Preparation method of high-hydrophobicity corrosion-resistant fluorine-containing polyurea material

Abstract

The invention discloses a preparation method of a fluorine-containing polyurea material with high hydrophobicity and corrosion resistance. An amino-terminated fluorine-containing polymer is used as a raw material and is subjected to a copolymerization reaction with an amino-containing oligomer, an amine compound and an isocyanate compound. Or an amino siloxane oligomer and an amino silane compound can be introduced, and then the amino siloxane oligomer and the amino silane compound react with the amino group-containing oligomer and other components. The process is simple and convenient, conditions are mild and efficient, the fluorine content of the fracture surface of the product reaches 25% or above, the fluorine content of the surface is higher than 50%, and due to introduction of fluorine-containing groups, the hydrophobicity and corrosion resistance of the material are remarkably improved on the basis that the original mechanical property of polyurea is reserved. The requirements for long-term reliability and extreme protection performance under extreme working conditions are met, the construction limitation caused by rapid curing of a traditional polyurea material is broken through, and dual optimization of material performance and process feasibility is achieved. The composite material is widely applied to the fields of ocean engineering facility protection, chemical equipment protection, electronic and electric appliance packaging, aerospace parts and the like.

Description

Technical Field

[0002] This invention relates to a method for preparing a fluorinated polyurea material with high hydrophobicity and corrosion resistance. Background Technology

[0003] Fluorinated polyurea materials combine the advantages of fluoropolymers and polyurea. The introduction of fluorinated groups gives polyurea superior hydrophobicity, corrosion resistance and acid and alkali resistance, while maintaining the advantages of strong mechanical properties of polyurea. This makes it an indispensable high-performance material in fields such as marine engineering facility protection, chemical equipment protection, electronic and electrical packaging, and aerospace components.

[0004] Studies have shown that traditional polyurea materials perform poorly in extreme environments. In high-humidity environments, these materials easily absorb water; the intrusion of water molecules damages their internal structure, causing swelling and deformation, thus reducing their mechanical properties and chemical stability, and shortening their service life. In highly corrosive media (such as strong acids, strong alkalis, and strong oxidizing substances), these materials are easily corroded, leading to the breakage of chemical bonds, reduced strength, and surface cracks, thus failing to maintain their protective and sealing effects for a long time. Besides insufficient long-term weather resistance and corrosion resistance, traditional polyurea materials have significant defects in application, with their excessively rapid reaction speed being particularly prominent. Polyurea materials are generally composed of component A (isocyanate component) and component B (amino compound component, including oligomers of amino groups and amine compounds), exhibiting an extremely short gel time during mixing. While this characteristic gives polyurea materials the advantage of rapid molding, it also places extremely high demands on construction equipment and processes, and makes it difficult to ensure the uniformity and density of the coating when working on complex surfaces or large areas. In order to systematically overcome the above-mentioned multiple limitations, researchers began to explore the molecular-level modification design of polyurea materials. Summary of the Invention

[0005] To overcome the aforementioned shortcomings, this invention synthesizes a fluorinated polyurea material with high hydrophobicity and corrosion resistance. This invention uses an amino-terminated fluorinated polymer as a raw material, dissolved in an organic solvent under mild conditions, and copolymerizes it with amino-containing oligomers, amine compounds, and isocyanate compounds. As a system extension, aminosiloxane oligomers and aminosilane compounds can be further introduced into this raw material system, and then reacted with the aforementioned amino-containing oligomers and other components to finally obtain the fluorinated polyurea material. This preparation process is characterized by mild conditions and high efficiency, and the hydrophobicity and corrosion resistance of the material are enhanced by increasing the fluorine content. The resulting product, with its excellent comprehensive performance, is expected to find wide application in marine engineering facility protection, chemical equipment protection, electronic and electrical packaging, aerospace components, and other fields. It meets the requirements for long-term reliability and ultimate protective performance under extreme working conditions, overcomes the construction limitations caused by the rapid curing of traditional polyurea materials, and achieves dual optimization of material performance and process feasibility.

[0006] The objective of this invention is achieved through the following technical solution: This invention discloses a method for preparing a fluorinated polyurea material with high hydrophobicity and corrosion resistance, specifically comprising the following steps: (a) Place the amine-terminated fluoropolymer in a reaction flask, add a polar organic solvent to prepare an amine-terminated fluoropolymer with a mass concentration of 16-25%, and stir until it is completely dissolved; (b) An oligomer containing an amino group, an amine compound, and an isocyanate compound are added sequentially to the above reaction flask, and the reaction is carried out under microwave radiation conditions; wherein the microwave power is adjusted in the range of 180~480 kW, preferably 220~440 kW. The reaction temperature is controlled at 40~80℃, preferably 40~60℃. The stirring speed is set at 150~300 rpm, preferably 180~250 rpm. The reaction duration is 240~540 minutes, preferably 300~480 minutes; the molar ratio of the amino group in the terminal amino-containing fluoropolymer to the amino-containing oligomer, isocyanate compound, and amine compound is 1:0.5~2:5~11.5:1~4, preferably 1:0.5~1.5:6~10:2~3 (based on the amino group in the terminal amino-containing fluoropolymer); (c) After the reaction is complete, some of the solvent is removed by rotary evaporation, and then the polymer after rotary evaporation is placed in a freeze dryer to completely remove the residual solvent by low-temperature freezing and vacuum drying.

[0007] Alternatively, in step (a), after the terminal amino-containing fluoropolymer is completely dissolved, aminosiloxane oligomer and aminosilane compound are added sequentially to the reaction flask, stirred evenly, and then steps (b) and (c) are performed; wherein the molar ratio of the terminal amino-containing fluoropolymer to the aminosiloxane oligomer and aminosilane compound is 1:0.5~1.5:0.5~1.5, preferably 1:0.5~1:0.5~1.

[0008] Furthermore, in the above technical solution, the fluorinated polymer with terminal amino groups is a polymer in which fluorine atoms are present on the carbon atoms of the main chain or side chain, and amino groups are present at the chain ends, with a number average molecular weight of 0.5 × 10⁻⁶. 3 ~5×10 4 Within the range.

[0009] Furthermore, in the above technical solution, the amine-terminated fluoropolymer can be a fluoroolefin copolymer containing amine terminates, selected from tetrafluoroethylene-vinylidene fluoride copolymer, vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride-vinyl fluoride copolymer, tetrafluoroethylene-hexafluoropropylene copolymer, hexafluoroisobutylene-vinylidene fluoride copolymer, vinylidene fluoride-monochlorotrifluoroethylene copolymer, trifluorochloroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoromethyl vinyl ether copolymer, vinylidene fluoride-perfluoromethyl vinyl ether copolymer, perfluoroethyl vinyl ether-tetrafluoroethylene copolymer, vinylidene fluoride-hexafluoropropylene amine-terminated copolymer, vinylidene fluoride-perfluoroethyl vinyl ether copolymer, vinylidene fluoride-perfluoropropyl vinyl ether copolymer, trifluorochloroethylene-perfluoromethyl vinyl ether copolymer, vinylidene fluoride-perfluoromethyl vinyl ether amino copolymer, vinylidene fluoride-tetrafluoroethylene-perfluoroethyl vinyl ether terpolymer, vinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether terpolymer, and vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer. Alternatively, it may be a copolymer of fluoroolefins and non-fluoroolefins, selected from vinylidene fluoride-ethylene copolymers, monochlorotrifluorochloroethylene-ethylene copolymers, tetrafluoroethylene-propylene copolymers, tetrafluoroethylene-ethylene copolymers, vinylidene fluoride-propylene copolymers, hexafluoropropylene-ethylene copolymers, vinylidene fluoride-butene copolymers, hexafluoropropylene-butene copolymers, trifluorochloroethylene-vinyl fluoride copolymers, perfluoromethyl vinyl ether-ethylene copolymers, hexafluoropropylene-vinyl fluoride copolymers, hexafluoroisobutylene-vinylidene fluoride copolymers, hexafluoropropylene-tetrafluoroethylene-propylene terpolymers, and vinylidene fluoride-tetrafluoroethylene-propylene terpolymers. Preferably, it is a vinylidene fluoride-hexafluoropropylene copolymer or a vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer.

[0010] Furthermore, in the above technical solution, the organic solvent is one or more compounded organic solvent systems. It is selected from one or more compounded solvent systems such as N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetone, and ethyl acetate. Preferably, it is a compound system of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and acetone.

[0011] Furthermore, in the above technical solution, the amine oligomer can be one or more of the following: diamino polyether D-230, diamino polyether D-400, diamino polyether D-2000, diamino polyether D-5000, monoamino polyether M-600, monoamino polyether M-1000, monoamino polyether M-2070, monoamino polyether M-3000, modified diamino polyether SD-231, modified diamino polyether SD-401, and triamino polyether XTJ-542. Preferably, it is diamino polyether D-2000, diamino polyether D-5000, monoamino polyether M-1000, monoamino polyether M-2070, or monoamino polyether M-3000.

[0012] Furthermore, in the above technical solution, the isocyanate compound may be isophorone diisocyanate, trifluoromethylbenzene isocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,4-cyclohexane diisocyanate, or lysine diisocyanate. Preferably, it isophorone diisocyanate, trifluoromethylbenzene isocyanate, hexamethylene diisocyanate, or dicyclohexylmethane-4,4'-diisocyanate is preferred.

[0013] Furthermore, in the above technical solution, the amine compound may be hexamethylenediamine, ethylenediamine, isophoronediamine, m-phenylenediamine, polyetherdiamine, perfluoropolyetherdiamine, 3,3'-difluorobenzidine, 4,4'-diaminodiphenylmethane, or 3,3'-dichloro-4,4'-diaminodiphenylmethane. Preferably, it is hexamethylenediamine, ethylenediamine, isophoronediamine, m-phenylenediamine, 3,3'-difluorobenzidine, or 4,4'-diaminodiphenylmethane.

[0014] Furthermore, in the above technical solution, the aminosiloxane oligomer can be one or more of α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(aminoethylaminopropyl)polydimethylsiloxane, side-chain aminopropyl polydimethylsiloxane, amino-terminated polymethyltrifluoropropylsiloxane, amino-terminated polydimethylsiloxane-polyfluoroalkyl ether block copolymer, amino-terminated polymethylphenylsiloxane, and amino-terminated epoxy-modified polydimethylsiloxane. Preferably, it is amino-terminated polymethyltrifluoropropylsiloxane or amino-terminated polymethylphenylsiloxane.

[0015] Furthermore, in the above technical solution, the aminosilane compound may be one or more selected from γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-ethyl-γ-aminopropyltrimethoxysilane, bis(γ-trimethoxysilylpropyl)amine, and N-aminoethyl-γ-aminopropyltrimethoxysilane. Preferably, it is γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, or bis(γ-trimethoxysilylpropyl)amine.

[0016] Beneficial effects of the invention This application introduces fluorinated groups into polyurea materials, which can improve their overall performance by utilizing the high hydrophobicity and corrosion resistance of fluorinated polymers. Compared with the second-level curing characteristics pursued by traditional polyurea materials, this solution significantly extends the curing time by controlling the reaction kinetics, thus breaking through the strict limitations of rapid prototyping on the construction window.

[0017] The main feature of this invention is that it uses an amino-terminated fluoropolymer as the base raw material, and copolymerizes it with amino-containing oligomers, amine compounds, and isocyanate compounds to obtain a fluorinated polyurea material. This invention features a simple, mild, and efficient process, producing a product with a cross-sectional fluorine content of over 25% and a surface fluorine content exceeding 50%. Furthermore, this fluorinated polyurea material combines the advantages of fluoropolymers and polyurea, exhibiting excellent hydrophobicity and corrosion resistance, making it more suitable for applications where long-term reliability and extreme protective performance requirements far outweigh construction speed. Detailed Implementation

[0018] The following non-limiting embodiments are intended to enable those skilled in the art to more fully understand the present invention, but do not limit the invention in any way.

[0019] Example 1 5g of an amino-terminated fluoropolymer (amino-terminated vinylidene fluoride-hexafluoropropylene copolymer, number average molecular weight 3000) was dissolved in 20ml of N,N-dimethylformamide and placed in a 250ml three-necked flask. Diamino polyether D-5000 (8333mg, 1.667mmol), trifluoromethylbenzene isocyanate (4363mg, 23.333mmol), and hexamethylenediamine (967mg, 8.333mmol) were added sequentially to the three-necked flask. The reaction was carried out under microwave-assisted synthesis at 220kW power, a reaction temperature of 50℃, and a stirring speed of 180 rpm for 480 minutes. After the reaction, some solvent was removed by rotary evaporation, and the evaporated polymer was then placed in a freeze dryer for low-temperature freezing and vacuum drying to completely remove residual solvent. The curing time at room temperature was 32 hours.

[0020] Fourier transform infrared spectroscopy (FTIR) characterization of the product revealed characteristic peaks corresponding to urea bond structures, fluorine-containing group structures, and amino groups. Energy-dispersive X-ray spectroscopy (EDS) analysis of the product's elemental composition showed that the fluorine content reached 27% in the cross-sectional area and 76% on the surface. Wettability assessment using a contact angle meter showed a static contact angle of 121°. Furthermore, the product was placed in 25% HCl and NaOH solutions for 72 consecutive hours at 35°C for corrosion resistance testing. The results showed no blistering or peeling on either product surface, only slight changes in gloss, with mass change rates of 0.52% and 0.23%, respectively.

[0021] The molar ratio of amino to diamino polyether D-5000 to trifluoromethylbenzene isocyanate to hexamethylenediamine in the amino-terminated fluoropolymer is 1:0.5:7:2.5.

[0022] Example 2 5 g of an amino-terminated fluoropolymer (amino-terminated vinylidene fluoride-hexafluoropropylene copolymer, number average molecular weight 2400) was dissolved in 20 ml of N,N-dimethylacetamide and placed in a 250 ml three-necked flask. Amino-terminated polymethyltrifluoropropylsiloxane (2500 mg, 1.042 mmol), γ-aminopropyltriethoxysilane (461 mg, 2.083 mmol), monoamino polyether M-3000 (9375 mg, 3.125 mmol), dicyclohexylmethane-4,4'-diisocyanate (4371 mg, 16.664 mmol), and isophorone diamine (1064 mg, 6.235 mmol) were added sequentially to the three-necked flask. The reaction was carried out under microwave-assisted synthesis conditions at 280 kW microwave power, a reaction temperature of 60 °C, and a stirring speed of 220 rpm for 300 minutes. After the reaction is complete, some of the solvent is removed by rotary evaporation. Then, the evaporated polymer is placed in a freeze dryer and dried at low temperature and under vacuum to completely remove the residual solvent. The curing time at room temperature is 36 hours.

[0023] Fourier transform infrared spectroscopy (FTIR) characterized the product, revealing characteristic peaks corresponding to urea bond structures, fluorine-containing group structures, and amino groups. EDS analysis of the product's elemental composition showed that the fluorine content reached 25% in the cross-sectional area and 60% on the surface. Wettability assessment using a contact angle meter showed a static contact angle of 134°. Further corrosion resistance tests were conducted at 35°C for 72 hours in 25% HCl and NaOH solutions. The results showed no blistering or peeling on either surface, only slight changes in gloss, with mass change rates of 0.49% and 0.16%, respectively.

[0024] The amino group in the amino-terminated fluoropolymer is: amino-terminated polymethyltrifluoropropylsiloxane: γ-aminopropyltriethoxysilane: monoamino polyether M-3000: dicyclohexylmethane-4,4'-diisocyanate: isophorone diamine molar ratio = 1:0.5:1:1.5:8:3.

[0025] Example 3 5 g of an amino-terminated fluoropolymer (amino-terminated vinylidene fluoride-hexafluoropropylene copolymer, number average molecular weight 2450) was dissolved in 20 ml of N,N-dimethylformamide and placed in a 250 ml three-necked flask. Monoamino polyether M-1000 (2041 mg, 2.041 mmol), trifluoromethylphenyl isocyanate (2290 mg, 12.246 mmol), and m-phenylenediamine (662 mg, 6.123 mmol) were added sequentially to the three-necked flask. The reaction was carried out under microwave-assisted synthesis at 300 kW power, a reaction temperature of 40 °C, and a stirring speed of 250 rpm for 420 minutes. After the reaction, some solvent was removed by rotary evaporation, and the evaporated polymer was then placed in a freeze dryer for low-temperature freezing and vacuum drying to completely remove residual solvent. The curing time at room temperature was 42 hours.

[0026] Fourier transform infrared spectroscopy (FTIR) characterized the product, revealing characteristic peaks corresponding to urea bond structures, fluorine-containing group structures, and amino groups. EDS analysis of the product's elemental composition showed that the fluorine content reached 29% in the cross-sectional area and 74% on the surface. Wettability assessment using a contact angle meter showed a static contact angle of 131°. Further corrosion resistance tests were conducted at 35°C for 72 hours in 25% HCl and NaOH solutions. The results showed no blistering or peeling on either surface, only slight changes in gloss, with mass change rates of 0.46% and 0.19%, respectively.

[0027] The molar ratio of amino group to monoamino polyether M-1000 to trifluoromethylbenzene isocyanate to m-phenylenediamine in the amino-terminated fluoropolymer is 1:1:6:3.

[0028] Example 4 5 g of an amino-terminated fluoropolymer (amino-terminated vinylidene fluoride-hexafluoropropylene copolymer, number average molecular weight 2770) was dissolved in 30 ml of a dimethyl sulfoxide and acetone mixture and placed in a 250 ml three-necked flask. The following compounds were added sequentially to the three-necked flask: amino-terminated polymethylphenylsiloxane (4513 mg, 1.805 mmol), γ-aminopropyltrimethoxysilane (243 mg, 1.354 mmol), monoamino polyether M-2070 (3736 mg, 1.805 mmol), hexamethylene diisocyanate (3188 mg, 18.953 mmol), and m-phenylenediamine (586 mg, 5.415 mmol). The reaction was carried out under microwave-assisted synthesis conditions at 400 kW microwave power, a reaction temperature of 60 °C, and a stirring speed of 220 rpm for 360 minutes. After the reaction is complete, some of the solvent is removed by rotary evaporation. Then, the evaporated polymer is placed in a freeze dryer and dried at low temperature and under vacuum to completely remove the residual solvent. The curing time at room temperature is 36 hours.

[0029] Fourier transform infrared spectroscopy (FTIR) characterized the product, revealing characteristic peaks corresponding to urea bond structures, fluorine-containing group structures, and amino groups. EDS analysis of the product's elemental composition showed that the fluorine content reached 26% in the cross-sectional area and 57% on the surface. Wettability assessment using a contact angle meter showed a static contact angle of 125°. Further corrosion resistance tests were conducted at 35°C for 72 hours in 25% HCl and NaOH solutions. The results showed no blistering or peeling on either surface, only slight changes in gloss, with mass change rates of 0.61% and 0.21%, respectively.

[0030] The amino group in the amino-terminated fluoropolymer is: amino-terminated polymethylphenylsiloxane: γ-aminopropyltrimethoxysilane: monoamino polyether M-2070: hexamethylene diisocyanate: hexafluorohexanediamine molar ratio = 1:1:0.75:1:10.5:3.

[0031] Example 5 5 g of an amino-terminated fluoropolymer (amino-terminated vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, number average molecular weight 2600) was dissolved in 20 ml of N-methylpyrrolidone and placed in a 250 ml three-necked flask. Monoamino polyether M-3000 (2884 mg, 0.962 mmol), dicyclohexylmethane-4,4'-diisocyanate (4792 mg, 18.269 mmol), and isophorone diamine (982 mg, 5.769 mmol) were added sequentially to the three-necked flask. The reaction was carried out under microwave-assisted synthesis at 440 kW microwave power, a reaction temperature of 40 °C, and a stirring speed of 220 rpm for 300 minutes. After the reaction, some solvent was removed by rotary evaporation, and the evaporated polymer was then placed in a freeze dryer for low-temperature freezing and vacuum drying to completely remove residual solvent. The curing time at room temperature was 40 hours.

[0032] Fourier transform infrared spectroscopy (FTIR) characterized the product, revealing characteristic peaks corresponding to urea bond structures, fluorine-containing group structures, and amino groups. EDS analysis of the product's elemental composition showed that the fluorine content reached 27% in the cross-sectional area and 72% on the surface. Wettability assessment using a contact angle meter showed a static contact angle of 126°. Further corrosion resistance tests were conducted at 35°C for 72 hours in 25% HCl and NaOH solutions. The results showed no blistering or peeling on either product surface, only slight changes in gloss, with mass change rates of 0.53% and 0.21%, respectively.

[0033] The molar ratio of amino group to monoamino polyether M-3000 to methylcyclohexyl diisocyanate to isophorone diamine in the amino-terminated fluoropolymer is 1:0.5:9.5:3.

[0034] Example 6 5g of an amino-terminated fluoropolymer (amino-terminated vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, number-average molecular weight 2850) was dissolved in 20ml of N-methylpyrrolidone and placed in a 250ml three-necked flask. Diamino polyether D-5000 (4386mg, 0.877mmol), dicyclohexylmethane-4,4'-diisocyanate (4142mg, 15.790mmol), and 4,4'-diaminodiphenylmethane (1043mg, 5.263mmol) were added sequentially to the three-necked flask. The reaction was carried out under microwave-assisted synthesis at 350kW power, a reaction temperature of 50℃, and a stirring speed of 180rpm for 300 minutes. After the reaction, some solvent was removed by rotary evaporation, and the evaporated polymer was then placed in a freeze dryer for low-temperature freezing and vacuum drying to completely remove residual solvent. The curing time at room temperature was 34 hours.

[0035] Fourier transform infrared spectroscopy (FTIR) characterized the product, revealing characteristic peaks corresponding to urea bond structures, fluorine-containing group structures, and amino groups. EDS analysis of the product's elemental composition showed that the fluorine content reached 27% in the cross-sectional area and 73% on the surface. Wettability assessment using a contact angle meter showed a static contact angle of 120°. Further corrosion resistance tests were conducted at 35°C for 72 hours in 25% HCl and NaOH solutions. The results showed no blistering or peeling on either surface, only slight changes in gloss, with mass change rates of 0.53% and 0.23%, respectively.

[0036] The molar ratio of amino group to diamino polyether D-5000 to dicyclohexylmethane-4,4'-diisocyanate to 4,4'-diaminodiphenylmethane in the amine-terminated fluoropolymer is 1:0.5:9:3.

[0037] Example 7 5 g of an amino-terminated fluoropolymer (amino-terminated vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, number average molecular weight 2500) was dissolved in 30 ml of a dimethyl sulfoxide and acetone mixture and placed in a 250 ml three-necked flask. Amino-terminated polymethylphenylsiloxane (4050 mg, 1.500 mmol), bis(γ-trimethoxysilylpropyl)amine (3415.5 mg, 1.000 mmol), diamino polyether D-2000 (4000 mg, 2.000 mmol), isophorone diisocyanate (2667 mg, 12.000 mmol), and hexamethylenediamine (465 mg, 4.000 mmol) were added sequentially to the three-necked flask. The reaction was carried out under microwave-assisted synthesis conditions at 280 kW, a reaction temperature of 60 °C, and a stirring speed of 180 rpm for 360 minutes. After the reaction is complete, some of the solvent is removed by rotary evaporation. Then, the evaporated polymer is placed in a freeze dryer and dried at low temperature and under vacuum to completely remove the residual solvent. The curing time at room temperature is 36 hours.

[0038] Fourier transform infrared spectroscopy (FTIR) characterized the product, revealing characteristic peaks corresponding to urea bond structures, fluorine-containing group structures, and amino groups. EDS analysis of the product's elemental composition showed that the fluorine content reached 25% in the cross-sectional area and 57% on the surface. Wettability assessment using a contact angle meter showed a static contact angle of 134°. Further corrosion resistance tests were conducted at 35°C for 72 hours in 25% HCl and NaOH solutions. The results showed no blistering or peeling on either surface, only slight changes in gloss, with mass change rates of 0.63% and 0.27%, respectively.

[0039] The amino group in the amino-terminated fluoropolymer is: amino-terminated polymethylphenylsiloxane: bis(γ-trimethoxysilylpropyl)amine: diamino polyether D-2000: isophorone diisocyanate: hexamethylenediamine molar ratio = 1:0.75:0.5:1:6:2.

[0040] Example 8 5g of an amino-terminated fluoropolymer (amino-terminated vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymer, number-average molecular weight 2550) was dissolved in 30ml of N,N-dimethylformamide and placed in a 250ml three-necked flask. Diamino polyether D-2000 (3922mg, 1.961mmol), isophorone diisocyanate (3705mg, 16.668mmol), and ethylenediamine (354mg, 5.883mmol) were added sequentially to the three-necked flask. The reaction was carried out under microwave-assisted synthesis at 360kW power, a reaction temperature of 40℃, and a stirring speed of 250rpm for 420 minutes. After the reaction, some solvent was removed by rotary evaporation, and the evaporated polymer was then placed in a freeze dryer for low-temperature freezing and vacuum drying to completely remove residual solvent. The curing time at room temperature was 35 hours.

[0041] Fourier transform infrared spectroscopy (FTIR) characterized the product, revealing characteristic peaks corresponding to urea bond structures, fluorine-containing group structures, and amino groups. EDS analysis of the product's elemental composition showed that the fluorine content reached 27% in the cross-sectional area and 73% on the surface. Wettability assessment using a contact angle meter showed a static contact angle of 126°. Further corrosion resistance tests were conducted at 35°C for 72 hours in 25% HCl and NaOH solutions. The results showed no blistering or peeling on either product surface, only slight changes in gloss, with mass change rates of 0.41% and 0.16%, respectively.

[0042] The molar ratio of amino to diamino polyether D-2000 to isophorone diisocyanate to ethylenediamine in the amino-terminated fluoropolymer is 1:1:8.5:3.

[0043] Examples 9-11 and Comparative Examples 1 and 2 The preparation, testing, and calculation methods were carried out according to Example 1, with the difference being the amount of organic solvent used. The specific results are shown in Table 1.

[0044] Table 1

[0045] Examples 12-14 and Comparative Example 3 The preparation, testing, and calculation methods were carried out according to Example 1, the difference being the type of organic solvent. The specific results are shown in Table 2.

[0046] Table 2

[0047] Examples 15-21 and Comparative Examples 4 and 5 The preparation, testing, and calculation methods were carried out according to Example 1, with the difference being the microwave power. The specific results are shown in Table 3.

[0048] Table 3

[0049] Examples 22-25 and Comparative Examples 6 and 7 The preparation, testing, and calculation methods were carried out according to Example 1, with the difference being the reaction temperature. The specific results are shown in Table 4.

[0050] Table 4

[0051] Examples 26-30 and Comparative Examples 8 and 9 The preparation, testing, and calculation methods were carried out according to Example 1, with the difference being the reaction time. The specific results are shown in Table 5.

[0052] Table 5

[0053] Examples 31-34 and Comparative Example 11 The preparation, testing, and calculation methods were carried out according to Example 1, with the difference being the stirring speed. The specific results are shown in Table 6.

[0054] Table 6

[0055] Examples 35-37 The preparation, testing, and calculation methods were carried out according to Example 1, with the difference being the addition and type of aminosiloxane oligomers and aminosilane compounds. The specific results are shown in Table 7.

[0056] Table 7

[0057] The embodiments of the present invention have been described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the scope of the technical concept of the present invention, various simple modifications can be made to the technical solution of the present invention, and these simple modifications all fall within the protection scope of the present invention.

[0058] Furthermore, various different embodiments of the present invention can be combined in any way, as long as they do not violate the spirit of the present invention, they should also be regarded as the content disclosed by the present invention.

Claims

1. A method for preparing a highly hydrophobic and corrosion-resistant fluorinated polyurea material, characterized in that... Specifically, the following steps are included: (a) Add a polar organic solvent to the amine-terminated fluoropolymer to prepare an amine-terminated fluoropolymer with a mass concentration of 16-25%, and stir until it is completely dissolved; (b) Add an amino-containing oligomer, an amine compound, and an isocyanate compound sequentially to the solution in (a) and carry out the reaction under microwave radiation conditions; wherein the microwave power is adjusted in the range of 180~480kW, the reaction temperature is controlled at 40~80℃, the stirring speed is set at 150~300 rpm, and the reaction duration is 240~540 minutes. (c) After the reaction is complete, some of the solvent is removed by rotary evaporation, and then the polymer after rotary evaporation is placed in a freeze dryer to completely remove the residual solvent by low-temperature freezing and vacuum drying. Alternatively, in step (a), after the terminal amino-containing fluoropolymer is completely dissolved, aminosiloxane oligomer and aminosilane compound are added to the reaction flask in sequence, stirred evenly, and then steps (b) and (c) are performed. In step (b), the molar ratio of the amino group in the terminal amino-containing fluoropolymer to the amino-containing oligomer, isocyanate compound, and amine compound is 1:0.5~2:5~11.5:1~4.

2. The preparation method according to claim 1, characterized in that, The molar ratio of the amino-terminated fluoropolymer to the aminosiloxane oligomer and aminosilane compound is 1:0.5~1.5:0.5~1.

5.

3. The method according to claim 1, characterized in that, The aforementioned amine-terminated fluoropolymer is a polymer containing fluorine atoms on the carbon atoms of the main chain or side chain, and containing amino groups at the chain ends; its number average molecular weight is 0.5 × 10⁻⁶. 3 ~5×10 4 Within the range.

4. The method according to claim 1, characterized in that, The amine-terminated fluoropolymers are fluoroolefin copolymers containing amine-terminated amino groups, selected from tetrafluoroethylene-vinylidene fluoride copolymers, vinylidene fluoride-hexafluoropropylene copolymers, vinylidene fluoride-vinyl fluoride copolymers, tetrafluoroethylene-hexafluoropropylene copolymers, hexafluoroisobutylene-vinylidene fluoride copolymers, vinylidene fluoride-monochlorotrifluoroethylene copolymers, trifluorochloroethylene-hexafluoropropylene copolymers, tetrafluoroethylene-perfluoromethyl vinyl ether copolymers, vinylidene fluoride-perfluoromethyl vinyl ether copolymers, perfluoroethyl vinyl ether-tetrafluoroethylene copolymers, vinylidene fluoride-hexafluoropropylene amine-terminated copolymers, vinylidene fluoride-perfluoroethyl vinyl ether copolymers, vinylidene fluoride-perfluoropropyl vinyl ether copolymers, trifluorochloroethylene-perfluoromethyl vinyl ether copolymers, vinylidene fluoride-perfluoromethyl vinyl ether amino copolymers, vinylidene fluoride-tetrafluoroethylene-perfluoroethyl vinyl ether terpolymers, vinylidene fluoride-tetrafluoroethylene-perfluoromethyl vinyl ether terpolymers, and vinylidene fluoride-hexafluoropropylene-tetrafluoroethylene terpolymers. It may be a copolymer of fluoroolefins and non-fluoroolefins, selected from vinylidene fluoride-ethylene copolymer, monochlorotrifluorochloroethylene-ethylene copolymer, tetrafluoroethylene-propylene copolymer, tetrafluoroethylene-ethylene copolymer, vinylidene fluoride-propylene copolymer, hexafluoropropylene-ethylene copolymer, vinylidene fluoride-butene copolymer, hexafluoropropylene-butene copolymer, trifluorochloroethylene-fluoroethylene copolymer, perfluoromethyl vinyl ether-ethylene copolymer, hexafluoropropylene-fluoroethylene copolymer, hexafluoroisobutylene-vinylidene fluoride copolymer, hexafluoropropylene-tetrafluoroethylene-propylene terpolymer, and vinylidene fluoride-tetrafluoroethylene-propylene terpolymer.

5. The method according to claim 1, characterized in that, The organic solvent is one or more compounded organic solvent systems; selected from one or more compounded solvent systems of N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetone, and ethyl acetate.

6. The method according to claim 1, characterized in that, The amine oligomers mentioned are one or more of the following: diamino polyether D-230, diamino polyether D-400, diamino polyether D-2000, diamino polyether D-5000, monoamino polyether M-600, monoamino polyether M-1000, monoamino polyether M-2070, monoamino polyether M-3000, modified diamino polyether SD-231, modified diamino polyether SD-401, and triamino polyether XTJ-542.

7. The method according to claim 1, characterized in that, The aminosiloxane oligomers mentioned herein are one or more of the following: α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(aminoethylaminopropyl)polydimethylsiloxane, side-chain aminopropyl polydimethylsiloxane, amino-terminated polymethyltrifluoropropylsiloxane, amino-terminated polydimethylsiloxane-polyfluoroalkyl ether block copolymer, amino-terminated polymethylphenylsiloxane, amino-terminated long-chain alkyl-modified polydimethylsiloxane, and amino-terminated epoxy-modified polydimethylsiloxane.

8. The method according to claim 1, characterized in that, The aminosilane compound is one or more selected from γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-ethyl-γ-aminopropyltrimethoxysilane, bis(γ-trimethoxysilylpropyl)amine, and N-aminoethyl-γ-aminopropyltrimethoxysilane.

9. The method according to claim 1, characterized in that, The isocyanate compounds mentioned are one or more of the following: isophorone diisocyanate, trifluoromethylbenzene isocyanate, hexamethylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,4-cyclohexane diisocyanate, and lysine diisocyanate.

10. The method according to claim 1, characterized in that, The amine compound is one or more selected from hexamethylenediamine, ethylenediamine, isophoronediamine, m-phenylenediamine, polyetherdiamine, perfluoropolyetherdiamine, 3,3'-difluorobenzidine, 4,4'-diaminodiphenylmethane, and 3,3'-dichloro-4,4'-diaminodiphenylmethane.

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