolic hydroxyl group at one end of hydroquinone undergoes a substitution reaction with the chlorine at both ends of diphenyldichlorosilane to obtain a silicon-containing compound; the phenolic hydroxyl group of the silicon-containing compound undergoes a substitution reaction with the chlorine of phosphorus oxychloride, and the hydroxyl group of the resulting product then reacts with the epoxy group of epichlorohydrin, and is then treated with sodium hydroxide to remove hydrogen chloride, to obtain an epoxidized phosphorus silicon compound.
[0006] Preferably, in step two, the preparation method of the multifunctional modifier is as follows: p-Nitrobenzaldehyde was added to methanol, followed by the addition of 2-acetylpyridine and a 25 wt% ammonia solution, and then a 15 wt% potassium hydroxide solution was added dropwise. The mixture was stirred for 64-72 hours and purified to obtain an intermediate. The mass ratio of p-nitrobenzaldehyde, methanol, 2-acetylpyridine, 25 wt% ammonia solution, and 15 wt% potassium hydroxide solution was (3.17-6.34):(150-250):(5-10):(13.65-27.3):(17.1-34.2). The intermediate and palladium on carbon were added to ethanol and heated to 80-85℃ for 48-60 h. Hydrazine hydrate was added, and ethanol was continuously added as solvent during the reaction. After purification, a tripyridyl compound was obtained. The mass ratio of the intermediate, palladium on carbon, ethanol and hydrazine hydrate was (1-2):(0.2-0.4):(200-300):(15.48-30.96). The epoxidized phosphorus silicon compound was added to ethanol and stirred. Then, the tripyridyl compound was added and stirred at 60-70℃ for 10-14 h. After purification, a multifunctional modifier was obtained. The mass ratio of the epoxidized phosphorus silicon compound, ethanol and tripyridyl compound was (7.07-14.14):(150-250):(4.87-9.74). In the above process, p-nitrobenzaldehyde reacts with 2-acetylpyridine to obtain an intermediate, which is then reduced by hydrazine hydrate to obtain a tripyridine compound. The amino group of the tripyridine compound reacts with the epoxy group of the epoxidized phosphorus silicon compound to generate a hydroxyl group, thus obtaining a multifunctional modifier. The multifunctional modifier contains nitrogen, phosphorus, and silicon flame retardant elements, and its aromatic rings provide a sufficient carbon source for the formation of the char layer. The pyridine groups promote further cross-linking of the caramel layer, resulting in a good flame retardant and fireproof effect under multiple effects. In addition, the presence of functional groups such as aromatic rings, polar hydroxyl groups, P=O, and pyridine rings in the multifunctional modifier allows it to combine with the metal surface through physical and chemical interactions, promoting strong adsorption of the coating on the metal surface, thereby forming a dense and firm protective film on the metal surface. Furthermore, the presence of hydroxyl groups in the multifunctional modifier gives it good compatibility with the bisphenol A type epoxy resin matrix.
[0007] Preferably, in step three, the components of the corrosion-resistant and fire-retardant coating, by weight, are: 35-55 parts epoxy resin, 0.4-1.1 parts loaded modified composite nanomaterials, 1-3 parts multifunctional modifier, 0.4-1.2 parts additives, and 10-15 parts curing agent; wherein the epoxy resin is bisphenol A type epoxy resin.
[0008] Preferably, in step three, the additives include: 0.1-0.3 parts of dispersant BYK-P104, 0.1-0.3 parts of defoamer BYK-66N, 0.1-0.3 parts of leveling agent BYK-333, and 0.1-0.3 parts of anti-settling agent BYK-410.
[0009] Preferably, in step three, the curing agent includes polyamide 650 curing agent; the mixed solvent is obtained by mixing xylene and n-butanol in a mass ratio of 3:1.
[0010] Furthermore, in step three, the preparation method of the supported modified composite nanomaterial is as follows: Step S1: Dissolve urea and cerium chloride in deionized water, stir, add hydrogen peroxide, react at 175-185°C for 9-11 hours, purify, and obtain hollow cerium oxide nanospheres with a diameter of 200-400 nm; wherein the mass ratio of urea, cerium chloride, deionized water, and hydrogen peroxide is (2.4-3.6):(2-3):(400-600):(5.86-11.72); Hollow cerium oxide nanospheres were dispersed in methanol, then 2-methylimidazole was added and stirred, followed by zinc nitrate hexahydrate. The mixture was stirred at 350-450 r / min for 20-40 min and purified to obtain composite nanomaterials. The mass ratio of hollow cerium oxide nanospheres, methanol, 2-methylimidazole, and zinc nitrate hexahydrate was (2-3):(150-250):(20-40):(2.4-4.8). 5,6-Dimethylbenzimidazole, triethylamine, and methanol were mixed in a mass ratio of (0.8-1.6):(0.8-1.6):(100-150) to obtain a modifier solution; the composite nanomaterials and methanol were mixed in a mass ratio of (1-2):(60-100), sonicated, and then the above modifier solution was added. The mixture was stirred at 500-600 r / min for 20-30 h at 55-65℃ and purified to obtain the surface-modified composite nanomaterials. Step S2: Mix the surface-modified composite nanomaterial, ethanol, and 1,10-phenanthroline in a mass ratio of (1-3):(100-120):(1-2) to obtain a suspension; treat the suspension under vacuum at -0.1MPa for 20-40 min, repeat the vacuum treatment 2-4 times, centrifuge, and dry to obtain the loaded modified composite nanomaterial. In the above process, firstly, hollow cerium oxide nanospheres were synthesized via a hydrothermal method based on the Ostwald ripening mechanism. These hollow cerium oxide nanospheres can release cerium ions, forming a stable oxide film on the metal surface to prevent oxidation and corrosion. Furthermore, cerium oxide can also form a dense and stable char layer during combustion by catalyzing polymer pyrolysis, exhibiting synergistic flame-retardant and fire-retardant effects. Then, ZIF-8 was grown in situ on the hollow cerium oxide nanospheres using 2-methylimidazole and zinc nitrate hexahydrate as raw materials to obtain a composite nanomaterial. Compared to the hollow cerium oxide nanospheres, this composite nanomaterial has increased porosity and specific surface area, higher loading capacity, and can encapsulate more corrosion inhibitor 1,10-phenanthroline. More importantly… Furthermore, ZIF-8 particles extend the penetration path of corrosive media to improve corrosion resistance, and because they can decompose to produce zinc oxide during combustion, they catalyze the formation of a char layer, thereby improving the flame retardant and fireproof performance of the composite nanomaterials. Further, by treating the composite nanomaterials with a 5,6-dimethylbenzimidazole modifier solution, through surface ligand exchange, the 5,6-dimethylbenzimidazole molecule has the same polar components as 2-methylimidazole, but contains more hydrophobic non-polar components, resulting in better corrosion resistance. In addition, ZIF-8 molecules have nitrogen atoms, which can crosslink with epoxy resin through epoxy resin ring-opening reactions, promoting the uniform dispersion of the loaded modified composite nanomaterials in the epoxy resin aggregate.
[0011] Preferably, in step four, the fireproof and explosion-proof substrate consists of a first stainless steel composite fireproof and explosion-proof board, a fireproof and heat-insulating fiber board, and a second stainless steel composite fireproof and explosion-proof board, from bottom to top, and the layers are bonded together with adhesive.
[0012] Preferably, in step four, the thickness of the first stainless steel composite fireproof and explosion-proof plate and the second stainless steel composite fireproof and explosion-proof plate is 8-10mm, the thickness of the fireproof and heat-insulating fiber board is 15-25mm, and the thickness of the corrosion-resistant and fireproof coating is 1-3mm.
[0013] Preferably, in step four, the first stainless steel composite fireproof and explosion-proof board and the second stainless steel composite fireproof and explosion-proof board include stainless steel composite magnesium sulfate fireproof board or stainless steel composite silicate fireproof board; the fireproof and heat-insulating fiber board includes aluminum silicate fiber board or ceramic fiber board.
[0014] Preferably, in step four, the curing conditions are: placing at 25°C for 20-30 hours, and then baking at 50-60°C for 10-14 hours.
[0015] The corrosion-resistant, fire-resistant, and explosion-proof material is prepared using the aforementioned method.
[0016] The corrosion-resistant, fire-resistant, and explosion-proof material can be used in power tunnels.
[0017] Compared with the prior art, the beneficial effects of the present invention are as follows: 1. This invention provides a corrosion-resistant, fire-resistant, and explosion-proof material, comprising a fire-resistant and explosion-proof substrate and a corrosion-resistant and fire-resistant coating applied to the surface of the substrate. The fire-resistant and explosion-proof substrate consists of, from bottom to top, a first stainless steel composite fire-resistant and explosion-proof plate, a fire-resistant and heat-insulating fiber plate, and a second stainless steel composite fire-resistant and explosion-proof plate. Through the synergy between the layers of the fire-resistant and explosion-proof substrate and the combined effect of the corrosion-resistant and fire-resistant coating, the corrosion-resistant, fire-resistant, and explosion-proof material of this invention possesses excellent corrosion resistance, fire resistance, and explosion-proof performance. It can be used in power tunnels to reduce the risk of explosions and fires, extend the service life of the corrosion-resistant, fire-resistant, and explosion-proof material, and improve the safety of power tunnels. 2. The corrosion-resistant and fire-retardant coating of the present invention plays an important role in improving the comprehensive performance of corrosion-resistant, fire-resistant, and explosion-proof materials. This is because the corrosion-resistant and fire-retardant coating of the present invention uses epoxy resin as a matrix, with the addition of multifunctional modifiers and loaded modified composite nanomaterials. The multifunctional modifier contains nitrogen, phosphorus, and silicon flame-retardant elements and functional groups such as aromatic rings, polar hydroxyl groups, P=O, and pyridine rings, which allows the corrosion-resistant and fire-retardant coating to be adsorbed onto the substrate, forming a dense and firm protective film, thus playing a role in fire prevention and corrosion resistance. The loaded modified composite nanomaterials are obtained by in-situ growth of ZIF-8 on hollow cerium oxide nanospheres to form composite nanomaterials. After loading 1,10-phenanthroline onto the composite nanomaterials, surface ligand exchange is performed. The hollow cerium oxide nanospheres, ZIF-8 particles, and 1,10-phenanthroline synergistically with the multifunctional modifier give the corrosion-resistant and fire-retardant coating better corrosion resistance and fire resistance. Furthermore, the surface ligand exchange of the loaded modified composite nanomaterials gives it better hydrophobicity, thereby further improving the corrosion resistance of the corrosion-resistant and fire-retardant coating. Attached Figure Description
[0018] Figure 1 This is a structural schematic diagram of the corrosion-resistant, fire-resistant, and explosion-proof material of the present invention. Among them, 1 is the first stainless steel composite fireproof and explosion-proof board, 2 is the fireproof and heat-insulating fiber board, 3 is the second stainless steel composite fireproof and explosion-proof board, and 4 is the corrosion-resistant and fireproof coating. Figure 2 This is a schematic diagram illustrating the synthesis of the tripyridyl compound of the present invention; Figure 3 This is a schematic diagram illustrating the synthesis of the silicon-containing compound of the present invention; Figure 4 This is a schematic diagram illustrating the synthesis of the epoxidized phosphosilicate compound of the present invention. Detailed Implementation
[0019] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without creative effort are within the scope of protection of the present invention.
[0020] Example 1 This embodiment discloses a method for preparing a loaded modified composite nanomaterial, including the following steps: Step S1: Dissolve 3g of urea and 2.5g of cerium chloride in 500g of deionized water and stir for 30min. Then add 8.79g of hydrogen peroxide and transfer the reaction mixture into a Teflon-lined autoclave. React at 180°C for 10h. Centrifuge, wash the precipitate with deionized water, and dry at 80°C for 12h to obtain hollow cerium oxide nanospheres. 2.5g of hollow cerium oxide nanospheres were dispersed in 200g of methanol, then 30g of 2-methylimidazole was added and stirred for 20min, then 3.6g of zinc nitrate hexahydrate was added and stirred at 400r / min for 30min. The precipitate was collected by centrifugation and washed 7 times with methanol. Then it was dried at 60℃ for 12h to obtain composite nanomaterials. 1.2 g of 5,6-dimethylbenzimidazole and 1.2 g of triethylamine were dissolved in 125 g of methanol to obtain a modifier solution; 1.5 g of composite nanomaterials were added to 80 g of methanol and ultrasonically treated for 30 min, then the above modifier solution was added, and the mixture was stirred at 550 r / min at 60 °C for 25 h. The precipitate was collected by centrifugation, washed 7 times with methanol, and then dried at 60 °C for 24 h to obtain surface-modified composite nanomaterials. Step S2: Disperse 2g of surface-modified composite nanomaterials in 110g of ethanol, then add 1.5g of 1,10-phenanthroline, stir for 30min to obtain a suspension; treat the suspension under vacuum at -0.1MPa for 30min, repeat the vacuum treatment 3 times, centrifuge, and dry to obtain the loaded modified composite nanomaterials.
[0021] Example 2 This embodiment discloses a method for preparing a corrosion-resistant, fire-resistant, and explosion-proof material, including the following steps: Step 1: Add 11.01g hydroquinone to 150g tetrahydrofuran and stir for 20min. Then add 11.13g triethylamine. Under a nitrogen atmosphere, at 0℃, add 5.06g diphenyldichlorosilane dropwise. After the addition is complete, continue the reaction at 38℃ for 5h to obtain a product mixture. The product mixture is filtered and rotary evaporated to obtain a silicon-containing compound. 7.83 g of the silicon-containing compound was added to 120 g of ethanol and stirred for 20 min. Then, 1 g of phosphorus oxychloride was added and the mixture was stirred at 38 °C for 50 h. Next, 1.8 g of epichlorohydrin was added and the mixture was stirred at 65 °C for 30 h. The mixture was cooled to 48 °C and then 1.56 g of 50 wt% sodium hydroxide aqueous solution was added and stirred for 7 h. After the reaction was completed, the organic phase was extracted with chloroform and then dried with anhydrous magnesium sulfate. The solvent was removed by rotary evaporation to obtain the epoxidized phosphorus silicon compound. Step 2: Add 3.17g of p-nitrobenzaldehyde to 150g of methanol, then add 5g of 2-acetylpyridine and 13.65g of 25wt% ammonia solution, followed by dropwise addition of 17.1g of 15wt% potassium hydroxide solution. Stir for 64h. After the reaction is complete, filter. Wash the residue with deionized water and methanol, and dry to obtain the intermediate. Add 1g of the intermediate and 0.2g of palladium on carbon to 200g of ethanol and heat to 80℃ for 60h. During heating, add 15.48g of hydrazine hydrate as a reducing agent. Continuously replenish the solvent ethanol during the reaction. After the reaction is complete, filter. Add 26.5wt% sodium chloride solution to the filtrate to precipitate the product. Filter again, wash, and dry to obtain the tripyridyl compound. 7.07 g of epoxidized phosphorus silicon compound was added to 150 g of ethanol and stirred for 40 min. Then, 4.87 g of tripyridyl compound was added and the mixture was stirred at 60 °C for 14 h. After the reaction was completed, the solvent was evaporated to obtain the multifunctional modifier. Step 3: By weight, disperse 35 parts epoxy resin and 0.4 parts loaded modified composite nanomaterials in 10 parts mixed solvent to obtain mixture A; disperse 1 part multifunctional modifier in 5 parts mixed solvent and sonicate for 30 min to obtain mixture B; mix mixture A and mixture B and stir at 1500 r / min for 80 min. During stirring, add 0.1 parts dispersant BYK-P104, 0.1 parts defoamer BYK-66N, 0.1 parts leveling agent BYK-333, and 0.1 parts anti-settling agent BYK-410. After stirring evenly, add 10 parts polyamide 650 curing agent and continue stirring for 20 min to obtain corrosion-resistant and fire-retardant coating; wherein, the mixed solvent is obtained by mixing xylene and n-butanol in a mass ratio of 3:1. Step 4: Spray the corrosion-resistant and fire-retardant coating onto the upper and lower surfaces of the fireproof and explosion-proof substrate, place it at 25°C for 20 hours, and then bake it at 50°C for 14 hours to form a corrosion-resistant and fire-retardant coating, thereby obtaining a corrosion-resistant, fireproof, and explosion-proof material. The fireproof and explosion-proof substrate, from bottom to top, consists of a first stainless steel composite fireproof and explosion-proof board, a fireproof and heat-insulating fiber board, and a second stainless steel composite fireproof and explosion-proof board, with each layer bonded together by adhesive. The thickness of the first and second stainless steel composite fireproof and explosion-proof boards is 9 mm, the thickness of the fireproof and heat-insulating fiber board is 20 mm, and the thickness of the corrosion-resistant and fire-retardant coating is 2 mm. The first and second stainless steel composite fireproof and explosion-proof boards are stainless steel composite magnesium sulfate fireproof boards; the fireproof and heat-insulating fiber board is an aluminum silicate fiber board.
[0022] Example 3 This embodiment discloses a method for preparing a corrosion-resistant, fire-resistant, and explosion-proof material, including the following steps: Step 1: Add 22.02g hydroquinone to 250g tetrahydrofuran and stir for 40min. Then add 22.26g triethylamine. Under a nitrogen atmosphere and at 0℃, add 10.12g diphenyldichlorosilane dropwise. After the addition is complete, continue the reaction at 42℃ for 3h to obtain a product mixture. The product mixture is filtered and rotary evaporated to obtain a silicon-containing compound. 15.66 g of the silicon-containing compound was added to 150 g of ethanol and stirred for 40 min. Then 2 g of phosphorus oxychloride was added and the mixture was stirred at 42 °C for 40 h. Next, 3.6 g of epichlorohydrin was added and the mixture was stirred at 75 °C for 20 h. The mixture was cooled to 52 °C and then 3.12 g of 50 wt% sodium hydroxide aqueous solution was added and stirred for 5 h. After the reaction was completed, the organic phase was extracted with chloroform and then dried with anhydrous magnesium sulfate. The solvent was removed by rotary evaporation to obtain the epoxidized phosphorus silicon compound. Step 2: Add 6.34g of p-nitrobenzaldehyde to 250g of methanol, then add 10g of 2-acetylpyridine and 27.3g of 25wt% ammonia solution, followed by dropwise addition of 34.2g of 15wt% potassium hydroxide solution. Stir for 64h. After the reaction is complete, filter. Wash the residue with deionized water and methanol, and dry to obtain the intermediate. Add 2g of the intermediate and 0.4g of palladium on carbon to 300g of ethanol and heat to 85℃ for 48h. During heating, add 30.96g of hydrazine hydrate as a reducing agent. Continuously replenish the solvent ethanol during the reaction. After the reaction is complete, filter. Add 26.5wt% sodium chloride solution to the filtrate to precipitate the product. Filter again, wash, and dry to obtain the tripyridyl compound. 14.14 g of epoxidized phosphorus silicon compound was added to 250 g of ethanol and stirred for 60 min. Then, 9.74 g of tripyridyl compound was added and the mixture was stirred at 70 °C for 10 h. After the reaction was completed, the solvent was evaporated to obtain the multifunctional modifier. Step 3: By weight, disperse 55 parts epoxy resin and 1.1 parts loaded modified composite nanomaterials in 15.7 parts mixed solvent to obtain mixture A; disperse 3 parts multifunctional modifier in 8 parts mixed solvent and sonicate for 60 min to obtain mixture B; mix mixture A and mixture B and stir at 2500 r / min for 80 min. During stirring, add 0.3 parts dispersant BYK-P104, 0.3 parts defoamer BYK-66N, 0.3 parts leveling agent BYK-333, and 0.3 parts anti-settling agent BYK-410. After stirring evenly, add 15 parts polyamide 650 curing agent and continue stirring for 40 min to obtain corrosion-resistant and fire-retardant coating; wherein, the mixed solvent is obtained by mixing xylene and n-butanol in a mass ratio of 3:1. Step 4: Spray the corrosion-resistant and fire-retardant coating onto the upper and lower surfaces of the fireproof and explosion-proof substrate, place it at 25°C for 30 hours, and then bake it at 60°C for 10 hours to form a corrosion-resistant and fire-retardant coating, thereby obtaining a corrosion-resistant, fireproof, and explosion-proof material. The fireproof and explosion-proof substrate consists of, from bottom to top, a first stainless steel composite fireproof and explosion-proof board, a fireproof and heat-insulating fiber board, and a second stainless steel composite fireproof and explosion-proof board, with each layer bonded together by adhesive. The thickness of the first and second stainless steel composite fireproof and explosion-proof boards is 9 mm, the thickness of the fireproof and heat-insulating fiber board is 20 mm, and the thickness of the corrosion-resistant and fire-retardant coating is 2 mm. The first and second stainless steel composite fireproof and explosion-proof boards are stainless steel composite magnesium sulfate fireproof boards; the fireproof and heat-insulating fiber board is an aluminum silicate fiber board.
[0023] Example 4 This embodiment discloses a method for preparing a corrosion-resistant, fire-resistant, and explosion-proof material, including the following steps: Step 1: Add 16.52g hydroquinone to 200g tetrahydrofuran and stir for 30min. Then add 16.70g triethylamine. Under a nitrogen atmosphere, at 0℃, add 7.59g diphenyldichlorosilane dropwise. After the addition is complete, continue the reaction at 40℃ for 4h to obtain a product mixture. The product mixture is filtered and rotary evaporated to obtain a silicon-containing compound. 11.75 g of the silicon-containing compound was added to 135 g of ethanol and stirred for 30 min. Then, 1.5 g of phosphorus oxychloride was added and the mixture was stirred at 40 °C for 45 h. Next, 2.7 g of epichlorohydrin was added and the mixture was stirred at 70 °C for 25 h. The mixture was cooled to 50 °C and then 2.34 g of 50 wt% sodium hydroxide aqueous solution was added and stirred for 8 h. After the reaction was completed, the organic phase was extracted with chloroform and then dried with anhydrous magnesium sulfate. The solvent was removed by rotary evaporation to obtain the epoxidized phosphorus silicon compound. Step 2: Add 4.76g of p-nitrobenzaldehyde to 200g of methanol, then add 7.5g of 2-acetylpyridine and 20.48g of 25wt% ammonia solution, followed by dropwise addition of 25.65g of 15wt% potassium hydroxide solution. Stir for 68h. After the reaction is complete, filter. Wash the residue with deionized water and methanol, and dry to obtain the intermediate. Add 1.5g of the intermediate and 0.3g of palladium on carbon to 250g of ethanol and heat to 83℃ for 54h. During heating, add 23.22g of hydrazine hydrate as a reducing agent. Continuously replenish the solvent ethanol during the reaction. After the reaction is complete, filter. Add 26.5wt% sodium chloride solution to the filtrate to precipitate the product. Filter again, wash, and dry to obtain the tripyridyl compound. 10.61 g of epoxidized phosphorus silicon compound was added to 200 g of ethanol and stirred for 50 min. Then 7.31 g of tripyridyl compound was added and the mixture was stirred at 65 °C for 12 h. After the reaction was completed, the solvent was evaporated to obtain the multifunctional modifier. Step 3: By weight, disperse 45 parts epoxy resin and 0.75 parts loaded modified composite nanomaterials in 12.85 parts mixed solvent to obtain mixture A; disperse 2 parts multifunctional modifier in 6.5 parts mixed solvent and sonicate for 45 min to obtain mixture B; mix mixture A and mixture B and stir at 2000 r / min for 60 min. During stirring, add 0.2 parts dispersant BYK-P104, 0.2 parts defoamer BYK-66N, 0.2 parts leveling agent BYK-333, and 0.2 parts anti-settling agent BYK-410. After stirring evenly, add 12.5 parts polyamide 650 curing agent and continue stirring for 30 min to obtain corrosion-resistant and fire-retardant coating; wherein, the mixed solvent is obtained by mixing xylene and n-butanol in a mass ratio of 3:1. Step 4: Spray the corrosion-resistant and fire-retardant coating onto the upper and lower surfaces of the fireproof and explosion-proof substrate, place it at 25°C for 25 hours, and then bake it at 55°C for 12 hours to form a corrosion-resistant and fire-retardant coating, thereby obtaining a corrosion-resistant, fireproof, and explosion-proof material. The fireproof and explosion-proof substrate consists of, from bottom to top, a first stainless steel composite fireproof and explosion-proof board, a fireproof and heat-insulating fiber board, and a second stainless steel composite fireproof and explosion-proof board, with each layer bonded together by adhesive. The thickness of the first and second stainless steel composite fireproof and explosion-proof boards is 9 mm, the thickness of the fireproof and heat-insulating fiber board is 20 mm, and the thickness of the corrosion-resistant and fire-retardant coating is 2 mm. The first and second stainless steel composite fireproof and explosion-proof boards are stainless steel composite magnesium sulfate fireproof boards; the fireproof and heat-insulating fiber board is an aluminum silicate fiber board.
[0024] The loaded modified composite nanomaterials in Examples 2-4 above are the loaded modified composite nanomaterials prepared in Example 1.
[0025] Comparative Example 1 This comparative example discloses a method for preparing cerium oxide-supported nanospheres, comprising the following steps: Step S1: Dissolve 3g of urea and 2.5g of cerium chloride in 500g of deionized water and stir for 30min. Then add 8.79g of hydrogen peroxide and transfer the reaction mixture into a Teflon-lined autoclave. React at 180°C for 10h. Centrifuge, wash the precipitate with deionized water, and dry at 80°C for 12h to obtain hollow cerium oxide nanospheres. 2g of hollow cerium oxide nanospheres were dispersed in 110g of ethanol, and then 1.5g of 1,10-phenanthroline was added. The mixture was stirred for 30min to obtain a suspension. The suspension was then subjected to vacuum treatment at -0.1MPa for 30min, and the vacuum treatment was repeated 3 times. After centrifugation and drying, the modified cerium oxide nanospheres were obtained.
[0026] Comparative Example 2 This comparative example discloses a method for preparing a loaded modified composite nanomaterial, comprising the following steps: Step S1: Dissolve 3g of urea and 2.5g of cerium chloride in 500g of deionized water and stir for 30min. Then add 8.79g of hydrogen peroxide and transfer the reaction mixture into a Teflon-lined autoclave. React at 180°C for 10h. Centrifuge, wash the precipitate with deionized water, and dry at 80°C for 12h to obtain hollow cerium oxide nanospheres. 2.5g of hollow cerium oxide nanospheres were dispersed in 200g of methanol, then 30g of 2-methylimidazole was added and stirred for 20min, then 3.6g of zinc nitrate hexahydrate was added and stirred at 400r / min for 30min. The precipitate was collected by centrifugation and washed 7 times with methanol. Then it was dried at 60℃ for 12h to obtain composite nanomaterials. Step S2: Disperse 2g of composite nanomaterial in 110g of ethanol, then add 1.5g of 1,10-phenanthroline, stir for 30min to obtain a suspension; treat the suspension under vacuum at -0.1MPa for 30min, repeat the vacuum treatment 3 times, centrifuge, and dry to obtain the loaded modified composite nanomaterial.
[0027] Comparative Example 3 Compared with Example 4, Comparative Example 3 used the loaded modified cerium oxide nanospheres prepared in Comparative Example 1 instead of the loaded modified composite nanomaterials prepared in Example 1 in the process of preparing the corrosion-resistant and fireproof coating, while keeping other conditions unchanged.
[0028] Comparative Example 4 Compared with Example 4, Comparative Example 4 used the loaded modified composite nanomaterial prepared in Comparative Example 2 instead of the loaded modified composite nanomaterial prepared in Example 1 in the process of preparing the corrosion-resistant and fireproof coating, while keeping all other conditions unchanged.
[0029] Comparative Example 5 Compared with Example 4, Comparative Example 5 used an epoxide phosphorus silicon compound instead of a multifunctional modifier in the preparation of the corrosion-resistant and fire-retardant coating, while keeping all other conditions unchanged.
[0030] Comparative Example 6 Compared with Example 4, Comparative Example 6 used a tripyridyl compound instead of a multifunctional modifier in the preparation of the corrosion-resistant and fire-retardant coating, while keeping all other conditions unchanged.
[0031] In the above examples and comparative examples, the epoxy resin was Nan Ya NPSN-901X75 epoxy resin with an epoxy equivalent of 450-500 g / eq and a viscosity (25℃) of 8000-15000 Pa·s, sourced from Nan Ya Epoxy Resin (Kunshan) Co., Ltd.; the curing agent was polyamide 650 curing agent with a density of 0.97 g / mL and an amine value of 170 mg KOH / g, sourced from Wuhan Jiyesheng Chemical Co., Ltd.; and the dispersant (BYK-P104), leveling agent (BYK-333), defoamer (BYK-66N), and anti-settling agent (BYK-410) were all sourced from BYK Additives (Shanghai) Co., Ltd.
[0032] Experimental Example Performance tests were conducted on the corrosion-resistant and fire-retardant coatings prepared in Examples 2-4 and Comparative Examples 3-6: I. Fire resistance performance test: conducted in accordance with standard GB 14907-2018 "Fire-retardant Coatings for Steel Structures"; II. Corrosion Resistance Test: The salt spray resistance of the coating was tested in accordance with the standard GB / T 1771-2024 "Determination of the resistance of paints and varnishes to neutral salt spray" to characterize the corrosion resistance of the coating.
[0033] The test results are shown in Table 1: Table 1 ; As can be seen from the test results in Table 1, the corrosion-resistant and fire-retardant coatings prepared in Examples 2-4 of the present invention have excellent corrosion-resistant and fire-retardant properties. Therefore, by coating them on the surface of the fireproof and explosion-proof substrate, the corrosion-resistant, fireproof, and explosion-proof materials are endowed with excellent corrosion-resistant and fire-retardant properties through the synergy between the layers of the fireproof and explosion-proof substrate and the combined effect of the corrosion-resistant and fire-retardant coating.
[0034] A comparison of Comparative Examples 3-4 and Example 4 shows that the composite nanomaterial obtained by in-situ growth of ZIF-8 on hollow cerium oxide nanospheres has increased porosity and specific surface area compared to hollow cerium oxide nanospheres, exhibiting higher loading capacity and the ability to encapsulate more corrosion inhibitor 1,10-phenanthroline. Furthermore, the ZIF-8 particles themselves possess certain corrosion resistance and fire retardant properties. Further, treatment of the composite nanomaterial with a 5,6-dimethylbenzimidazole modifier solution enhances the hydrophobicity of the surface-modified composite nanomaterial through surface ligand exchange, thereby improving its corrosion resistance. In addition, the ZIF-8 molecule contains nitrogen atoms, which can crosslink with epoxy resin through ring-opening reactions, promoting uniform dispersion of the loaded modified composite nanomaterial within the epoxy resin matrix, thus improving the overall performance of the corrosion-resistant and fire-retardant coating. As can be seen from the comparison between Comparative Examples 5-6 and Example 4, the multifunctional modifier of the present invention contains nitrogen, phosphorus, and silicon flame retardant elements, and the aromatic rings therein provide sufficient carbon source for the formation of the char layer. The pyridine groups promote the further cross-linking of the caramel layer. Under multiple effects, it plays a very good flame retardant and fireproof effect. In addition, the presence of functional groups such as aromatic rings, polar hydroxyl groups, P=O, and pyridine rings in the multifunctional modifier allows it to combine with the metal surface through physical and chemical interactions, promoting the strong adsorption of the coating on the metal surface and forming a dense and firm protective film on the metal surface. Furthermore, the multifunctional modifier has good compatibility with the bisphenol A type epoxy resin matrix, thereby giving the corrosion-resistant and fireproof coating better performance.
[0035] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.
Claims
1. A method for preparing a corrosion-resistant, fire-resistant, and explosion-proof material, characterized in that, Includes the following steps: Step 1: Hydroquinone and diphenyldichlorosilane are reacted to obtain a silicon-containing compound; the silicon-containing compound is then reacted with phosphorus oxychloride, epichlorohydrin, and sodium hydroxide to obtain an epoxidized phosphorus silicon compound. Step 2: p-Nitrobenzaldehyde reacts with 2-acetylpyridine to obtain an intermediate; the intermediate is reduced by hydrazine hydrate to obtain a tripyridyl compound; the epoxidized phosphosilicate compound reacts with the tripyridyl compound to obtain a multifunctional modifier; Step 3: Disperse epoxy resin and loaded modified composite nanomaterials in a mixed solvent to obtain mixture A; disperse multifunctional modifier in a mixed solvent to obtain mixture B; mix mixture A and mixture B, add additives and curing agent to obtain corrosion-resistant and fire-retardant coating; Step 3: Spray the corrosion-resistant and fire-retardant coating onto the upper and lower surfaces of the fireproof and explosion-proof substrate, and cure it to form a corrosion-resistant and fire-retardant coating, thereby obtaining a corrosion-resistant, fireproof, and explosion-proof material.
2. The method for preparing the corrosion-resistant, fire-resistant, and explosion-proof material according to claim 1, characterized in that, In step one, the preparation method of the epoxidized phosphorus silicon compound is as follows: Hydroquinone was added to tetrahydrofuran and stirred. Then triethylamine was added. Under a nitrogen atmosphere, diphenyldichlorosilane was added at 0°C. After the addition was complete, the reaction was continued at 38-42°C for 3-5 hours. After purification, a silicon-containing compound was obtained. The mass ratio of hydroquinone, tetrahydrofuran, triethylamine, and diphenyldichlorosilane was (11.01-22.02):(150-250):(11.13-22.26):(5.06-10.12). The silicon-containing compound was added to ethanol and stirred. Then phosphorus oxychloride was added and the mixture was stirred and reacted at 38-42℃ for 40-50 h. Epichlorohydrin was then added and the mixture was reacted at 65-75℃ for 20-30 h. The mixture was cooled to 48-52℃ and then 50wt% sodium hydroxide aqueous solution was added. The mixture was stirred for 5-7 h and purified to obtain the epoxidized phosphorus silicon compound. The mass ratio of the silicon-containing compound, ethanol, phosphorus oxychloride, epichlorohydrin, and 50wt% sodium hydroxide aqueous solution was (7.83-15.66):(120-150):(1-2):(1.8-3.6):(1.56-3.12).
3. The method for preparing the corrosion-resistant, fire-resistant, and explosion-proof material according to claim 1, characterized in that, In step two, the preparation method of the multifunctional modifier is as follows: p-Nitrobenzaldehyde was added to methanol, followed by the addition of 2-acetylpyridine and a 25 wt% ammonia solution, and then a 15 wt% potassium hydroxide solution was added dropwise. The mixture was stirred for 64-72 hours and purified to obtain an intermediate. The mass ratio of p-nitrobenzaldehyde, methanol, 2-acetylpyridine, 25 wt% ammonia solution, and 15 wt% potassium hydroxide solution was (3.17-6.34):(150-250):(5-10):(13.65-27.3):(17.1-34.2). The intermediate and palladium on carbon were added to ethanol and heated to 80-85℃ for 48-60 h. Hydrazine hydrate was added and the mixture was purified to obtain a tripyridyl compound. The mass ratio of the intermediate, palladium on carbon, ethanol and hydrazine hydrate was (1-2):(0.2-0.4):(200-300):(15.48-30.96). The epoxidized phosphorus silicon compound was added to ethanol and stirred. Then, the tripyridyl compound was added and stirred at 60-70℃ for 10-14 h. After purification, a multifunctional modifier was obtained. The mass ratio of the epoxidized phosphorus silicon compound, ethanol and tripyridyl compound was (7.07-14.14):(150-250):(4.87-9.74).
4. The method for preparing the corrosion-resistant, fire-resistant, and explosion-proof material according to claim 1, characterized in that, In step three, the components of the corrosion-resistant and fireproof coating, by weight, are: 35-55 parts epoxy resin, 0.4-1.1 parts loaded modified composite nanomaterials, 1-3 parts multifunctional modifier, 0.4-1.2 parts additives, and 10-15 parts curing agent.
5. The method for preparing the corrosion-resistant, fire-resistant, and explosion-proof material according to claim 1, characterized in that, In step three, the preparation method of the supported modified composite nanomaterial is as follows: Step S1: Dissolve urea and cerium chloride in deionized water, stir, add hydrogen peroxide, react at 175-185°C for 9-11 hours, purify, and obtain hollow cerium oxide nanospheres with a diameter of 200-400 nm; wherein the mass ratio of urea, cerium chloride, deionized water, and hydrogen peroxide is (2.4-3.6):(2-3):(400-600):(5.86-11.72); Hollow cerium oxide nanospheres were dispersed in methanol, then 2-methylimidazole was added and stirred, followed by zinc nitrate hexahydrate. The mixture was stirred at 350-450 r / min for 20-40 min and purified to obtain composite nanomaterials. The mass ratio of hollow cerium oxide nanospheres, methanol, 2-methylimidazole, and zinc nitrate hexahydrate was (2-3):(150-250):(20-40):(2.4-4.8). 5,6-Dimethylbenzimidazole, triethylamine, and methanol were mixed in a mass ratio of (0.8-1.6):(0.8-1.6):(100-150) to obtain a modifier solution; the composite nanomaterials and methanol were mixed in a mass ratio of (1-2):(60-100), sonicated, and then the above modifier solution was added. The mixture was stirred at 500-600 r / min for 20-30 h at 55-65℃ and purified to obtain the surface-modified composite nanomaterials. Step S2: Mix the surface-modified composite nanomaterial, ethanol, and 1,10-phenanthroline in a mass ratio of (1-3):(100-120):(1-2) to obtain a suspension; treat the suspension under vacuum at -0.1 MPa for 20-40 min, repeat the vacuum treatment 2-4 times, centrifuge, and dry to obtain the loaded modified composite nanomaterial.
6. The method for preparing the corrosion-resistant, fire-resistant, and explosion-proof material according to claim 1, characterized in that, In step four, the fireproof and explosion-proof substrate consists of, from bottom to top, a first stainless steel composite fireproof and explosion-proof board, a fireproof and heat-insulating fiber board, and a second stainless steel composite fireproof and explosion-proof board, with each layer bonded together by an adhesive.
7. The method for preparing the corrosion-resistant, fire-resistant, and explosion-proof material according to claim 1, characterized in that, In step four, the thickness of the first stainless steel composite fireproof and explosion-proof plate and the second stainless steel composite fireproof and explosion-proof plate is 8-10mm, the thickness of the fireproof and heat-insulating fiber board is 15-25mm, and the thickness of the corrosion-resistant and fireproof coating is 1-3mm.
8. The method for preparing the corrosion-resistant, fire-resistant, and explosion-proof material according to claim 1, characterized in that, In step four, the first stainless steel composite fireproof and explosion-proof board and the second stainless steel composite fireproof and explosion-proof board include stainless steel composite magnesium sulfate fireproof board or stainless steel composite silicate fireproof board; the fireproof and heat-insulating fiber board includes aluminum silicate fiber board or ceramic fiber board.
9. A corrosion-resistant, fire-resistant, and explosion-proof material prepared by the method for preparing corrosion-resistant, fire-resistant, and explosion-proof material as described in any one of claims 1-8.
10. The application of the corrosion-resistant, fire-resistant, and explosion-proof material according to claim 9 in power tunnels.