Salt fog resistant boat membrane and method of making same

Abstract

The application discloses a kind of salt fog resistant yacht membranes and preparation method thereof, it is related to film material technical field.The application is prepared when preparing salt fog resistant yacht membrane, diphenyl dichlorosilane, p-hydroxybenzaldehyde is reacted to obtain intermediate;Intermediate is sequentially reacted with 3-amino-1-propanol, 5,5-dimethyl-1,3,2-dioxaphosphacyclohexane-2-ketone to obtain phosphorus-silicon composite flame-retardant monomer;Graphene oxide is sequentially reacted with ethylenediamine, epoxidized benzophenone to obtain modified graphene oxide;Isophorone diisocyanate, polytetrahydrofuran, trispyridine glycol monomer, phosphorus-silicon composite flame-retardant monomer are polymerized to obtain polyurethane;Polyurethane, modified graphene oxide are mixed with solvent, and cast film is prepared to obtain salt fog resistant yacht membrane.The salt fog resistant yacht membrane prepared by the application has salt fog resistance, flame retardance and weather resistance.

Description

Technical Field

[0001] This invention relates to the field of membrane technology, specifically to a salt spray resistant yacht membrane and its preparation method. Background Technology

[0002] Yacht membranes are membrane materials attached to the surface of yachts, primarily serving functions such as corrosion prevention, slip resistance, heat insulation, and aesthetics. Commonly used film-forming materials include polymers such as polyethylene, polyurethane, polytetrafluoroethylene, and polyester. Yachts frequently operate in marine environments where seawater, with its high salt content, strong conductivity, and abundance of microorganisms, is a naturally corrosive medium. Long-term exposure to seawater can cause corrosion of the yacht's metal components, leading to hull damage, equipment malfunctions, and a range of other problems. Yacht membranes can prevent direct contact between corrosive media and metal components, providing some corrosion protection. However, traditional membrane materials only offer physical barriers and have relatively weak corrosion resistance. Furthermore, yacht membranes are prone to photoaging due to prolonged outdoor exposure, leading to yellowing, chalking, and decreased strength, affecting both aesthetics and lifespan.

[0003] Polyurethane possesses high elasticity, wear resistance, low-temperature resistance, and self-healing properties, making it one of the ideal materials for preparing yacht membranes. This invention improves the salt spray and weather resistance of polyurethane membranes through a series of chemical modifications. Considering that polyurethane has a low limiting oxygen index (LOI), typically less than 20%, classifying it as a flammable material and posing certain safety hazards when used over large areas, this invention also improves the flame retardancy of polyurethane, resulting in a polyurethane membrane material with excellent safety, durability, and protective properties, greatly meeting the application requirements of yacht membranes. Summary of the Invention

[0004] The purpose of this invention is to provide a salt spray resistant yacht membrane and its preparation method, so as to solve the problems existing in the prior art.

[0005] A method for preparing a salt spray resistant yacht membrane, the method comprising the following preparation steps: S1: 2,2':6',2"-terpyridine-4'-carboxaldehyde and 2-amino-2-methyl-1,3-propanediol were added to N,N-dimethylformamide in 10 to 14 times the mass of 2,2':6',2"-terpyridine-4'-carboxaldehyde. The mixture was stirred at 70 to 80 °C for 6 to 7 h. The N,N-dimethylformamide was removed by vacuum distillation to obtain the terpyridinediol monomer. S2: Dissolve the intermediate and 3-amino-1-propanol in 16-20 times the mass of the intermediate in N,N-dimethylformamide, stir and react at 50-60℃ for 8-10h, add 5,5-dimethyl-1,3,2-dioxophosphazenecyclohexane-2-one, raise the temperature to 110-120℃, continue stirring and reacting for 12-14h, remove N,N-dimethylformamide by vacuum distillation, and obtain the phosphorus-silicon composite flame retardant monomer; S3: Mix 2,4-dihydroxybenzophenone and 2 mol / L sodium hydroxide aqueous solution at a mass ratio of 1:(5~6) until homogeneous. Stir at room temperature for 10~20 min. Add epichlorohydrin dropwise at a uniform rate over 30 min. After the addition is complete, heat to 85~95℃ and react in an oil bath for 4~5 h. Wash with deionized water at 70~80℃, allow to stand and separate into layers. Take the organic phase and dry it with anhydrous magnesium sulfate for 20~24 h. Remove excess epichlorohydrin by vacuum distillation to obtain epoxidized benzophenone. S4: Aminated graphene oxide, epoxidized benzophenone, and N,N-dimethylformamide are mixed evenly in a mass ratio of 1:(8~10):(70~80), stirred at 50~60℃ for 7~9h, filtered, washed with anhydrous ethanol, and dried at 50~60℃ for 18~22h to obtain modified graphene oxide. S5: Dissolve terpyridine diol monomer and phosphorus-silicon composite flame retardant monomer in N,N-dimethylformamide at 5-6 times the mass of terpyridine diol monomer, and mix evenly to obtain a chain extender solution; Under nitrogen protection, mix isophorone diisocyanate and polytetrahydrofuran, stir at 70-80℃ for 1-2 hours, add chain extender solution and dibutyltin dilaurate at 0.002-0.003 times the mass of isophorone diisocyanate, continue stirring and reacting for 2-3 hours, and vacuum dry at 60-70℃ for 20-24 hours to obtain polyurethane; Mix polyurethane, modified graphene oxide and N,N-dimethylformamide evenly, stir at room temperature for 4-5 hours, degas under vacuum, pour into a mold, and dry at 60-70℃ to constant weight to obtain salt spray resistant yacht film.

[0006] Further, in step S1, the molar ratio of 2,2':6',2"-terpyridine-4'-carboxaldehyde and 2-amino-2-methyl-1,3-propanediol is 1:1.

[0007] Furthermore, the reaction chemical formula of the terpyridinediol monomer mentioned in step S1 is as follows: .

[0008] Further, the intermediate in step S2 is prepared as follows: Diphenyldichlorosilane, p-hydroxybenzaldehyde, and triethylamine are weighed in a molar ratio of 1:2:2; p-hydroxybenzaldehyde and tetrahydrofuran are mixed evenly in a mass ratio of 1:(15~18), stirred at room temperature for 10~20 min, triethylamine is added, and stirring is continued for 10~20 min; diphenyldichlorosilane is added under ice-water bath conditions, and the mixture is stirred and reacted at 40~50℃ for 3~4 h; the mixture is filtered, and distilled under reduced pressure to obtain the intermediate.

[0009] Further, the molar ratio of the intermediate, 3-amino-1-propanol, and 5,5-dimethyl-1,3,2-dioxophosphazenecyclohexane-2-one in step S2 is 1:2:2.

[0010] Furthermore, the chemical formula for the reaction of the phosphorus-silicon composite flame-retardant monomer described in step S2 is as follows: .

[0011] Further, the molar ratio of 2,4-dihydroxybenzophenone and epichlorohydrin in step S3 is 1:(3~4).

[0012] Furthermore, the chemical formula for the epoxidation of benzophenone in step S3 is as follows: .

[0013] Further, the preparation method of the aminated graphene oxide in step S4 is as follows: graphene oxide and N,N-dimethylformamide are mixed at a mass ratio of 1:(200~300), stirred at room temperature for 1~2 hours, ethylenediamine with a mass of 80~100 times that of graphene oxide is added, stirring is continued for 40~60 minutes, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride with a mass of 0.05~0.07 times that of graphene oxide is added, and the mixture is reacted in a water bath at 55~65℃ for 6~8 hours. After filtration, the mixture is washed with anhydrous ethanol and dried at 50~60℃ for 10~12 hours to obtain aminated graphene oxide.

[0014] Further, the molar ratio of isophorone diisocyanate, polytetrahydrofuran, terpyridinediol monomer, and phosphorus-silicon composite flame retardant monomer in step S5 is (10~12):(6~7):(2~3):(3~4).

[0015] Further, the dosage relationship of polyurethane, modified graphene oxide, and N,N-dimethylformamide in step S5 is as follows: by mass parts, polyurethane 80-90 parts, modified graphene oxide 3-3.4 parts, and N,N-dimethylformamide 200-220 parts.

[0016] A salt spray resistant yacht membrane is prepared by the above-described method.

[0017] Compared with the prior art, the above-described technical solutions conceived in this invention can achieve the following beneficial effects: 1. Tripyridine diol monomer is prepared by reacting 2,2':6',2"-terpyridine-4'-carboxaldehyde and 2-amino-2-methyl-1,3-propanediol. The terpyridine diol monomer can be used as a chain extender in the polymerization of polyurethane, introducing a large number of terpyridine structures into the side chain of polyurethane. Terpyridine is a commonly used metal ion ligand that can chelate with metal ions escaping from the surface of metal materials to form a complex protective layer, which can delay corrosion and improve the salt spray resistance of the membrane material.

[0018] 2. An intermediate is prepared by reacting diphenyldichlorosilane and p-hydroxybenzaldehyde; the intermediate is then reacted sequentially with 3-amino-1-propanol and 5,5-dimethyl-1,3,2-dioxophosphazenecyclohexane-2-one to prepare a phosphorus-silicon composite flame retardant monomer; the hydroxyl groups at both ends of the phosphorus-silicon composite flame retardant monomer can participate in the polymerization of polyurethane, introducing a phosphorus-silicon composite flame retardant component into the polyurethane main chain, effectively improving the flame retardant performance of the membrane material.

[0019] 3. Epoxybenzophenone was prepared by reacting 2,4-dihydroxybenzophenone with epichlorohydrin, and then reacted with ethylenediamine-modified aminated graphene oxide to obtain modified graphene oxide. Graphene oxide, as a two-dimensional sheet-like nanomaterial, has been widely used in the corrosion protection of coating materials. It can improve the corrosion resistance of the film material through physical barrier. Surface modification of graphene oxide improves its dispersion ability in polymer materials. On the other hand, the benzophenone structure grafted onto the graphene oxide belongs to the benzophenone class of ultraviolet absorbers, which can absorb ultraviolet light and improve the weather resistance of the film material. Detailed Implementation

[0020] 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.

[0021] Raw material information: Graphene oxide: sheet diameter 50-500nm, purity 99wt%, Shanghai Maoguo Nanotechnology Co., Ltd. Polytetrahydrofuran: Model PTMEG-2000, purity 99.9%, Yangtian Petrochemical (Nanjing) Co., Ltd.

[0022] Example 1: A method for preparing a salt spray resistant yacht membrane includes the following preparation steps: S1: 2,2':6',2"-terpyridine-4'-carboxaldehyde and 2-amino-2-methyl-1,3-propanediol were added to N,N-dimethylformamide at a molar ratio of 1:1 to 10 times the mass of 2,2':6',2"-terpyridine-4'-carboxaldehyde. The mixture was stirred at 70°C for 7 hours. N,N-dimethylformamide was removed by vacuum distillation to obtain the terpyridinediol monomer. S2: Weigh diphenyldichlorosilane, p-hydroxybenzaldehyde, and triethylamine in a molar ratio of 1:2:2; mix p-hydroxybenzaldehyde and tetrahydrofuran in a mass ratio of 1:15, stir at room temperature for 10 min, add triethylamine, continue stirring for 10 min, add diphenyldichlorosilane under ice-water bath conditions, stir and react at 40℃ for 4 h, filter, and distill under reduced pressure to obtain the intermediate; weigh the intermediate and 3-amino-1- Propanol, 5,5-dimethyl-1,3,2-dioxophosphanecyclohexane-2-one; the intermediate and 3-amino-1-propanol were dissolved in N,N-dimethylformamide at 16 times their weight of the intermediate, and the mixture was stirred at 50°C for 10 h. Then, 5,5-dimethyl-1,3,2-dioxophosphanecyclohexane-2-one was added, the temperature was raised to 110°C, and the mixture was stirred for another 14 h. The N,N-dimethylformamide was removed by vacuum distillation to obtain the phosphorus-silicon composite flame retardant monomer. S3: Weigh 2,4-dihydroxybenzophenone and epichlorohydrin in a molar ratio of 1:3; mix 2,4-dihydroxybenzophenone and 2 mol / L sodium hydroxide aqueous solution in a mass ratio of 1:5, stir at room temperature for 10 min, add epichlorohydrin dropwise at a uniform rate over 30 min, and after the addition is complete, heat to 85℃ and react in an oil bath for 5 h. Wash with deionized water at 70℃, allow to stand and separate into layers, take the organic phase and dry it with anhydrous magnesium sulfate for 20 h, remove excess epichlorohydrin by vacuum distillation, and obtain epoxidized benzophenone; S4: Graphene oxide and N,N-dimethylformamide were mixed at a mass ratio of 1:200 and stirred at room temperature for 1 h. 80 times the mass of graphene oxide was added to ethylenediamine, and stirring was continued for 40 min. 0.05 times the mass of graphene oxide was added to 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and the mixture was reacted in a 55°C water bath for 8 h. After filtration, the mixture was washed with anhydrous ethanol and dried at 50°C for 12 h to obtain aminated graphene oxide. Aminated graphene oxide, epoxide benzophenone, and N,N-dimethylformamide were mixed evenly at a mass ratio of 1:8:70 and stirred at 50°C for 9 h. After filtration, the mixture was washed with anhydrous ethanol and dried at 50°C for 22 h to obtain modified graphene oxide. S5: Weigh isophorone diisocyanate, polytetrahydrofuran, terpyridine glycol monomer, and phosphosilicate composite flame retardant monomer in a molar ratio of 10:6:2:3; dissolve the terpyridine glycol monomer and phosphosilicate composite flame retardant monomer in N,N-dimethylformamide at 5 times the mass of the terpyridine glycol monomer, and mix evenly to obtain a chain extender solution; under nitrogen protection, mix isophorone diisocyanate and polytetrahydrofuran, stir at 70°C for 2 hours, add the chain extender solution and dibutyltin dilaurate at 0.002 times the mass of isophorone diisocyanate, continue stirring and reacting for 3 hours, and vacuum dry at 60°C for 24 hours to obtain polyurethane; mix 80 parts of polyurethane, 3 parts of modified graphene oxide, and 200 parts of N,N-dimethylformamide evenly, stir at room temperature for 4 hours, degas under vacuum, pour into a mold, and dry at 60°C to constant weight to obtain a salt spray resistant yacht film.

[0023] Example 2: A method for preparing a salt spray resistant yacht membrane includes the following preparation steps: S1: 2,2':6',2"-terpyridine-4'-carboxaldehyde and 2-amino-2-methyl-1,3-propanediol were added to N,N-dimethylformamide at a molar ratio of 1:1 to 12 times the mass of 2,2':6',2"-terpyridine-4'-carboxaldehyde. The mixture was stirred at 75°C for 6.5 h. N,N-dimethylformamide was removed by vacuum distillation to obtain the terpyridinediol monomer. S2: Weigh diphenyldichlorosilane, p-hydroxybenzaldehyde, and triethylamine in a molar ratio of 1:2:2; mix p-hydroxybenzaldehyde and tetrahydrofuran in a mass ratio of 1:16.5, stir at room temperature for 15 min, add triethylamine, continue stirring for 15 min, add diphenyldichlorosilane under ice-water bath conditions, stir and react at 45℃ for 3.5 h, filter, and distill under reduced pressure to obtain the intermediate; weigh the intermediate and 3-amino- 1-Propanol, 5,5-Dimethyl-1,3,2-dioxophosphanecyclohexane-2-one; the intermediate and 3-amino-1-propanol were dissolved in N,N-dimethylformamide at 18 times their weight of the intermediate, and the mixture was stirred at 55°C for 9 h. Then, 5,5-dimethyl-1,3,2-dioxophosphanecyclohexane-2-one was added, the temperature was raised to 115°C, and the mixture was stirred for another 13 h. The N,N-dimethylformamide was removed by vacuum distillation to obtain the phosphorus-silicon composite flame retardant monomer. S3: Weigh 2,4-dihydroxybenzophenone and epichlorohydrin at a molar ratio of 1:3.5; mix 2,4-dihydroxybenzophenone and 2 mol / L sodium hydroxide aqueous solution at a mass ratio of 1:5.5, stir at room temperature for 15 min, add epichlorohydrin dropwise at a uniform rate over 30 min, and after the addition is complete, heat to 90℃ and react in an oil bath for 4.5 h. Wash with deionized water at 75℃, allow to stand and separate into layers, take the organic phase and dry it with anhydrous magnesium sulfate for 22 h, remove excess epichlorohydrin by vacuum distillation, and obtain epoxidized benzophenone; S4: Graphene oxide and N,N-dimethylformamide were mixed at a mass ratio of 1:250 and stirred at room temperature for 1.5 h. 90 times the mass of graphene oxide was added to ethylenediamine, and stirring was continued for 50 min. 0.06 times the mass of graphene oxide was added to 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride, and the mixture was reacted in a 60°C water bath for 7 h. After filtration, the mixture was washed with anhydrous ethanol and dried at 55°C for 11 h to obtain aminated graphene oxide. Aminated graphene oxide, epoxide benzophenone, and N,N-dimethylformamide were mixed evenly at a mass ratio of 1:9:75 and stirred at 55°C for 8 h. After filtration, the mixture was washed with anhydrous ethanol and dried at 55°C for 20 h to obtain modified graphene oxide. S5: Weigh isophorone diisocyanate, polytetrahydrofuran, terpyridine glycol monomer, and phosphorus-silicon composite flame retardant monomer in a molar ratio of 11:6.5:2.5:3.5; dissolve the terpyridine glycol monomer and phosphorus-silicon composite flame retardant monomer in 5.5 times the mass of the terpyridine glycol monomer in N,N-dimethylformamide, and mix thoroughly to obtain a chain extender solution; under nitrogen protection, mix isophorone diisocyanate and polytetrahydrofuran, and stir at 75°C. After 1.5 hours, a chain extender solution and 0.0025 times the mass of isophorone diisocyanate dibutyltin dilaurate were added, and the reaction was continued with stirring for 2.5 hours. The mixture was then vacuum dried at 65°C for 22 hours to obtain polyurethane. 85 parts of polyurethane, 3.2 parts of modified graphene oxide, and 210 parts of N,N-dimethylformamide were mixed evenly and stirred at room temperature for 4.5 hours. The mixture was then degassed under vacuum, poured into a mold, and dried at 65°C to constant weight to obtain a salt spray resistant yacht membrane.

[0024] Example 3: A method for preparing a salt spray resistant yacht membrane includes the following preparation steps: S1: 2,2':6',2"-terpyridine-4'-carboxaldehyde and 2-amino-2-methyl-1,3-propanediol were added to N,N-dimethylformamide at a molar ratio of 1:1 to 14 times the mass of 2,2':6',2"-terpyridine-4'-carboxaldehyde. The mixture was stirred and reacted at 80°C for 6 hours. N,N-dimethylformamide was removed by vacuum distillation to obtain the terpyridinediol monomer. S2: Weigh diphenyldichlorosilane, p-hydroxybenzaldehyde, and triethylamine in a molar ratio of 1:2:2; mix p-hydroxybenzaldehyde and tetrahydrofuran in a mass ratio of 1:18, stir at room temperature for 20 min, add triethylamine, continue stirring for 20 min, add diphenyldichlorosilane under ice-water bath conditions, stir and react at 50℃ for 3 h, filter, and distill under reduced pressure to obtain the intermediate; weigh the intermediate and 3-amino-1- Propanol, 5,5-dimethyl-1,3,2-dioxophosphanecyclohexane-2-one; the intermediate and 3-amino-1-propanol were dissolved in N,N-dimethylformamide at 20 times their weight of the intermediate, and the mixture was stirred at 60°C for 8 hours. Then, 5,5-dimethyl-1,3,2-dioxophosphanecyclohexane-2-one was added, the temperature was raised to 120°C, and the mixture was stirred for another 12 hours. The N,N-dimethylformamide was removed by vacuum distillation to obtain the phosphorus-silicon composite flame retardant monomer. S3: Weigh 2,4-dihydroxybenzophenone and epichlorohydrin at a molar ratio of 1:4; mix 2,4-dihydroxybenzophenone and 2 mol / L sodium hydroxide aqueous solution at a mass ratio of 1:6, stir at room temperature for 20 min, add epichlorohydrin dropwise at a uniform rate over 30 min, and after the addition is complete, heat to 95℃ and react in an oil bath for 4 h. Wash with deionized water at 80℃, allow to stand and separate into layers, take the organic phase and dry it with anhydrous magnesium sulfate for 24 h, remove excess epichlorohydrin by vacuum distillation, and obtain epoxidized benzophenone; S4: Graphene oxide and N,N-dimethylformamide were mixed at a mass ratio of 1:300 and stirred at room temperature for 2 hours. Ethylenediamine with a mass ratio of 100 times that of graphene oxide was added, and stirring was continued for 60 minutes. 1-Ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride with a mass ratio of 0.07 times that of graphene oxide was added, and the mixture was reacted in a water bath at 65°C for 6 hours. After filtration, the mixture was washed with anhydrous ethanol and dried at 60°C for 10 hours to obtain aminated graphene oxide. Aminated graphene oxide, benzophenone epoxide, and N,N-dimethylformamide were mixed evenly at a mass ratio of 1:10:80 and stirred at 60°C for 7 hours. After filtration, the mixture was washed with anhydrous ethanol and dried at 60°C for 18 hours to obtain modified graphene oxide. S5: Weigh isophorone diisocyanate, polytetrahydrofuran, terpyridine glycol monomer, and phosphosilicate composite flame retardant monomer in a molar ratio of 12:7:3:4; dissolve the terpyridine glycol monomer and phosphosilicate composite flame retardant monomer in N,N-dimethylformamide at 6 times the mass of the terpyridine glycol monomer, and mix evenly to obtain a chain extender solution; under nitrogen protection, mix isophorone diisocyanate and polytetrahydrofuran, stir at 80°C for 1 hour, add the chain extender solution and dibutyltin dilaurate at 0.003 times the mass of isophorone diisocyanate, continue stirring and react for 2 hours, and vacuum dry at 70°C for 20 hours to obtain polyurethane; mix 90 parts of polyurethane, 3.4 parts of modified graphene oxide, and 220 parts of N,N-dimethylformamide evenly, stir at room temperature for 5 hours, degas under vacuum, pour into a mold, and dry at 70°C to constant weight to obtain a salt spray resistant yacht film.

[0025] Comparative Example 1: The difference between Comparative Example 1 and Example 2 is that step S1 is omitted, and the "terpyridinediol monomer" in step S5 is replaced with "1,4-butanediol". The remaining steps are the same as in Example 2.

[0026] Comparative Example 2: The difference between Comparative Example 2 and Example 2 is that step S2 is omitted, and the "phosphorus-silicon composite flame retardant monomer" in step S5 is replaced with "1,4-butanediol". The remaining steps are the same as in Example 2.

[0027] Comparative Example 3: The difference between Comparative Example 3 and Example 2 is that steps S3 and S4 are omitted, and "modified graphene oxide" in step S5 is replaced with "graphene oxide". The remaining steps are the same as in Example 2.

[0028] Comparative Example 4: The difference between Comparative Example 4 and Example 2 is that steps S3 and S4 are omitted, and "modified graphene oxide" is not added in step S5. The remaining steps are the same as in Example 2.

[0029] Experimental example: Salt spray resistance test: Salt spray resistance test was conducted in accordance with the national standard GB / T1771-2016. Tinplate sheet was used as the substrate material. The samples from the examples and comparative examples were degassed under vacuum and coated onto the tinplate sheet. The samples were dried at 70℃ for 24 hours to obtain test specimens. The test specimens were placed in a salt spray test chamber with a 5% sodium chloride aqueous solution as the corrosion solution. The temperature inside the chamber was 35℃. After 240 hours, the test specimens were taken out, cleaned, and the corrosion of the paint film (cracking, peeling, blistering) was observed.

[0030] Weather resistance testing: The examples and comparative examples were placed in a UV aging test chamber at an UV intensity of 400 μW / cm². 2Irradiated for 160 hours at a relative humidity of 2%, and the yellow index was tested using a CR-10 colorimeter.

[0031] Flame retardant performance testing: Refer to the limiting oxygen index of the test examples and comparative examples in GB / T 2406.2-2009.

[0032] The results of the above experiments are recorded in Table 1; As can be seen from the test data in the table above, the salt spray resistant yacht membrane prepared in this application has excellent salt spray resistance, weather resistance and flame retardant properties.

[0033] The specific embodiments described above further illustrate the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only a specific embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing a salt spray resistant yacht membrane, characterized in that, The preparation method of the salt spray resistant yacht membrane includes the following preparation steps: S1: 2,2':6',2"-terpyridine-4'-carboxaldehyde and 2-amino-2-methyl-1,3-propanediol were added to N,N-dimethylformamide and stirred at 70~80℃ for 6~7h. The mixture was then distilled under reduced pressure to obtain the terpyridinediol monomer. S2: Dissolve the intermediate and 3-amino-1-propanol in N,N-dimethylformamide, stir and react at 50~60℃ for 8~10h, add 5,5-dimethyl-1,3,2-dioxophosphazenecyclohexane-2-one, raise the temperature to 110~120℃, continue stirring and reacting for 12~14h, and distill under reduced pressure to obtain the phosphorus-silicon composite flame retardant monomer; S3: Mix 2,4-dihydroxybenzophenone and sodium hydroxide aqueous solution evenly, stir at room temperature for 10-20 min, add epichlorohydrin dropwise, and after the addition is complete, heat to 85-95℃ and react in an oil bath for 4-5 h. Wash with deionized water at 70-80℃, let stand to separate the layers, take the organic phase and dry it with anhydrous magnesium sulfate, and distill under reduced pressure to obtain epoxidized benzophenone. S4: Mix aminated graphene oxide, epoxidized benzophenone, and N,N-dimethylformamide evenly, stir and react at 50~60℃ for 7~9h, filter, wash, and dry to obtain modified graphene oxide. S5: Dissolve terpyridine diol monomer and phosphorus silicon composite flame retardant monomer in N,N-dimethylformamide and mix evenly to obtain a chain extender solution; under nitrogen protection, mix isophorone diisocyanate and polytetrahydrofuran, stir at 70~80℃ for 1~2h, add chain extender solution and dibutyltin dilaurate, continue stirring and react for 2~3h, dry to obtain polyurethane; mix polyurethane, modified graphene oxide and N,N-dimethylformamide evenly, stir at room temperature, degas under vacuum, pour into a mold, dry to constant weight to obtain salt spray resistant yacht film.

2. The method for preparing the salt spray resistant yacht membrane as described in claim 1, characterized in that, The molar ratio of 2,2':6',2"-terpyridine-4'-carboxaldehyde and 2-amino-2-methyl-1,3-propanediol in step S1 is 1:

1.

3. The method for preparing the salt spray resistant yacht membrane as described in claim 1, characterized in that, The intermediate in step S2 is prepared as follows: Diphenyldichlorosilane, p-hydroxybenzaldehyde, and triethylamine are weighed in a molar ratio of 1:2:2; p-hydroxybenzaldehyde and tetrahydrofuran are mixed evenly and stirred at room temperature; triethylamine is added and stirring is continued; diphenyldichlorosilane is added under ice-water bath conditions; the mixture is stirred and reacted at 40-50°C for 3-4 hours; the mixture is filtered and distilled under reduced pressure to obtain the intermediate.

4. The method for preparing the salt spray resistant yacht membrane as described in claim 1, characterized in that, The molar ratio of the intermediate, 3-amino-1-propanol, and 5,5-dimethyl-1,3,2-dioxophosphanecyclohexane-2-one in step S2 is 1:2:

2.

5. The method for preparing the salt spray resistant yacht membrane as described in claim 1, characterized in that, The molar ratio of 2,4-dihydroxybenzophenone and epichlorohydrin in step S3 is 1:(3~4).

6. The method for preparing the salt spray resistant yacht membrane as described in claim 1, characterized in that, The preparation method of the aminated graphene oxide in step S4 is as follows: graphene oxide and N,N-dimethylformamide are mixed at a mass ratio of 1:(200~300), stirred at room temperature, ethylenediamine at 80~100 times the mass of graphene oxide is added, stirring is continued, 1-ethyl-(3-dimethylaminopropyl)carbodiimide hydrochloride at 0.05~0.07 times the mass of graphene oxide is added, and the mixture is reacted in a water bath at 55~65℃ for 6~8 hours. After filtration, washing, and drying, aminated graphene oxide is obtained.

7. The method for preparing the salt spray resistant yacht membrane as described in claim 1, characterized in that, In step S4, the mass ratio of aminated graphene oxide to epoxide benzophenone is 1:(8~10).

8. The method for preparing the salt spray resistant yacht membrane as described in claim 1, characterized in that, The molar ratio of isophorone diisocyanate, polytetrahydrofuran, terpyridine diol monomer, and phosphorus-silicon composite flame retardant monomer in step S5 is (10~12):(6~7):(2~3):(3~4).

9. The method for preparing the salt spray resistant yacht membrane as described in claim 1, characterized in that, The dosage relationship of polyurethane, modified graphene oxide, and N,N-dimethylformamide in step S5 is as follows: by mass parts, polyurethane 80-90 parts, modified graphene oxide 3-3.4 parts, and N,N-dimethylformamide 200-220 parts.

10. A salt spray resistant yacht membrane, characterized in that, It is prepared by the preparation method described in any one of claims 1 to 9.

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