Corrosion-resistant fireproof plate and preparation method thereof

Abstract

The application discloses a kind of corrosion-resistant fireproof plate and preparation method thereof, it is related to functional composite material technical field.The application first phosphorizes graphene oxide and obtains phosphorized graphene oxide;With 1,4-ditolyl dibromide and 1-(3-aminopropyl) imidazole as raw material, double-cation ionic liquid is synthesized, and then phosphorized graphene oxide is reacted with double-cation ionic liquid under the action of condensing agent to obtain ionic liquid functionalized graphene oxide, which is further reacted with molybdenum acetylacetone to obtain ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide;Bis (4-fluorophenyl) sulfone, bis (3-amino-4-hydroxyphenyl) sulfone and hexafluorobisphenol A are polycondensed to obtain fluorine-containing and amino-containing polyether sulfone;Finally, epoxy resin, fluorine-containing and amino-containing polyether sulfone, ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide and curing agent are mixed, defoamed and cured to obtain the corrosion-resistant fireproof plate.The corrosion-resistant fireproof plate prepared by the application has high flame retardancy, low smoke toxicity and excellent corrosion resistance.

Description

Technical Field

[0001] This invention relates to the field of functional composite materials technology, specifically to a corrosion-resistant and fireproof board and its preparation method. Background Technology

[0002] Epoxy resin possesses strong adhesion, excellent mechanical properties, and good formability, making it an ideal substrate for preparing high-performance fireproof boards. However, epoxy resin itself is flammable, produces a large amount of smoke when burning, and its corrosion resistance still has room for improvement in complex and harsh environments, limiting its application in high-end fireproofing fields. Traditional fireproof boards often suffer from limited functionality; epoxy resin-based fireproof boards also struggle to balance flame retardancy and corrosion resistance. In humid, acidic, or alkaline environments, they are prone to corrosion and aging, leading to decreased board strength, reduced flame retardant effect, and even loss of fire protection. Furthermore, some fireproof boards release large amounts of smoke and toxic gases during combustion, further exacerbating fire hazards. Meanwhile, the flame retardants used in traditional fireproof boards often suffer from poor environmental performance and incompatible compatibility with epoxy resin substrates.

[0003] While some existing technologies attempt to improve the flame retardant or corrosion-resistant properties of epoxy resin-based fireproof boards, they often suffer from complex manufacturing processes, high costs, or limited improvements in the overall performance of the modified boards, failing to simultaneously achieve a unified combination of excellent flame retardancy, smoke suppression, corrosion resistance, and mechanical properties. Therefore, to meet the high-end application requirements of fireproof boards in various fields and address the performance deficiencies of traditional epoxy resin-based fireproof boards, developing a rational, environmentally friendly, and efficient method for preparing epoxy resin-based fireproof boards that combines excellent flame retardant, smoke suppression, and corrosion resistance is of significant practical importance and application value. Summary of the Invention

[0004] The purpose of this invention is to provide a corrosion-resistant and fireproof board and its preparation method, so as to solve the problems existing in the prior art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: A corrosion-resistant and fireproof board is prepared by mixing, degassing, and curing epoxy resin, ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide, fluorinated and ammonia-containing polyethersulfone, and a curing agent.

[0006] As an optimization, the ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide is prepared by reacting phosphorylated graphene oxide with a dual-cationic ionic liquid under the action of a condensing agent, followed by further reaction with molybdenum acetylacetonate.

[0007] As an optimization, the phosphorylated graphene oxide is prepared by reacting graphene oxide with an 85 wt% aqueous solution of phosphoric acid.

[0008] As an optimization, the dual-cationic ionic liquid is prepared by reacting 1,4-xylenedibromo and 1-(3-aminopropyl)imidazolium.

[0009] As an optimization, the fluorinated and ammonia-containing polyethersulfone is prepared by polycondensation of bis(4-fluorophenyl)sulfone, bis(3-amino-4-hydroxyphenyl)sulfone and hexafluorobisphenol A.

[0010] A method for preparing a corrosion-resistant and fireproof board includes the following preparation steps: (1) Graphene oxide and 85wt% phosphoric acid aqueous solution are mixed at a mass ratio of 1:(70~90), stirred at 45~55℃ for 10~14h, washed with deionized water until the pH of the washing solution is 4~5, and dried in an oven at 65~75℃ to obtain phosphorylated graphene oxide; 1,4-xylene dibromide, 1-(3-aminopropyl)imidazolium, dichloromethane and anhydrous ethanol are weighed at a mass ratio of 1:(0.9~1):(10~12):(6~8), 1,4-xylene dibromide is dissolved in dichloromethane, and added dropwise to a 1-(3-aminopropyl)imidazolium solution dissolved in anhydrous ethanol under stirring at 25~30℃. After the addition is completed, the mixture is stirred for 22~26h, rotary evaporated, washed with ethyl acetate, and dried under vacuum to obtain a dicationic ionic liquid; phosphorylated graphene oxide, dicationic ionic liquid, condensing agent The ionic liquid-functionalized graphene oxide was prepared by mixing N,N-dimethylformamide at a mass ratio of 1:(30~35):(30~35):(580~600), ultrasonicating at 100W for 10~20 min, stirring at 45~55℃ for 45~50 h, washing with N,N-dimethylformamide, deionized water and methanol in sequence, and drying in an oven at 65~75℃. The ionic liquid-functionalized graphene oxide was then mixed with acetone at a mass ratio of 1:(30~35), ultrasonicated at 100W for 10~20 min, and 1.8~2 times the mass of acetylacetone molybdenum was added. The mixture was stirred at 25~30℃ for 22~26 h, filtered, washed with ethanol, and dried in an oven at 65~75℃. (2) Bis(4-fluorophenyl) sulfone, bis(3-amino-4-hydroxyphenyl) sulfone, hexafluorobisphenol A, N,N-dimethylacetamide, toluene and potassium carbonate are mixed in a mass ratio of 1:(0.4~0.5):(0.55~0.65):(9~10):(7~8):(0.6~0.65), and reacted at 150~160℃ for 4~5h in a nitrogen atmosphere. The temperature is then raised to 175~185℃ and reacted for 4~5h. Excess ether is used to precipitate the precipitate, which is then washed with deionized water and dried under vacuum at 50℃ to obtain fluorinated and ammonia-containing polyether sulfone. (3) Mix epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:(0.05~0.15), add 0.01~0.02 times the mass of epoxy resin of ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide, sonicate at 100W for 30~60min, add 0.5~0.6 times the mass of epoxy resin of methyltetrahydrophthalic anhydride curing agent, stir at 25~30℃ for 20~30min to remove bubbles, place in an oven, heat at 90℃ for 0.5h, at 120℃ for 2h, and at 150℃ for 2h to obtain corrosion-resistant fireproof board.

[0011] As an optimization, the graphene oxide in step (1) is reagent grade and manufactured by Kaisa New Materials Co., Ltd.; the condensing agent is benzotriazol-1-yl-oxytripyrrolidinephosphine hexafluorophosphate (PyBOP).

[0012] As an optimization, the epoxy resin in step (3) is bisphenol A type E-51 epoxy resin; the preheating of fluorinated and ammonia polyether sulfone is to stir the fluorinated and ammonia polyether sulfone at 90°C for 30 min.

[0013] Compared with the prior art, the beneficial effects achieved by the present invention are: In preparing the corrosion-resistant and fireproof board, this invention uses 1,4-xylenedibromo and 1-(3-aminopropyl)imidazolium as raw materials to synthesize a dual-cationic ionic liquid. Then, phosphorylated graphene oxide is reacted with the dual-cationic ionic liquid under the action of a condensing agent to obtain ionic liquid-functionalized graphene oxide. Further reaction with molybdenum acetylacetonate yields ionic liquid-functionalized flame-retardant and smoke-suppressing graphene oxide. Bis(4-fluorophenyl)sulfone, bis(3-amino-4-hydroxyphenyl)sulfone, and hexafluorobisphenol A are condensed to obtain fluorinated and ammonia-containing polyethersulfone. Finally, epoxy resin, fluorinated and ammonia-containing polyethersulfone, ionic liquid-functionalized flame-retardant and smoke-suppressing graphene oxide, and a curing agent are mixed, degassed, and cured to obtain the corrosion-resistant and fireproof board.

[0014] First, ionic liquid-functionalized flame-retardant and smoke-suppressing graphene oxide is added to the epoxy resin matrix. Phosphate groups are introduced onto the surface of this functionalized graphene oxide through phosphorylation. During combustion, these phosphate groups catalyze the dehydration of the epoxy resin into char, forming a dense char layer that blocks heat and oxygen transfer, thus exerting a highly efficient condensed-phase flame-retardant effect. Simultaneously, the surface-grafted dual-cationic ionic liquid not only introduces amino and imidazole cations but also further coordinates molybdenum acetylacetonate. The molybdenum compound inhibits smoke generation and promotes char formation, achieving low-smoke and low-toxicity emissions. Imidazole cations catalyze the ring-opening curing of the epoxy resin, significantly improving the curing reaction efficiency and participating in the construction of the cross-linking network. Amino groups form chemical bonds with the resin matrix, improving the interfacial compatibility between the functional filler and the epoxy resin. The two-dimensional graphene sheets form a physical barrier during combustion and also provide corrosion resistance. This multi-element synergistic effect enables the board to achieve a high flame-retardant rating and excellent smoke suppression effect with low additive amounts, while simultaneously improving the mechanical properties of the resin matrix.

[0015] Secondly, this invention introduces fluorinated and amino-containing polyethersulfone into epoxy resin, which is copolymerized from bis(4-fluorophenyl)sulfone, bis(3-amino-4-hydroxyphenyl)sulfone, and hexafluorobisphenol A. The molecular chain simultaneously contains amino, fluorinated aromatic rings, and ethersulfone structures. The amino groups participate in the curing process of the epoxy resin and, together with the amino groups on the surface of ionic liquid-functionalized graphene oxide, form a multi-point cross-linking network, allowing the polyethersulfone segments to diffuse uniformly in the resin matrix. This effectively solves the drawbacks of stress concentration and limited mechanical properties caused by the large difference in mechanical properties between graphene oxide and epoxy resin. The fluorinated aromatic rings and hexafluorobisphenol A structure endow the resin matrix with extremely low surface energy and excellent hydrophobic and oleophobic properties, significantly improving the corrosion resistance and long-term service stability of the board under harsh environments such as high temperature, strong acid, strong alkali, and salt spray. The amino groups on the surface of ionic liquid-functionalized flame-retardant and smoke-suppressing graphene oxide and the amino groups in fluorinated and ammonia-containing polyether sulfone synergistically participate in curing and cross-linking, jointly constructing a multi-layered composite structure, enabling the fireproof board to simultaneously possess comprehensive properties such as high-efficiency flame retardancy, low smoke and low toxicity, excellent mechanical properties and long-term corrosion resistance. Detailed Implementation

[0016] 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. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0017] To more clearly illustrate the method provided by the present invention, the following embodiments will be described in detail.

[0018] Example 1: A method for preparing a corrosion-resistant and fireproof board includes the following preparation steps: (1) Graphene oxide and 85wt% phosphoric acid aqueous solution were mixed at a mass ratio of 1:70, stirred at 45℃ for 10h, washed with deionized water until the pH of the washing solution was 4, and dried in an oven at 65℃ to obtain phosphorylated graphene oxide; 1,4-xylenedibromo, 1-(3-aminopropyl)imidazole, dichloromethane and anhydrous ethanol were weighed at a mass ratio of 1:0.9:10:6, 1,4-xylenedibromo was dissolved in dichloromethane, and added dropwise to a 1-(3-aminopropyl)imidazole solution dissolved in anhydrous ethanol under stirring at 25℃. After the addition was completed, the mixture was stirred for 22h, rotary evaporated, washed with ethyl acetate, and dried under vacuum to obtain a dicationic ionic liquid; phosphorylated graphene oxide and dicationic ionic liquid were then mixed. Liquid, condensing agent, and N,N-dimethylformamide were mixed at a mass ratio of 1:30:30:580, ultrasonicated at 100W for 10 min, stirred at 45℃ for 45 h, washed successively with N,N-dimethylformamide, deionized water, and methanol, and dried in an oven at 65℃ to obtain ionic liquid functionalized graphene oxide. The ionic liquid functionalized graphene oxide was mixed with acetone at a mass ratio of 1:30, ultrasonicated at 100W for 10 min, and 1.8 times the mass of acetylacetone molybdenum was added. The mixture was stirred at 25℃ for 22 h, filtered, washed with ethanol, and dried in an oven at 65℃ to obtain ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide. (2) Bis(4-fluorophenyl) sulfone, bis(3-amino-4-hydroxyphenyl) sulfone, hexafluorobisphenol A, N,N-dimethylacetamide, toluene and potassium carbonate were mixed in a mass ratio of 1:0.4:0.55:9:7:0.6 and reacted at 150°C for 4 h in a nitrogen atmosphere. The temperature was then raised to 175°C and reacted for another 4 h. Excess ether was used to precipitate the precipitate. The precipitate was washed with deionized water and dried under vacuum at 50°C to obtain fluorinated and ammonia-containing polyether sulfone. (3) Mix epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:0.1, add 0.015 times the mass of epoxy resin of ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide, sonicate at 100W for 30 min, add 0.5 times the mass of epoxy resin of methyltetrahydrophthalic anhydride curing agent, stir at 25℃ for 20 min to remove bubbles, place in an oven, heat at 90℃ for 0.5 h, at 120℃ for 2 h, and at 150℃ for 2 h to obtain corrosion-resistant fireproof board.

[0019] Example 2: A method for preparing a corrosion-resistant and fireproof board includes the following preparation steps: (1) Graphene oxide and 85wt% phosphoric acid aqueous solution were mixed at a mass ratio of 1:80, stirred at 50℃ for 12h, washed with deionized water until the pH of the washing solution was 4.5, and dried in an oven at 70℃ to obtain phosphorylated graphene oxide; 1,4-xylenedibromo, 1-(3-aminopropyl)imidazole, dichloromethane and anhydrous ethanol were weighed at a mass ratio of 1:0.95:11:7, 1,4-xylenedibromo was dissolved in dichloromethane, and added dropwise to a 1-(3-aminopropyl)imidazole solution dissolved in anhydrous ethanol under stirring at 27℃. After the addition was completed, the mixture was stirred for 24h, rotary evaporated, washed with ethyl acetate, and dried under vacuum to obtain a dicationic ionic liquid; phosphorylated graphene oxide and dicationic ionic liquid were then mixed. Ionic liquid, condensing agent, and N,N-dimethylformamide were mixed in a mass ratio of 1:33:33:590, ultrasonicated at 100W for 15 min, stirred at 50℃ for 48 h, washed successively with N,N-dimethylformamide, deionized water, and methanol, and dried in an oven at 70℃ to obtain ionic liquid-functionalized graphene oxide. Ionic liquid-functionalized graphene oxide was mixed with acetone in a mass ratio of 1:33, ultrasonicated at 100W for 15 min, and 1.9 times the mass of acetylacetone molybdenum was added. The mixture was stirred at 27℃ for 24 h, filtered, washed with ethanol, and dried in an oven at 70℃ to obtain ionic liquid-functionalized flame-retardant and smoke-suppressing graphene oxide. (2) Bis(4-fluorophenyl) sulfone, bis(3-amino-4-hydroxyphenyl) sulfone, hexafluorobisphenol A, N,N-dimethylacetamide, toluene and potassium carbonate were mixed in a mass ratio of 1:0.45:0.6:9.5:7.5:0.63 and reacted at 155°C for 4.5 h in a nitrogen atmosphere. The temperature was then raised to 180°C and reacted for another 4.5 h. Excess ether was used to precipitate the precipitate. The precipitate was washed with deionized water and dried under vacuum at 50°C to obtain fluorinated and ammonia-containing polyether sulfone. (3) Mix epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:0.1, add 0.015 times the mass of epoxy resin of ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide, sonicate at 100W for 45 min, add 0.55 times the mass of epoxy resin of methyltetrahydrophthalic anhydride curing agent, stir at 27℃ for 25 min to remove bubbles, place in an oven, heat at 90℃ for 0.5 h, at 120℃ for 2 h, and at 150℃ for 2 h to obtain corrosion-resistant fireproof board.

[0020] Example 3: A method for preparing a corrosion-resistant and fireproof board includes the following preparation steps: (1) Graphene oxide and 85wt% phosphoric acid aqueous solution were mixed at a mass ratio of 1:90, stirred at 55℃ for 14h, washed with deionized water until the pH of the washing solution was 5, and dried in an oven at 75℃ to obtain phosphorylated graphene oxide; 1,4-xylenedibromo, 1-(3-aminopropyl)imidazole, dichloromethane and anhydrous ethanol were weighed at a mass ratio of 1:1:12:8, 1,4-xylenedibromo was dissolved in dichloromethane, and added dropwise to a 1-(3-aminopropyl)imidazole solution dissolved in anhydrous ethanol under stirring at 30℃. After the addition was completed, the mixture was stirred for 26h, rotary evaporated, washed with ethyl acetate, and dried under vacuum to obtain a dicationic ionic liquid; phosphorylated graphene oxide and dicationic ionic liquid were then mixed. Liquid, condensing agent, and N,N-dimethylformamide were mixed in a mass ratio of 1:35:35:600, ultrasonicated at 100W for 20 min, stirred at 55℃ for 50 h, washed successively with N,N-dimethylformamide, deionized water, and methanol, and dried in an oven at 75℃ to obtain ionic liquid functionalized graphene oxide. The ionic liquid functionalized graphene oxide was mixed with acetone in a mass ratio of 1:35, ultrasonicated at 100W for 20 min, and acetylacetone molybdenum (twice the mass of the ionic liquid functionalized graphene oxide) was added. The mixture was stirred at 30℃ for 26 h, filtered, washed with ethanol, and dried in an oven at 75℃ to obtain ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide. (2) Bis(4-fluorophenyl) sulfone, bis(3-amino-4-hydroxyphenyl) sulfone, hexafluorobisphenol A, N,N-dimethylacetamide, toluene and potassium carbonate were mixed in a mass ratio of 1:0.5:0.65:10:8:0.65 and reacted at 160°C for 5 h in a nitrogen atmosphere. The temperature was then raised to 185°C and reacted for another 5 h. Excess ether was used to precipitate the precipitate. The precipitate was washed with deionized water and dried under vacuum at 50°C to obtain fluorinated and ammonia-containing polyether sulfone. (3) Mix epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:0.1, add 0.015 times the mass of epoxy resin of ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide, sonicate at 100W for 60 min, add 0.6 times the mass of epoxy resin of methyltetrahydrophthalic anhydride curing agent, stir at 30℃ for 30 min to remove bubbles, place in an oven, heat at 90℃ for 0.5 h, at 120℃ for 2 h, and at 150℃ for 2 h to obtain corrosion-resistant fireproof board.

[0021] Comparative Example 1: The only difference from Example 2 is step (3), which changes "mixing epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:0.1" to "mixing epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:0.025".

[0022] Comparative Example 2: The only difference from Example 2 is step (3), which changes "mixing epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:0.1" to "mixing epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:0.05".

[0023] Comparative Example 3: The only difference from Example 2 is the step (3), which changes "mixing epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:0.1" to "mixing epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:0.15".

[0024] Comparative Example 4: The only difference from Example 2 is step (3), which changes "mixing epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:0.1" to "mixing epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:0.175".

[0025] Comparative Example 5: The only difference from Example 2 is step (3), in which “adding 0.015 times the mass of epoxy resin to ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide” is changed to “adding 0.005 times the mass of epoxy resin to ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide”.

[0026] Comparative Example 6: The only difference from Example 2 is step (3), in which “adding 0.015 times the mass of epoxy resin to ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide” is changed to “adding 0.01 times the mass of epoxy resin to ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide”.

[0027] Comparative Example 7: The only difference from Example 2 is step (3), in which “adding 0.015 times the mass of epoxy resin to ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide” is changed to “adding 0.02 times the mass of epoxy resin to ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide”.

[0028] Comparative Example 8: The only difference from Example 2 is step (3), in which “adding 0.015 times the mass of epoxy resin to ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide” is changed to “adding 0.025 times the mass of epoxy resin to ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide”.

[0029] Comparative Example 9: A method for preparing a corrosion-resistant and fireproof board includes the following preparation steps: (1) Weigh 1,4-xylenedibromo, 1-(3-aminopropyl)imidazole, dichloromethane, and anhydrous ethanol in a mass ratio of 1:0.95:11:7. Dissolve 1,4-xylenedibromo in dichloromethane and add it dropwise to a solution of 1-(3-aminopropyl)imidazole dissolved in anhydrous ethanol under stirring at 27°C. After the addition is complete, stir for 24 h, evaporate by rotary evaporation, wash with ethyl acetate, and dry under vacuum to obtain a dicationic ionic liquid. Mix graphene oxide, the dicationic ionic liquid, the condensing agent, and N,N-dimethylformamide in a mass ratio of 1:33:33:590 and add them to a solution of 1,4-xylenedibromo, 1-(3-aminopropyl)imidazole ... The graphene oxide was ultrasonically treated with 100W for 15 min, stirred at 50℃ for 48 h, washed successively with N,N-dimethylformamide, deionized water and methanol, and dried in an oven at 70℃ to obtain ionic liquid functionalized graphene oxide. The ionic liquid functionalized graphene oxide was mixed with acetone at a mass ratio of 1:33, ultrasonically treated with 100W for 15 min, and 1.9 times the mass of acetylacetone molybdenum was added. The mixture was stirred at 27℃ for 24 h, filtered, washed with ethanol, and dried in an oven at 70℃ to obtain ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide. (2) Bis(4-fluorophenyl) sulfone, bis(3-amino-4-hydroxyphenyl) sulfone, hexafluorobisphenol A, N,N-dimethylacetamide, toluene and potassium carbonate were mixed in a mass ratio of 1:0.45:0.6:9.5:7.5:0.63 and reacted at 155°C for 4.5 h in a nitrogen atmosphere. The temperature was then raised to 180°C and reacted for another 4.5 h. Excess ether was used to precipitate the precipitate. The precipitate was washed with deionized water and dried under vacuum at 50°C to obtain fluorinated and ammonia-containing polyether sulfone. (3) Mix epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:0.1, add 0.015 times the mass of epoxy resin of ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide, sonicate at 100W for 45 min, add 0.55 times the mass of epoxy resin of methyltetrahydrophthalic anhydride curing agent, stir at 27℃ for 25 min to remove bubbles, place in an oven, heat at 90℃ for 0.5 h, at 120℃ for 2 h, and at 150℃ for 2 h to obtain corrosion-resistant fireproof board.

[0030] Comparative Example 10: A method for preparing a corrosion-resistant and fireproof board includes the following preparation steps: (1) Graphene oxide was mixed with 85wt% phosphoric acid aqueous solution at a mass ratio of 1:80, stirred at 50℃ for 12h, washed with deionized water until the pH of the washing solution was 4.5, and dried in an oven at 70℃ to obtain phosphorylated graphene oxide; 1,4-xylenedibromo, 1-(3-aminopropyl)imidazolium, dichloromethane and anhydrous ethanol were weighed at a mass ratio of 1:0.95:11:7, 1,4-xylenedibromo was dissolved in dichloromethane, and 1-(3-aminopropyl)imidazolium dissolved in anhydrous ethanol was added dropwise under stirring at 27℃. Add propylimidazolium chloride to a solution of imidazole and stir for 24 h after the addition is complete. Then, evaporate by rotary evaporation, wash with ethyl acetate, and dry under vacuum to obtain a dicationic ionic liquid. Mix phosphorylated graphene oxide, the dicationic ionic liquid, a condensing agent, and N,N-dimethylformamide in a mass ratio of 1:33:33:590, sonicate at 100 W for 15 min, stir at 50 °C for 48 h, wash successively with N,N-dimethylformamide, deionized water, and methanol, and dry in an oven at 70 °C to obtain ionic liquid functionalized graphene oxide. (2) Bis(4-fluorophenyl) sulfone, bis(3-amino-4-hydroxyphenyl) sulfone, hexafluorobisphenol A, N,N-dimethylacetamide, toluene and potassium carbonate were mixed in a mass ratio of 1:0.45:0.6:9.5:7.5:0.63 and reacted at 155°C for 4.5 h in a nitrogen atmosphere. The temperature was then raised to 180°C and reacted for another 4.5 h. Excess ether was used to precipitate the precipitate. The precipitate was washed with deionized water and dried under vacuum at 50°C to obtain fluorinated and ammonia-containing polyether sulfone. (3) Mix epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:0.1, add 0.015 times the mass of epoxy resin of ionic liquid functionalized graphene oxide, sonicate at 100W for 45 min, add 0.55 times the mass of epoxy resin of methyltetrahydrophthalic anhydride curing agent, stir at 27℃ for 25 min to remove bubbles, place in an oven, heat at 90℃ for 0.5 h, at 120℃ for 2 h, and at 150℃ for 2 h to obtain corrosion-resistant fireproof board.

[0031] Comparative Example 11: A method for preparing a corrosion-resistant and fireproof board includes the following preparation steps: (1) Bis(4-fluorophenyl) sulfone, bis(3-amino-4-hydroxyphenyl) sulfone, hexafluorobisphenol A, N,N-dimethylacetamide, toluene and potassium carbonate were mixed in a mass ratio of 1:0.45:0.6:9.5:7.5:0.63 and reacted at 155°C for 4.5 h in a nitrogen atmosphere. The temperature was then raised to 180°C and reacted for another 4.5 h. Excess ether was used to precipitate the precipitate. The precipitate was washed with deionized water and dried under vacuum at 50°C to obtain fluorinated and ammonia-containing polyether sulfone. (2) Mix epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:0.1, add 0.55 times the mass of epoxy resin as methyltetrahydrophthalic anhydride curing agent, stir at 27°C for 25 min to remove air bubbles, place in an oven, heat at 90°C for 0.5 h, at 120°C for 2 h, and at 150°C for 2 h to obtain a corrosion-resistant fireproof board.

[0032] Comparative Example 12: A method for preparing a corrosion-resistant and fireproof board includes the following preparation steps: (1) Graphene oxide and 85wt% phosphoric acid aqueous solution were mixed at a mass ratio of 1:80, stirred at 50℃ for 12h, washed with deionized water until the pH of the washing solution was 4.5, and dried in an oven at 70℃ to obtain phosphorylated graphene oxide; 1,4-xylenedibromo, 1-(3-aminopropyl)imidazole, dichloromethane and anhydrous ethanol were weighed at a mass ratio of 1:0.95:11:7, 1,4-xylenedibromo was dissolved in dichloromethane, and added dropwise to a 1-(3-aminopropyl)imidazole solution dissolved in anhydrous ethanol under stirring at 27℃. After the addition was completed, the mixture was stirred for 24h, rotary evaporated, washed with ethyl acetate, and dried under vacuum to obtain a dicationic ionic liquid; phosphorylated graphene oxide and dicationic ionic liquid were then mixed. Ionic liquid, condensing agent, and N,N-dimethylformamide were mixed in a mass ratio of 1:33:33:590, ultrasonicated at 100W for 15 min, stirred at 50℃ for 48 h, washed successively with N,N-dimethylformamide, deionized water, and methanol, and dried in an oven at 70℃ to obtain ionic liquid-functionalized graphene oxide. Ionic liquid-functionalized graphene oxide was mixed with acetone in a mass ratio of 1:33, ultrasonicated at 100W for 15 min, and 1.9 times the mass of acetylacetone molybdenum was added. The mixture was stirred at 27℃ for 24 h, filtered, washed with ethanol, and dried in an oven at 70℃ to obtain ionic liquid-functionalized flame-retardant and smoke-suppressing graphene oxide. (2) Epoxy resin and ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide were mixed at a mass ratio of 1:0.015 and ultrasonically treated at 100W for 45 min. Methyltetrahydrophthalic anhydride curing agent of 0.55 times the mass of epoxy resin was added and stirred at 27℃ for 25 min to remove air bubbles. The mixture was then placed in an oven and heated at 90℃ for 0.5 h, 120℃ for 2 h, and 150℃ for 2 h to obtain a corrosion-resistant fireproof board.

[0033] Experimental Example 1: Determination of the optimal addition amount of fluorinated and ammonia-containing polyethersulfone and ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide Test method: Determined by mechanical properties. The tensile and flexural strengths of the corrosion-resistant fireproof board were tested using a WDW-100KN universal testing machine according to GBT2567-2008 standard at a test speed of 10 mm / min. The results are shown in Table 1.

[0034] Table 1

[0035] A comparison of Example 2 and Comparative Examples 1-4 reveals that the tensile strength and flexural strength of the corrosion-resistant fireproof board initially increase and then decrease with increasing fluorinated and ammonia-containing polyethersulfone content. When the fluorinated and ammonia-containing polyethersulfone content is 10% of the epoxy resin mass, both the tensile strength and flexural strength of the board reach their maximum values. When the content is below 10%, the polyethersulfone segments diffuse uniformly in the resin matrix, effectively solving the problem of stress concentration and limited mechanical properties caused by the large difference in mechanical properties between graphene oxide and epoxy resin. Simultaneously, the side-chain amino groups participate in curing and cross-linking, forming a chemically bonded network, effectively improving mechanical properties. When the content exceeds 15%, the cross-linked network structure increases linearly, introducing network defects and leading to an increase in free volume, further weakening intermolecular interactions. Therefore, a fluorinated and ammonia-containing polyethersulfone content of 10% of the epoxy resin mass is selected as the optimal content.

[0036] A comparison of Examples 2 and Comparative Examples 5-8 reveals that the tensile and flexural strengths of the corrosion-resistant fireproof board initially increase and then decrease with increasing addition of ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide. When the amount of functionalized graphene added is 1.5% of the epoxy resin mass, both the tensile and flexural strengths of the board reach their maximum values. When the addition amount is less than 1.5%, the amino and imidazole cations on the surface of the functionalized graphene participate in the curing and cross-linking of the epoxy resin, forming chemical bonds. Simultaneously, the two-dimensional sheet structure of graphene is uniformly dispersed in the matrix, playing a role in reinforcement and stress transfer, effectively improving mechanical properties. When the addition amount exceeds 1.5%, excessive functionalized graphene agglomerates in the resin matrix, forming stress concentration points and interface defects, leading to loose internal bonding of the composite material and a decrease in mechanical properties. Therefore, a functionalized graphene addition amount of 1.5% of the epoxy resin mass is selected.

[0037] Experimental Example 2: Flame retardant performance, smoke suppression performance, and corrosion resistance tests Flame retardant performance test method: The limiting oxygen index of the corrosion-resistant fireproof boards obtained in each embodiment and the materials of comparative examples 9 to 12 was tested according to GB / T2406.2-2009. The sample size was 80mm×6.5mm×6mm.

[0038] Smoke suppression performance test method: The corrosion-resistant fireproof boards obtained in each embodiment and the materials of Comparative Examples 9-12 were subjected to smoke production tests according to ISO5659-2:2017. The optical density was measured by single-chamber testing. The sample size was 25mm × 25mm × 6mm. The test was conducted under conditions where no guiding flame was present.

[0039] Corrosion resistance test method: The corrosion-resistant fireproof boards obtained in each example and the materials of comparative examples 9 to 12 were respectively placed in sulfuric acid aqueous solution with pH value of 4, sodium hydroxide aqueous solution with pH value of 10, and 5wt% sodium chloride aqueous solution with pH value of 7 and water bath heating temperature of 80°C, and immersed for corrosion for 360 hours. After removal, the bending performance was tested according to the same mechanical property test method as in test example 1.

[0040] The results are shown in Table 2.

[0041] Table 2

[0042] A comparison of the experimental data from Examples 1-3 and Comparative Examples 9-12 in Table 2 reveals that the corrosion-resistant fireproof board prepared by this invention has good flame retardant properties, smoke suppression properties, and corrosion resistance properties.

[0043] By comparing Examples 1-3 and Comparative Example 9, it can be found that phosphorylation of graphene oxide can effectively improve the limiting oxygen index of the material.

[0044] By comparing Examples 1-3 and Comparative Example 10, it can be found that in the preparation of ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide, the coordination of molybdenum acetylacetone, the molybdenum compound therein inhibits smoke generation, promotes char formation, achieves low smoke and low toxicity emissions, and significantly improves smoke suppression performance.

[0045] A comparison of Examples 1-3 and Comparative Example 11 reveals that introducing ionic liquid-functionalized flame-retardant and smoke-suppressing graphene oxide during the preparation of the corrosion-resistant fireproof board allows the phosphate groups on its surface to catalyze the dehydration of epoxy resin into carbon during combustion, forming a dense carbon layer that blocks heat and oxygen transfer. The imidazole cations and molybdenum elements in the dual-cationic ionic liquid synergistically exert flame-retardant and smoke-suppressing effects. Molybdenum can catalyze the oxidation of carbon particles in smoke, thereby suppressing smoke. Phosphorus, nitrogen, and molybdenum elements work together to promote cross-linking and carbonization and reduce the heat release rate. At the same time, the two-dimensional graphene sheets act as a physical barrier to further prevent the diffusion of combustible gases, thus achieving high-efficiency flame retardancy and low smoke and low toxicity. In terms of corrosion resistance, the ionic liquid-functionalized graphene oxide is uniformly dispersed in the resin matrix, and the amino groups on its surface participate in epoxy curing and cross-linking, improving the density of the cross-linking network and the interfacial bonding strength. The sheet structure of graphene can effectively extend the penetration path of corrosive media, forming a physical barrier layer, thereby significantly enhancing the corrosion resistance of the board to media such as acids, alkalis, and salts.

[0046] A comparison of Examples 1-3 and Comparative Example 12 reveals that introducing fluorinated and ammonia-containing polyethersulfone (PES) during the preparation of corrosion-resistant and fireproof boards can significantly improve both the corrosion resistance and mechanical properties of the boards. This is because the fluorinated and ammonia-containing PES molecular chain contains amino, fluorinated aromatic rings, and ether sulfone structures. The amino groups participate in the epoxy resin curing process and, together with the amino groups on the surface of ionic liquid-functionalized flame-retardant and smoke-suppressing graphene oxide, form a multi-point cross-linking network. This allows the PES segments to diffuse uniformly in the resin matrix, effectively solving the stress concentration and interface defect problems caused by the large difference in mechanical properties between graphene oxide and the epoxy resin matrix. The rigid aromatic rings and ether sulfone segments provide the matrix with excellent reinforcement, thereby significantly improving the bending strength of the boards. At the same time, fluorine atoms have extremely low surface energy and excellent hydrophobic and oleophobic properties, effectively repelling the adsorption and penetration of water molecules and corrosive ions. The introduction of the hexafluorobisphenol A structure further improves the hydrophobicity and thermal stability of the cross-linking network, enabling the boards to maintain excellent corrosion resistance in harsh environments such as acids, alkalis, and salt spray, significantly extending the service life of the materials.

[0047] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from the spirit or essential characteristics of the invention. Therefore, the embodiments should be considered illustrative and non-limiting in all respects, and the scope of the invention is defined by the appended technical solutions rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the technical solutions are intended to be included within the present invention.

Claims

1. A corrosion-resistant and fireproof board, characterized in that, The corrosion-resistant and fireproof board is made by mixing epoxy resin, ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide, fluorinated and ammonia-containing polyethersulfone and curing agent, followed by degassing and curing.

2. The corrosion-resistant and fireproof board according to claim 1, characterized in that, The ionic liquid-functionalized flame-retardant and smoke-suppressing graphene oxide is prepared by reacting phosphorylated graphene oxide with a dual-cationic ionic liquid under the action of a condensing agent, followed by a further reaction with molybdenum acetylacetonate.

3. The corrosion-resistant and fireproof board according to claim 2, characterized in that, The phosphorylated graphene oxide was prepared by reacting graphene oxide with an 85 wt% aqueous solution of phosphoric acid.

4. The corrosion-resistant and fireproof board according to claim 2, characterized in that, The dual-cationic ionic liquid was prepared by reacting 1,4-xylenedibromo and 1-(3-aminopropyl)imidazolium.

5. The corrosion-resistant and fireproof board according to claim 1, characterized in that, The fluorinated and ammonia-containing polyether sulfone is prepared by polycondensation of bis(4-fluorophenyl) sulfone, bis(3-amino-4-hydroxyphenyl) sulfone and hexafluorobisphenol A.

6. A method for preparing a corrosion-resistant and fireproof board, characterized in that, The preparation steps include the following: (1) Graphene oxide and 85wt% phosphoric acid aqueous solution are mixed at a mass ratio of 1:(70~90), stirred at 45~55℃ for 10~14h, washed with deionized water until the pH of the washing solution is 4~5, and dried in an oven at 65~75℃ to obtain phosphorylated graphene oxide; 1,4-xylene dibromide, 1-(3-aminopropyl)imidazolium, dichloromethane and anhydrous ethanol are weighed at a mass ratio of 1:(0.9~1):(10~12):(6~8), 1,4-xylene dibromide is dissolved in dichloromethane, and added dropwise to a 1-(3-aminopropyl)imidazolium solution dissolved in anhydrous ethanol under stirring at 25~30℃. After the addition is completed, the mixture is stirred for 22~26h, rotary evaporated, washed with ethyl acetate, and dried under vacuum to obtain a dicationic ionic liquid; phosphorylated graphene oxide, dicationic ionic liquid, condensing agent The ionic liquid-functionalized graphene oxide was prepared by mixing N,N-dimethylformamide at a mass ratio of 1:(30~35):(30~35):(580~600), ultrasonicating at 100W for 10~20 min, stirring at 45~55℃ for 45~50 h, washing with N,N-dimethylformamide, deionized water and methanol in sequence, and drying in an oven at 65~75℃. The ionic liquid-functionalized graphene oxide was then mixed with acetone at a mass ratio of 1:(30~35), ultrasonicated at 100W for 10~20 min, and 1.8~2 times the mass of acetylacetone molybdenum was added. The mixture was stirred at 25~30℃ for 22~26 h, filtered, washed with ethanol, and dried in an oven at 65~75℃. (2) Bis(4-fluorophenyl) sulfone, bis(3-amino-4-hydroxyphenyl) sulfone, hexafluorobisphenol A, N,N-dimethylacetamide, toluene and potassium carbonate are mixed in a mass ratio of 1:(0.4~0.5):(0.55~0.65):(9~10):(7~8):(0.6~0.65), and reacted at 150~160℃ for 4~5h in a nitrogen atmosphere. The temperature is then raised to 175~185℃ and reacted for 4~5h. Excess ether is used to precipitate the precipitate, which is then washed with deionized water and dried under vacuum at 50℃ to obtain fluorinated and ammonia-containing polyether sulfone. (3) Mix epoxy resin and preheated fluorinated and ammonia-containing polyethersulfone at a mass ratio of 1:(0.05~0.15), add 0.01~0.02 times the mass of epoxy resin of ionic liquid functionalized flame-retardant and smoke-suppressing graphene oxide, sonicate at 100W for 30~60min, add 0.5~0.6 times the mass of epoxy resin of methyltetrahydrophthalic anhydride curing agent, stir at 25~30℃ for 20~30min to remove bubbles, place in an oven, heat at 90℃ for 0.5h, at 120℃ for 2h, and at 150℃ for 2h to obtain corrosion-resistant fireproof board.

7. The method for preparing a corrosion-resistant and fireproof board according to claim 6, characterized in that, The graphene oxide in step (1) is reagent grade; the condensing agent is benzotriazol-1-yl-oxytripyrrolidinylphosphine hexafluorophosphate (PyBOP).

8. The method for preparing a corrosion-resistant and fireproof board according to claim 6, characterized in that, The epoxy resin in step (3) is bisphenol A type E-51 epoxy resin; the preheating of fluorinated and ammonia polyether sulfone is to stir the fluorinated and ammonia polyether sulfone at 90°C for 30 min.

Images