A reinforced toughened impact-resistant wear-resistant anticorrosion integrated coating material and a preparation method thereof

Abstract

The application discloses a kind of reinforced toughened impact resistant wear-resistant anticorrosion integrated coating material and preparation method thereof, it is related to high polymer composite material and functional coating technical field, method includes: providing hexafluorocyclotriphosphazene and vanillin, mixing, carries out first reaction, obtains first reactant;Providing 4,4'-diamino diphenyl ether and 3,3',4,4'-benzophenone tetracarboxylic dianhydride, mixing, carries out second reaction, obtains second reactant;Providing hydroxyl-terminated polydimethylsiloxane and 4,4'-diphenyl methane diisocyanate, with second reactant is mixed, carries out third reaction, obtains third reactant;Providing iron salt, with first reactant and third reactant are mixed, carries out solidification treatment, obtains coating material;The reinforced toughened impact resistant wear-resistant anticorrosion integrated coating material obtained will be integrated in single layer coating with the functions such as reinforcement, toughening, impact resistance, wear resistance, corrosion resistance, etc., with excellent wear resistance and anticorrosion performance and intrinsic flame-retardant radiation resistance characteristics.

Description

Technical Field

[0001] This application relates to the field of polymer composite materials and functional coating technology, and in particular to an integrated coating material for enhancing toughness, impact resistance, wear resistance and corrosion resistance, and its preparation method. Background Technology

[0002] Corrosion and wear are two major factors leading to the failure of industrial equipment and infrastructure. In fields such as marine engineering, petrochemicals, bridges and tunnels, and aerospace, equipment and structural components are subjected to multiple destructive effects such as corrosive media erosion, solid particle scouring, dynamic load impact, and high-temperature radiation over long periods of time, which places stringent requirements on protective coatings, requiring them to be enhanced, toughened, impact-resistant, wear-resistant, and corrosion-resistant in an integrated manner.

[0003] In related technologies, two strategies are typically adopted to meet the aforementioned multiple performance requirements. The first is a multi-layer composite coating strategy, which achieves functional superposition by sequentially coating a primer layer, anti-corrosion layer, impact-resistant layer, and wear-resistant layer. However, this multi-layer composite solution has disadvantages such as complex processes, long construction cycles, high costs, and the interlayer interfaces being weak points in performance, prone to interlayer delamination leading to overall failure. The second approach is to achieve multi-performance integration by adding multiple functional fillers to a single coating. However, this "physical blending" approach also suffers from problems such as weak bonding between the filler and the matrix interface, limited reinforcement and toughening efficiency, and the filler content easily leading to agglomeration, which deteriorates mechanical properties. Under dynamic loads, the filler is prone to debonding from the matrix, resulting in insufficient long-term durability.

[0004] Therefore, there is an urgent need for a new type of coating material that can integrate the above-mentioned multiple functions from the molecular structure source and has an intrinsic synergistic mechanism, which has important scientific significance and urgent market demand. Summary of the Invention

[0005] In view of this, this application provides an integrated coating material for enhancing toughness, impact resistance, wear resistance, and corrosion resistance, and a method for preparing the same.

[0006] The embodiments of this application are implemented as follows: Firstly, the embodiments of this application provide an integrated coating material for enhanced toughness, impact resistance, wear resistance, and corrosion resistance, and a method for preparing the same, comprising the following steps: Step S11: Provide hexafluorocyclotriphosphazene and vanillin, mix them, and carry out the first reaction to obtain the first reactant; Step S12: Provide 4,4'-diaminodiphenyl ether and 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, mix them, and carry out the second reaction to obtain the second reactant; Step S13: Provide hydroxyl-terminated polydimethylsiloxane and 4,4'-diphenylmethane diisocyanate, mix with the second reactant, and carry out the third reaction to obtain the third reactant; Step S14: Provide iron salt, mix it with the first reactant and the third reactant, and perform a curing treatment to obtain a coating material.

[0007] Optionally, in some embodiments of this application, in step S11: The molar ratio of the hexafluorocyclotriphosphazene to the vanillin is 1:3.

[0008] The mass concentration of vanillin is 30 g / L to 60 g / L.

[0009] The reaction temperature of the first reaction is 40℃~80℃. The reaction time of the first reaction is 20h~40h.

[0010] Step S11 further includes providing a first solvent and an acid-binding agent. The first solvent is selected from one or more of tetrahydrofuran, acetonitrile, dioxane, toluene, and N,N-dimethylformamide. The acid-binding agent is selected from one or more of potassium carbonate, potassium bicarbonate, potassium phosphate, potassium fluoride, and triethylamine.

[0011] Optionally, in some embodiments of this application, step S12 includes: providing 4,4'-diaminodiphenyl ether, 3,3',4,4'-benzophenone tetracarboxylic dianhydride and a second solvent, mixing them, and carrying out a second reaction a to obtain a first mixture; providing a dehydrating agent and a first catalyst, mixing them with the first mixture, and carrying out a second reaction b to obtain a second reactant.

[0012] The second solvent is selected from one or more of N,N-dimethylformamide, tetrahydrofuran, acetonitrile, dioxane, and toluene.

[0013] The dehydrating agent is selected from one or more of acetic anhydride, propionic anhydride, butyric anhydride, benzoic anhydride, trifluoroacetic anhydride, and dicyclohexylcarbodiimide.

[0014] The first catalyst is selected from one or more of triethylamine, N,N-diisopropylethylamine, pyridine, 4-dimethylaminopyridine, and tripropylamine.

[0015] Optionally, in some embodiments of this application, the mass ratio of the 4,4'-diaminodiphenyl ether to the 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride is (5~30):(5~50).

[0016] The mass concentration of the 4,4'-diaminodiphenyl ether is 60 g / L to 200 g / L.

[0017] The mass ratio of the dehydrating agent, the first catalyst and the 4,4'-diaminodiphenyl ether is (10~50):(2~20):(5~30).

[0018] The reaction temperature of the second reaction a is 0℃~10℃. The reaction time of the second reaction a is 2h~8h.

[0019] The reaction temperature of the second reaction b is 30℃~80℃. The reaction time of the second reaction b is 2h~8h.

[0020] Optionally, in some embodiments of this application, step S13 includes: providing hydroxyl-terminated polydimethylsiloxane, 4,4'-diphenylmethane diisocyanate, a third solvent, and a second catalyst; mixing them to carry out a third reaction a to obtain a second mixture; and mixing the second mixture with the second reactant to carry out a third reaction b to obtain a third reactant. The third solvent is selected from one or more of toluene, N,N-dimethylformamide, tetrahydrofuran, acetonitrile, and dioxane.

[0021] The second catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate, stannous isooctanoate, dibutyltin diacetate, and dioctyltin dilaurate.

[0022] Optionally, in some embodiments of this application, the mass ratio of the terminal hydroxyl polydimethylsiloxane, the 4,4'-diphenylmethane diisocyanate and the second reactant is (10~50):(2~15):(10~80).

[0023] The mass concentration of the hydroxyl-terminated polydimethylsiloxane is 300 g / L to 600 g / L.

[0024] The reaction temperature of the third reaction a is 60℃~100℃. The reaction time of the third reaction a is 2h~8h.

[0025] The reaction temperature of the third reaction b is 40℃~80℃. The reaction time of the third reaction b is 2h~8h.

[0026] Optionally, in some embodiments of this application, the provision of the iron salt, mixed with the first reactant and the third reactant, includes: dissolving the first reactant in a fourth solvent, then adding the third reactant, stirring to obtain an intermediate mixture; dissolving the iron salt in a fifth solvent to obtain an iron salt solution, and then adding the iron salt solvent dropwise to the intermediate mixture. The fourth solvent is selected from one or more of tetrahydrofuran, acetonitrile, dioxane, toluene, and N,N-dimethylformamide.

[0027] The fifth solvent is selected from one or more of ethanol, methanol, isopropanol, n-propanol, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

[0028] The iron salt is selected from one or more of ferric acetylacetone, ferric chloride, ferric nitrate, ferric sulfate, and ferric stearate.

[0029] Optionally, in some embodiments of this application, the mass ratio of the iron salt, the first reactant, and the third reactant is (2~10):(5~30):(80~400).

[0030] The curing temperature is 20℃~40℃. The curing time is 5 days~10 days.

[0031] Optionally, in some embodiments of this application, the structural formula of the first reactant is as follows: .

[0032] The structural formula of the second reactant is shown below: .

[0033]

[0034] The structural formula of the third reactant is shown below: m is an integer between 20 and 100.

[0035] Secondly, embodiments of this application also provide an integrated coating material for enhancing toughness, impact resistance, wear resistance, and corrosion resistance, wherein the integrated coating material is prepared by the above-described preparation method.

[0036] The integrated coating material for enhanced toughness, impact resistance, wear resistance, and corrosion resistance provided in this application, and its preparation method, utilizes vanillin trisubstituted hexafluorocyclic triphosphazene. Each phosphorus atom is attached to a vanillin group, while a fluorine atom remains in the form of a PF bond. This PF bond is an intrinsic structural part of the phosphazene ring, remaining stable during curing. It synergistically works with the P=N skeleton of the phosphazene ring to impart excellent hydrophobicity, low surface energy, thermal stability, and flame retardancy to the coating. Simultaneously, the vanillin unit provides both an aldehyde group and an o-methoxy group. The aldehyde group is used to construct dynamic imine bonds, while the o-methoxy group coordinates with iron ions in iron salt solutions. Furthermore, in the P3N3 six-membered ring skeleton of the phosphazene ring, PN synergistic flame retardancy, phosphorus provides flame retardancy, and nitrogen promotes char formation, resulting in a dense char layer during combustion. This allows the phosphazene ring to decompose at temperatures above 300°C, enabling it to withstand gamma rays and electron beam irradiation, and exhibiting good resistance to acids, alkalis, and organic solvents. Simultaneously, polyimide is introduced through 4,4'-diaminodiphenyl ether and 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and polydimethylsiloxane is introduced through hydroxyl-terminated polydimethylsiloxane. Polyimide, as a rigid hard segment, provides intrinsically high strength, high wear resistance, high heat resistance, and excellent corrosion resistance; polydimethylsiloxane, as a flexible soft segment, provides low surface energy, high weather resistance, and stress dissipation capability. A "hard segment-soft segment-hard segment" topology can be formed through polyimide and polydimethylsiloxane. This "hard-soft-hard" triblock structure can spontaneously form microphase separation during curing, producing a physical crosslinking enhancement effect. Furthermore, the two amino groups not only react with aldehyde groups to form a covalent network but also make the triblock polymer a "rigid-flexible-rigid" structural unit of the network, rather than a simple suspended chain. Finally, the Fe³⁺ provided by the iron salt solution… + Simultaneously, the imine bond coordinates with the nitrogen atom of the imine bond and the oxygen atom of the ortho-methoxy group, directly anchoring the dynamic coordination bond to the dynamic covalent nodes of the network, forming a unique topological structure of "dynamic bonds on dynamic bonds." The imine bond (dynamic covalent) provides the network with rearrangement capability and macroscopic self-repair function, capable of breaking and recombining under thermal or acidic conditions; Fe³ + Coordinate bonds (supramolecular dynamics), acting as "sacrificial bonds," preferentially break and dissipate energy under external forces, endowing the coating with excellent toughness and impact resistance; after the external force is removed, the coordinate bonds can be rapidly reassembled. Imine bonds ensure the overall reconfigurability of the network, while coordinate bonds ensure efficient local energy dissipation.

[0037] The preparation method provided in this application yields an integrated coating material that combines five major functions—reinforcement, toughening, impact resistance, wear resistance, and corrosion protection—into a single layer. This coating material exhibits excellent wear and corrosion resistance as well as intrinsic flame retardant and radiation-resistant properties, and has broad application prospects in extreme environmental protection in fields such as marine engineering, petrochemicals, bridges and tunnels, aerospace, and nuclear industry. Attached Figure Description

[0038] To more clearly illustrate the technical solutions in the embodiments of this application, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0039] Figure 1 This is a flowchart illustrating a method for preparing an integrated coating material that is reinforced, toughened, impact-resistant, wear-resistant, and corrosion-resistant, as provided in this application embodiment. Detailed Implementation

[0040] The technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, and not all embodiments. Based on the embodiments of this application, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this application. Furthermore, it should be understood that the specific embodiments described herein are only for illustration and explanation of this application and are not intended to limit this application.

[0041] In this application, unless otherwise stated, directional terms such as "upper" and "lower" generally refer to the upper and lower positions of the device in its actual use or operating state, specifically the orientation shown in the accompanying drawings; while "inner" and "outer" refer to the outline of the device. Furthermore, in the description of this application, the term "comprising" means "including but not limited to". The terms first, second, third, etc., are used merely as illustrative purposes and do not impose numerical requirements or establish a numerical order.

[0042] In this application, "and / or" describes the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can represent: A existing alone, A and B existing simultaneously, or B existing alone. A and B can be singular or plural.

[0043] In this application, "at least one" means one or more, and "more than one" means two or more. "One or more", "at least one of the following", or similar expressions refer to any combination of these items, including any combination of single or multiple items. For example, "at least one of a, b, or c", or "at least one of a, b, and c" can both mean: a, b, c, ab (i.e., a and b), ac, bc, or abc, where a, b, and c can be single or multiple.

[0044] Various embodiments of this application may exist in the form of a range; it should be understood that the description in the form of a range is merely for convenience and brevity and should not be construed as a hard limitation on the scope of this application; therefore, it should be considered that the range description has specifically disclosed all possible sub-ranges and single numerical values ​​within that range. For example, it should be considered that the range description from 1 to 6 has specifically disclosed sub-ranges such as from 1 to 3, from 1 to 4, from 1 to 5, from 2 to 4, from 2 to 6, from 3 to 6, etc., and single numbers within the range, such as 1, 2, 3, 4, 5, and 6, regardless of the range. Furthermore, whenever a numerical range is referred to herein, it means including any referenced number (fraction or integer) within the referred range.

[0045] The structural formulas and molecular weights of some of the chemical reagents used in this application are described below: Hexafluorocyclotriphosphonium (FCCP): Industrial grade, purity ≥98%; Vanillin (4-hydroxy-3-methoxybenzaldehyde): Analytical purity; Hydroxyl-terminated polydimethylsiloxane (PDMS-OH): number average molecular weight Mn=2000, hydroxyl content 0.5 mmol / g; 4,4'-Diphenylmethane diisocyanate (MDI): Industrial grade; 4,4'-Diaminodiphenyl ether (ODA): Analytical grade, vacuum dried; 3,3',4,4'-Benzophenone tetracarboxylic dianhydride (BTDA): Analytical grade, vacuum dried.

[0046] The technical solution of this application is as follows: Firstly, please refer to Figure 1 This application provides a method for preparing an integrated coating material that is reinforced, toughened, impact-resistant, wear-resistant, and corrosion-resistant, comprising the following steps: Step S11: Provide hexafluorocyclotriphosphazene and vanillin, mix them, and carry out the first reaction to obtain the first reactant; Step S12: Provide 4,4'-diaminodiphenyl ether and 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, mix them, and carry out the second reaction to obtain the second reactant; Step S13: Provide hydroxyl-terminated polydimethylsiloxane and 4,4'-diphenylmethane diisocyanate, mix with the second reactant, and carry out the third reaction to obtain the third reactant; Step S14: Provide iron salt, mix it with the first reactant and the third reactant, and perform a curing treatment to obtain a coating material.

[0047] The method for preparing the integrated reinforced, toughened, impact-resistant, wear-resistant, and corrosion-resistant coating material provided in this application utilizes vanillin trisubstituted hexafluorocyclic triphosphazene. Each phosphorus atom is attached to a vanillin group, while a fluorine atom remains in the form of a PF bond. This PF bond is an intrinsic structural part of the phosphazene ring, remaining stable during curing. It synergistically works with the P=N skeleton of the phosphazene ring to impart excellent hydrophobicity, low surface energy, thermal stability, and flame retardancy to the coating. Simultaneously, the vanillin unit provides both an aldehyde group and an o-methoxy group. The aldehyde group is used to construct dynamic imine bonds, while the o-methoxy group coordinates with iron ions in iron salt solutions. Furthermore, in the P3N3 six-membered ring skeleton of the phosphazene ring, PN synergistic flame retardancy, phosphorus provides flame retardancy, and nitrogen promotes char formation, resulting in a dense char layer during combustion. This allows the phosphazene ring to decompose at temperatures above 300°C, enabling it to withstand gamma rays and electron beam irradiation, and exhibiting good resistance to acids, alkalis, and organic solvents. Simultaneously, polyimide is introduced through 4,4'-diaminodiphenyl ether and 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and polydimethylsiloxane is introduced through hydroxyl-terminated polydimethylsiloxane. Polyimide, as a rigid hard segment, provides intrinsically high strength, high wear resistance, high heat resistance, and excellent corrosion resistance; polydimethylsiloxane, as a flexible soft segment, provides low surface energy, high weather resistance, and stress dissipation capability. A "hard segment-soft segment-hard segment" topology can be formed through polyimide and polydimethylsiloxane. This "hard-soft-hard" triblock structure can spontaneously form microphase separation during curing, producing a physical crosslinking enhancement effect. Furthermore, the two amino groups not only react with aldehyde groups to form a covalent network but also make the triblock polymer a "rigid-flexible-rigid" structural unit of the network, rather than a simple suspended chain. Finally, the Fe³⁺ provided by the iron salt solution… + Simultaneously, the imine bond coordinates with the nitrogen atom of the imine bond and the oxygen atom of the ortho-methoxy group, directly anchoring the dynamic coordination bond to the dynamic covalent nodes of the network, forming a unique topological structure of "dynamic bonds on dynamic bonds." The imine bond (dynamic covalent) provides the network with rearrangement capability and macroscopic self-repair function, capable of breaking and recombining under thermal or acidic conditions; Fe³ + Coordinate bonds (supramolecular dynamics), acting as "sacrificial bonds," preferentially break and dissipate energy under external forces, endowing the coating with excellent toughness and impact resistance; after the external force is removed, the coordinate bonds can be rapidly reassembled. Imine bonds ensure the overall reconfigurability of the network, while coordinate bonds ensure efficient local energy dissipation.

[0048] The preparation method provided in this application yields an integrated coating material that combines five major functions—reinforcement, toughening, impact resistance, wear resistance, and corrosion protection—into a single layer. This coating material exhibits excellent wear and corrosion resistance as well as intrinsic flame retardant and radiation-resistant properties, and has broad application prospects in extreme environmental protection in fields such as marine engineering, petrochemicals, bridges and tunnels, aerospace, and nuclear industry.

[0049] In step S11: In some embodiments, the molar ratio of the hexafluorocyclotriphosphazene to the vanillin is 1:3. This molar ratio, as described above, favors the trisubstituted reaction of the vanillin with the hexafluorocyclotriphosphazene, resulting in a vanillin group attached to each phosphorus atom while retaining one fluorine atom.

[0050] In some embodiments, step S11 further includes providing a first solvent and an acid-binding agent.

[0051] In some embodiments, the first solvent is selected from one or more of tetrahydrofuran, acetonitrile, dioxane, toluene, and N,N-dimethylformamide.

[0052] In some embodiments, the acid-binding agent is selected from one or more of potassium carbonate, potassium bicarbonate, potassium phosphate, potassium fluoride, and triethylamine. It is understood that an acid-binding agent refers to an alkaline substance that can absorb acid-forming substances in the reaction system, thereby promoting the forward reaction. Therefore, an appropriate amount of acid-binding agent can be selected according to actual needs.

[0053] In some embodiments, the vanillin concentration is 30 g / L to 60 g / L; for example, it can be 30 g / L, 40 g / L, 45 g / L, 57 g / L, or any range between two of the above values. Within the mass concentration range described above, it is beneficial for the vanillin and the hexafluorocyclotriphosphazene to dissolve sufficiently in the first solvent; wherein, the vanillin concentration is the ratio of the mass of the vanillin to the volume of the first solvent.

[0054] In some embodiments, the reaction temperature of the first reaction is 40°C to 80°C, for example, 40°C, 55°C, 60°C, 80°C or any two of the above values; the reaction time of the first reaction is 20h to 40h, for example, 20h, 24h, 33h, 37h, 39h or any two of the above values; under the reaction conditions described above, it is beneficial for the vanillin group in the vanillin to fully replace the fluorine atom in the hexafluorocyclotriphosphazene, thereby increasing the reaction yield.

[0055] In some embodiments, the reaction progress of the first reaction can be monitored by thin layer chromatography (TLC). The developing solvent used in TLC can be a mixed solution of petroleum ether and ethyl acetate at a volume ratio of 3:1.

[0056] In some embodiments, the reaction solution of the first reaction can be subjected to processes such as filtration, concentration, precipitation, vacuum filtration, washing, and drying to obtain the first reactant.

[0057] In some embodiments, the first reactant is a vanillin-based hexafluorocyclotriphosphazene crosslinking agent (FCTP-VA-3), and the structural formula of the first reactant is shown below: .

[0058] In some embodiments, the synthetic route for the formation of the first reactant from the hexafluorocyclotriphosphazene and the vanillin is shown below: .

[0059] In step S12: In some embodiments, step S12 includes: Step S121: Provide 4,4'-diaminodiphenyl ether, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride and a second solvent, mix them, and carry out the second reaction a to obtain the first mixture; Step S122: Provide a dehydrating agent and a first catalyst, mix them with the first mixture, and carry out the second reaction b to obtain the second reactant.

[0060] In step S121: In some embodiments, the mass ratio of the 4,4'-diaminodiphenyl ether to the 3,3',4,4'-benzophenone tetracarboxylic dianhydride is (5~30):(5~50), for example, it can be 5:6, 12:16, 16:24, 19:28, 27:36, or any range between two of the above ratios. Within the mass ratio range described above, the ratio of the 4,4'-diaminodiphenyl ether to the 3,3',4,4'-benzophenone tetracarboxylic dianhydride is suitable, which is beneficial for reducing reaction byproducts and increasing the yield of the second reactant.

[0061] In some embodiments, the second solvent is selected from one or more of N,N-dimethylformamide, tetrahydrofuran, acetonitrile, dioxane, and toluene.

[0062] In some embodiments, the mass concentration of the 4,4'-diaminodiphenyl ether is 60 g / L to 200 g / L; for example, it can be 60 g / L, 120 g / L, 145 g / L, 157 g / L, 180 g / L, or any range between two of the above values. Within the mass concentration range described above, it is beneficial for the 4,4'-diaminodiphenyl ether to dissolve sufficiently in the second solvent; wherein, the mass concentration of the 4,4'-diaminodiphenyl ether is the ratio of the mass of the 4,4'-diaminodiphenyl ether to the volume of the second solvent.

[0063] In some embodiments, the reaction temperature of the second reaction a is 0℃~10℃, for example, it can be 0℃, 1.5℃, 2℃, 5℃, 8℃ or any two of the above values; the reaction time of the second reaction a is 2h~8h, for example, it can be 2h, 4h, 5h, 6.7h, 8h or any two of the above values; under the reaction conditions described above, it is beneficial for the second reaction a to proceed fully.

[0064] In some embodiments, the second solvent may be mixed with the 4,4'-diaminodiphenyl ether first, and then the 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride may be added in batches, making the reaction process more controllable and the reaction more complete.

[0065] In step S122: In some embodiments, the dehydrating agent is selected from one or more of acetic anhydride, propionic anhydride, butyric anhydride, benzoic anhydride, trifluoroacetic anhydride, and dicyclohexylcarbodiimide.

[0066] In some embodiments, the first catalyst is selected from one or more of triethylamine, N,N-diisopropylethylamine, pyridine, 4-dimethylaminopyridine, and tripropylamine.

[0067] In some embodiments, the mass ratio of the dehydrating agent, the first catalyst, and the 4,4'-diaminodiphenyl ether is (10~50):(2~20):(5~30), for example, it can be 10:2:6, 16:4:7.8, 27:5.8:11, 32:8:13, 44:15:24, or any range between two of the above ratios. Within the mass ratio range described above, the appropriate amounts of the dehydrating agent and the first catalyst are beneficial for improving the yield of the second reactant.

[0068] In some embodiments, the reaction temperature of the second reaction b is 30°C to 80°C, for example, it can be 50°C, 45°C, 52°C, 65°C, 78°C or any two of the above values; the reaction time of the second reaction b is 2h to 8h, for example, it can be 2h, 4h, 5h, 6.7h, 8h or any two of the above values; under the reaction conditions described above, it is beneficial for the second reaction b to proceed fully.

[0069] In some embodiments, the reaction solution of the second reaction b can be subjected to precipitation, filtration, washing, drying, or other treatments to obtain the second reactant.

[0070] It is understandable that the product of the second reaction a is polyamic acid. After imidization by the dehydrating agent and the first catalyst, the second reactant is an amino-terminated polyimide precursor (ODA-BTDA type).

[0071] In some embodiments, the structural formula of the second reactant is shown in the figure below: .

[0072] In some embodiments, the synthetic route for the formation of the second reactant from the 4,4'-diaminodiphenyl ether and the 3,3',4,4'-benzophenone tetracarboxylic dianhydride is shown in the figure below: .

[0073] In step S13: In some embodiments, the mass ratio of the hydroxyl-terminated polydimethylsiloxane, the 4,4'-diphenylmethane diisocyanate, and the second reactant is (10~50):(2~15):(10~80), for example, 10:2:14, 16:4.1:24, 19:5:28, 20:5:30, 42:11:64, or any range between two of the above ratios. Within the mass ratio range described above, the appropriate ratio of the hydroxyl-terminated polydimethylsiloxane, the 4,4'-diphenylmethane diisocyanate, and the second reactant is beneficial for reducing reaction byproducts and increasing the yield of the third reactant.

[0074] In some embodiments, step S13 includes: Step S131: Provide hydroxyl-terminated polydimethylsiloxane, 4,4'-diphenylmethane diisocyanate, a third solvent and a second catalyst, mix them, and carry out the third reaction a to obtain a second mixture; Step S132: Mix the second mixture with the second reactant to carry out the third reaction b, and obtain the third reactant.

[0075] In step S131: In some embodiments, the third solvent is selected from one or more of toluene, N,N-dimethylformamide, tetrahydrofuran, acetonitrile, and dioxane.

[0076] In some embodiments, the mass concentration of the hydroxyl-terminated polydimethylsiloxane is 300 g / L to 600 g / L; for example, it can be 300 g / L, 400 g / L, 445 g / L, 557 g / L, 600 g / L, or any range between two of the above values. Within the mass concentration range described above, it is beneficial for the hydroxyl-terminated polydimethylsiloxane to dissolve sufficiently in the third solvent; wherein, the mass concentration of the hydroxyl-terminated polydimethylsiloxane is the ratio of the mass of the hydroxyl-terminated polydimethylsiloxane to the volume of the third solvent.

[0077] In some embodiments, the second catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate, stannous isooctanoate, dibutyltin diacetate, and dioctyltin dilaurate.

[0078] In some embodiments, the reaction temperature of the third reaction a is 60°C to 100°C, for example, 60°C, 75°C, 82°C, 87°C, 95°C or any two of the above values; the reaction time of the third reaction a is 2h to 8h, for example, 2h, 4h, 5h, 7h, 8h or any two of the above values; under the reaction conditions described above, it is beneficial for the hydroxyl-terminated polydimethylsiloxane and the 4,4'-diphenylmethane diisocyanate to fully polymerize.

[0079] In some embodiments, Fourier transform infrared spectroscopy (FT-IR monitoring) can be used to monitor 2270 cm⁻¹. - The characteristic peak of -NCO is observed at ¹. Once the peak intensity stabilizes, the third reaction a is determined to have stopped.

[0080] In some embodiments, the second mixture contains an intermediate prepolymer, which is an NCO-terminated polydimethylsiloxane prepolymer (PDMS-NCO), the structural formula of which is shown in the figure below: ; Where m is an integer between 20 and 100.

[0081] In step S132: In some embodiments, the reaction temperature of the third reaction b is 40°C to 80°C, for example, 40°C, 55°C, 60°C, 75°C, 80°C or any two of the above values; the reaction time of the third reaction b is 2h to 8h, for example, 2h, 4h, 5h, 7h, 8h or any two of the above values; under the reaction conditions described above, it is beneficial for the intermediate prepolymer contained in the second mixture to fully polymerize with the second reactant to obtain the third reactant.

[0082] In some embodiments, the reaction solution of the third reaction b can be subjected to operations such as precipitation, filtration, washing, and drying to obtain the third reactant.

[0083] In some embodiments, the third reactant is an amino-terminated PI-PDMS-PI (polyimide-polydimethylsiloxane-polyimide) triblock polymer, the structural formula of which is shown in the figure below: ; Where m is an integer between 20 and 100.

[0084] In step S14: In some embodiments, the mass ratio of the iron salt, the first reactant, and the third reactant is (2~10):(5~30):(80~400), for example, 3:10:100, 5:14:180, 7:22:210, 8:25:330, 9:27:380, or any range between two of the above ratios. Within the mass ratio range described above, the iron salt provides Fe³⁺. + It can fully coordinate with the imine provided by the third reactant and the o-methoxy group provided by the first reactant.

[0085] In some embodiments, the iron salt may be selected from one or more of ferric acetylacetone, ferric chloride, ferric nitrate, ferric sulfate, and ferric stearate.

[0086] In some embodiments, the first reactant can be dissolved in a fourth solvent first, then the third reactant can be added and stirred to obtain an intermediate mixture; the iron salt can be dissolved in a fifth solvent to obtain an iron salt solution, and the iron salt solvent can be added dropwise to the intermediate mixture.

[0087] The fourth solvent may be selected from one or more of tetrahydrofuran, acetonitrile, dioxane, toluene, and N,N-dimethylformamide.

[0088] The fifth solvent may be selected from one or more of ethanol, methanol, isopropanol, n-propanol, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether.

[0089] In some embodiments, the curing temperature is 20°C to 40°C, for example, 20°C, 25°C, 30°C, 40°C or any two of the above values; the curing time is 5 days to 10 days, for example, 5 days, 7 days, 9 days, 10 days or any two of the above values; under the curing conditions described above, it is beneficial for the full formation of dynamic covalent bonds and coordination bonds, making the crosslinked network uniform and dense, while avoiding the damage of high temperature to the coating structure and dynamic properties, and obtaining a coating material with stable comprehensive performance.

[0090] Secondly, this application provides an integrated coating material for enhanced toughness, impact resistance, wear resistance, and corrosion protection, wherein the integrated coating material is prepared by the above-described preparation method.

[0091] The integrated coating material for enhanced toughness, impact resistance, wear resistance, and corrosion protection provided in this application integrates five major functions—reinforcement, toughening, impact resistance, wear resistance, and corrosion protection—into a single layer coating. It possesses excellent wear resistance and corrosion protection properties, as well as intrinsic flame retardant and radiation-resistant characteristics, and has broad application prospects in extreme environmental protection in fields such as marine engineering, petrochemicals, bridges and tunnels, aerospace, and nuclear industry.

[0092] The present application will be specifically described below through specific embodiments. The following embodiments are only some embodiments of the present application and are not intended to limit the present application.

[0093] Example 1

[0094] This embodiment provides an integrated coating material for enhanced toughness, impact resistance, wear resistance, and corrosion protection. The preparation method of this integrated coating material includes the following steps: Step 1: Under dry nitrogen protection, add 2.85 g of hexafluorocyclotriphosphazene (FCCP), 4.56 g of vanillin, 4.14 g of anhydrous potassium carbonate (acid-binding agent), and 100 mL of anhydrous THF to a 250 mL three-necked flask. Heat to 65 °C with stirring and react for 24 hours; monitor the reaction progress by TLC (developing solvent is a mixture of petroleum ether and ethyl acetate in a volume ratio of 3:1). After the reaction is complete, cool to room temperature, filter to remove inorganic salts, and concentrate the filtrate under reduced pressure. Pour the concentrate into 200 mL of anhydrous ethanol, and a pale yellow precipitate will form. Filter under vacuum, wash the filter cake three times with ethanol, and dry under vacuum at 60 °C for 24 hours to obtain a pale yellow powder product, which is the vanillin trisubstituted hexafluorocyclotriphosphazene crosslinking agent (FCTP-VA-3), i.e., the first reactant; Step 2: Under dry nitrogen protection, add 12.01 g of 4,4'-diaminodiphenyl ether (ODA) and 100 mL of anhydrous N,N-dimethylformamide (DMF) to a 500 mL four-necked flask and stir to dissolve. Cool the system to 2 °C and add 16.11 g of 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride (BTDA) in portions, controlling the temperature not to exceed 10 °C. After the addition is complete, react at 2 °C for 4 hours to obtain a polyamic acid (PAA) solution. Then, add 32.4 g of acetic anhydride and 7.26 g of triethylamine sequentially, and heat to 50 °C for 6 hours to carry out chemical imidization. After the reaction is complete, slowly add the reaction solution dropwise to 500 mL of anhydrous ethanol to precipitate, filter, wash the filter cake with ethanol and water, and dry under vacuum at 60 °C for 24 hours to obtain a pale yellow powdery terminal amino polyimide precursor, i.e., the second reactant. Step 3: Under a dry nitrogen atmosphere, add 20.0 g of hydroxyl-terminated PDMS and 50 mL of anhydrous toluene to the reaction flask and stir to dissolve. Add 5.0 g of MDI (4,4'-diphenylmethane diisocyanate) and 2 drops of DBTDL (dibutyltin dilaurate), and heat to 80 °C for 4 hours. Monitor the reaction temperature at 2270 cm⁻¹ using FT-IR. -The -NCO characteristic peak was observed at ¹, and the reaction was stopped once the peak intensity stabilized. Toluene was removed by vacuum distillation to obtain the NCO-terminated PDMS prepolymer (PDMS-NCO). PDMS-NCO was dissolved in 30 mL of anhydrous DMF and slowly added dropwise to a DMF solution of 30.0 g of polyimide precursor (i.e., the second reactant), controlling the dropping rate to keep the temperature below 40 °C. After the addition was complete, the temperature was raised to 60 °C and the reaction was carried out for 6 hours. The reaction was stopped once the -NCO peak completely disappeared as monitored by FT-IR. The reaction solution was poured into ethanol to precipitate, filtered, and the filter cake was washed three times with ethanol and dried under vacuum at 60 °C for 24 hours to obtain the amino-terminated PI-PDMS-PI triblock polymer, i.e., the third reactant. Step 4: Dissolve 10 parts by mass of FCTP-VA-3 (i.e., the first reactant) in 20 parts by mass of anhydrous DMF, add 100 parts by mass of amino-terminated PI-PDMS-PI triblock polymer (i.e., the third reactant), and stir at room temperature for 30 minutes until completely dissolved; dissolve 1.5 parts by mass of acetylacetone iron in 5 parts by mass of anhydrous ethanol, and slowly add it dropwise to the above mixture, and stir at room temperature for 2 hours to obtain a homogeneous, dark reddish-brown coating slurry; apply the above slurry to a cleaned and polished Q235 steel plate (150mm×70mm×2mm) using a scraper, control the wet film thickness at 200μm, and cure for 7 days at 25℃ and 50% relative humidity to obtain a coating material with a dry film thickness of 50μm.

[0095] Example 2

[0096] This embodiment is basically the same as Embodiment 1, except that the amount of acetylacetone iron used in step 4 is 3 parts by mass.

[0097] Example 3

[0098] This embodiment is basically the same as Embodiment 1, except that the amount of iron acetylacetone used in step 4 is 4.5 parts by mass.

[0099] Example 4

[0100] This embodiment is basically the same as embodiment 1, except that in step 4, the amount of acetylacetone iron is 3 parts by mass and the amount of FCTP-VA-3 is 8 parts by mass.

[0101] Example 5

[0102] This embodiment is basically the same as embodiment 1, except that in step 4, the amount of acetylacetone iron is 3 parts by mass and the amount of FCTP-VA-3 is 12 parts by mass.

[0103] Example 6

[0104] This embodiment is basically the same as Embodiment 1, except that acetylacetone iron is not added in step 4.

[0105] Comparative Example 1

[0106] This embodiment is basically the same as Embodiment 1, except that in step 4, acetylacetone iron is not added, and 4.9 parts by mass of HDI trimer (hexamethylene diisocyanate trimer) is used to replace 10 parts by mass of FCTP-VA-3 to form an irreversible urea bond (non-dynamic covalent bond) cross-linking network.

[0107] Comparative Example 2

[0108] This embodiment is basically the same as that of embodiment 1, except that in step 4, 100 parts by mass of terminal amino PDMS are used to replace 100 parts by mass of terminal amino PI-PDMS-PI triblock polymer.

[0109] Comparative Example 3

[0110] This embodiment is basically the same as that of Embodiment 1, except that in step 4, 70 parts by mass of polyimide homopolymer and 30 parts by mass of terminal amino PDMS are used to replace 100 parts by mass of terminal amino PI-PDMS-PI triblock polymer.

[0111] The coating materials provided in Examples 1-6 and Comparative Examples 1-3 were used to test mechanical properties, hydrophobicity, impact resistance, self-healing properties, interfacial electrical properties, and abrasion resistance. The test results are shown in Table 1.

[0112] The tensile strength / elongation at break test was performed in accordance with standard GB / T 2567-2021. The specific operation was as follows: the coating was poured into a polytetrafluoroethylene mold, and after curing, it was cut into a type I dumbbell-shaped specimen (gauge length 25mm, width 6mm, thickness 2mm). The specimen was then subjected to tensile testing using a universal testing machine at a tensile rate of 10mm / min.

[0113] The flexural modulus test was performed in accordance with standard GB / T 2567-2021. The specific operation was as follows: the coating was poured into a polytetrafluoroethylene mold, and after curing, it was cut into rectangular strip samples (80mm×10mm×4mm). The test was performed using the three-point bending method, where the span was 64mm and the indentation rate was 2 mm / min.

[0114] The adhesion (pull-off test) shall be performed in accordance with GB / T 5210-2006. The specific operation is as follows: a 20mm diameter aluminum ingot is bonded to the coating surface, cured with adhesive for 24 hours, and tested with an adhesion tester. The pull-off rate is 1 MPa / s.

[0115] Impact resistance shall be performed in accordance with GB / T 1732-2020. The specific operation is as follows: Coating the steel plate with the coating material, dropping a 1kg hammer freely from different heights, and recording the maximum height (cm) from which the coating does not crack.

[0116] The wear resistance shall be performed in accordance with GB / T 1768-2006. The specific operation is as follows: use a Taber abrasion tester, select a CS-10 grinding wheel, and conduct the test under a 1000g load condition; after 1000 revolutions of wear, calculate the wear loss (unit: mg) by weighing the mass change.

[0117] The pencil hardness shall be determined in accordance with GB / T 6739-2006. The specific operation is as follows: scratch the coating surface with a pencil from hardest to softest, and record the highest pencil hardness that does not scratch the coating.

[0118] The water contact angle shall be performed in accordance with GB / T 30693-2014. The specific operation is as follows: using a contact angle measuring instrument, 5 μL of deionized water is added to the coating surface, and 5 points are measured for each sample and the average value is taken.

[0119] Electrochemical impedance spectroscopy was performed using an electrochemical workstation. The tests were conducted in a 3.5% NaCl solution using a three-electrode system, with a frequency range of 10 Hz. 5 ~10 - 2Hz, the amplitude of the sinusoidal excitation signal is 10mV.

[0120] The limiting oxygen index was performed in accordance with GB / T 2406.2-2009. The specific operation was as follows: using an oxygen index tester, the combustion behavior of the coated sample in an oxygen-nitrogen mixed atmosphere was tested, and the minimum oxygen concentration (%) required to maintain stable combustion of the sample was recorded.

[0121] The self-healing efficiency was evaluated using a laboratory-made method. Scratches approximately 30 μm wide were prepared on the sample surface using a blade. After heat treatment at 60 °C for 24 h, the change in scratch width was observed under a microscope, and the scratch width recovery rate was calculated.

[0122] Table 1

[0123] The test data above shows that: Comparing Example 2 (complete dual dynamic network) and Example 6 (without Fe³)... + The tensile strength of the control group (containing only imine bonds) and Comparative Example 1 (containing no dynamic bonds) were 66.5 MPa vs 53.5 MPa vs 45.2 MPa (an improvement of 24-47%); the elongation at break were 44.5% vs 23.1% vs 12.5% ​​(an improvement of 93-256%); the impact resistance was 78 cm vs 41 cm vs 28 cm (an improvement of 90-179%); and the self-healing efficiency was 89.2% vs 0% vs 0%.

[0124] Data shows that while the imine bond network (Example 6) has a certain reinforcing effect (53.5 MPa), its toughness is insufficient (23.1%) and its self-healing function is lacking (0%), proving that a single dynamic covalent bond cannot achieve efficient energy dissipation. The network without dynamic bonds (Comparative Example 1) shows a complete deterioration in all properties, with a strength of only 45.2 MPa and an elongation of only 12.5%, demonstrating the decisive role of the dynamic network in overall performance. Only the dual dynamic network (Example 2) achieves a strength of 66.5 MPa (47% higher than Comparative Example 1), an elongation of 44.5% (256% higher than Comparative Example 1), an impact resistance of 78 cm (179% higher than Comparative Example 1), and a self-healing efficiency of 89.2%. The data demonstrates the interaction between imine bonds and Fe³⁺. + The synergistic effect of coordinate bonds, rather than a simple additive effect.

[0125] Meanwhile, compared with Comparative Example 2 (PI-PDMS-PI triblock), Comparative Example 2 (PI hard segment missing), and Comparative Example 3 (physical blend without blocks), the tensile strengths were 66.5 MPa vs 42.3 MPa vs 39.6 MPa, respectively; the flexural modulus were 2450 MPa vs 1310 MPa vs 1180 MPa, respectively; the abrasion resistances were 14.8 mg vs 38.5 mg vs 40.2 mg, respectively; and the electrochemical impedances were 5.8 × 10⁻⁶. 9 (Ω·cm²) vs 1.1×10 7 (Ω·cm²) vs 8.5×10 6 (Ω·cm²).

[0126] Data shows that the absence of PI hard segments (Comparative Example 2) leads to a sharp decline in strength and corrosion resistance; the physical blending of the non-block structure (Comparative Example 3) also results in performance degradation. This proves that the PI-PDMS-PI triblock structure constructed through chemical bonds is the basis for achieving intrinsic reinforcement, wear resistance, and corrosion resistance, and cannot be replaced by physical blending.

[0127] Furthermore, the design of this application, which employs hexafluorocyclotriphosphazene and retains the CF bond, offers significant advantages. Example 2 shows a wear rate of only 14.8 mg / 1000 r, significantly better than the comparative system using hexafluorocyclotriphosphazene (typically >25 mg / 1000 r). Example 2 achieves a water contact angle of 115°, higher than similar dynamic network coatings (typically <100°), demonstrating that the retained CF bond effectively reduces surface energy. Example 2 also achieves a limiting oxygen index of 30.5%, better than similar systems in the prior art (approximately 28%), proving that the PF bond synergistically contributes to flame retardancy. While Comparative Example 2 introduces Fe³⁺... +However, because FCTP-VA is replaced by a common dialdehyde, it cannot form an effective secondary coordination network and lacks CF bonds, resulting in a wear resistance (38.5 mg) that is far lower than the 14.8 mg of Example 2. This demonstrates the originality and necessity of the FCTP-VA trifunctional molecule design of "aldehyde group + ortho-methoxy group + CF bond".

[0128] In summary, this application utilizes the "one substance, three functions" molecular design (aldehyde group + o-methoxy group + CF bond) of vanillin-based hexafluorocyclotriphosphazene crosslinking agent, the "rigid-flexible" segment design of PI-PDMS-PI triblock polymer, and the imine bond -Fe³ + The synergistic design of the "dual dynamic network" of coordinate bonds enables the resulting coating material to integrate reinforcement, toughening, impact resistance, wear resistance, and corrosion resistance, exhibiting excellent wear and corrosion resistance as well as intrinsic flame retardant and radiation-resistant properties.

[0129] The preparation method provided in this application yields an integrated coating material that combines five major functions—reinforcement, toughening, impact resistance, wear resistance, and corrosion protection—into a single layer. This coating material exhibits excellent wear and corrosion resistance as well as intrinsic flame retardant and radiation-resistant properties, and has broad application prospects in extreme environmental protection in fields such as marine engineering, petrochemicals, bridges and tunnels, aerospace, and nuclear industry.

[0130] The technical solutions provided by the embodiments of this application have been described in detail above. Specific examples have been used to illustrate the principles and implementation methods of this application. The description of the above embodiments is only for the purpose of helping to understand the method and core ideas of this application. At the same time, for those skilled in the art, there will be changes in the specific implementation methods and application scope based on the ideas of this application. Therefore, the content of this specification should not be construed as a limitation of this application.

Claims

1. A method for preparing an integrated coating material that is reinforced, toughened, impact-resistant, wear-resistant, and corrosion-resistant, characterized in that, Includes the following steps: Step S11: Provide hexafluorocyclotriphosphazene and vanillin, mix them, and carry out the first reaction to obtain the first reactant; Step S12: Provide 4,4'-diaminodiphenyl ether and 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, mix them, and carry out the second reaction to obtain the second reactant; Step S13: Provide hydroxyl-terminated polydimethylsiloxane and 4,4'-diphenylmethane diisocyanate, mix with the second reactant, and carry out the third reaction to obtain the third reactant; Step S14: Provide iron salt, mix it with the first reactant and the third reactant, and perform a curing treatment to obtain a coating material.

2. The preparation method according to claim 1, characterized in that, In step S11: The molar ratio of the hexafluorocyclotriphosphazene to the vanillin is 1:3; The mass concentration of vanillin is 30 g / L to 60 g / L; The reaction temperature of the first reaction is 40℃~80℃; the reaction time of the first reaction is 20h~40h; Step S11 further includes: providing a first solvent and an acid-binding agent; wherein the first solvent is selected from one or more of tetrahydrofuran, acetonitrile, dioxane, toluene, and N,N-dimethylformamide; and the acid-binding agent is selected from one or more of potassium carbonate, potassium bicarbonate, potassium phosphate, potassium fluoride, and triethylamine.

3. The preparation method according to claim 1, characterized in that, Step S12 includes: providing 4,4'-diaminodiphenyl ether, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, and a second solvent, mixing them, and carrying out a second reaction a to obtain a first mixture; providing a dehydrating agent and a first catalyst, mixing them with the first mixture, and carrying out a second reaction b to obtain a second reactant; wherein... The second solvent is selected from one or more of N,N-dimethylformamide, tetrahydrofuran, acetonitrile, dioxane, and toluene; The dehydrating agent is selected from one or more of acetic anhydride, propionic anhydride, butyric anhydride, benzoic anhydride, trifluoroacetic anhydride, and dicyclohexylcarbodiimide; The first catalyst is selected from one or more of triethylamine, N,N-diisopropylethylamine, pyridine, 4-dimethylaminopyridine, and tripropylamine.

4. The preparation method according to claim 3, characterized in that, The mass ratio of the 4,4'-diaminodiphenyl ether to the 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride is (5~30):(5~50); The mass concentration of the 4,4'-diaminodiphenyl ether is 60 g / L to 200 g / L; The mass ratio of the dehydrating agent, the first catalyst and the 4,4'-diaminodiphenyl ether is (10~50):(2~20):(5~30); The reaction temperature of the second reaction a is 0℃~10℃; the reaction time of the second reaction a is 2h~8h; The reaction temperature of the second reaction b is 30℃~80℃; the reaction time of the second reaction b is 2h~8h.

5. The preparation method according to claim 1, characterized in that, Step S13 includes: providing hydroxyl-terminated polydimethylsiloxane, 4,4'-diphenylmethane diisocyanate, a third solvent, and a second catalyst; mixing them to carry out a third reaction a to obtain a second mixture; mixing the second mixture with the second reactant to carry out a third reaction b to obtain a third reactant; wherein... The third solvent is selected from one or more of toluene, N,N-dimethylformamide, tetrahydrofuran, acetonitrile, and dioxane; The second catalyst is selected from one or more of dibutyltin dilaurate, stannous octoate, stannous isooctanoate, dibutyltin diacetate, and dioctyltin dilaurate.

6. The preparation method according to claim 5, characterized in that, The mass ratio of the hydroxyl-terminated polydimethylsiloxane, the 4,4'-diphenylmethane diisocyanate and the second reactant is (10~50):(2~15):(10~80); The mass concentration of the hydroxyl-terminated polydimethylsiloxane is 300 g / L to 600 g / L; The reaction temperature of the third reaction a is 60℃~100℃; the reaction time of the third reaction a is 2h~8h; The reaction temperature of the third reaction b is 40℃~80℃; the reaction time of the third reaction b is 2h~8h.

7. The preparation method according to claim 1, characterized in that, The provision of the iron salt, mixed with the first reactant and the third reactant, comprises: dissolving the first reactant in a fourth solvent, then adding the third reactant and stirring to obtain an intermediate mixture; dissolving the iron salt in a fifth solvent to obtain an iron salt solution, and adding the iron salt solvent dropwise to the intermediate mixture; wherein... The fourth solvent is selected from one or more of tetrahydrofuran, acetonitrile, dioxane, toluene, and N,N-dimethylformamide; The fifth solvent is selected from one or more of ethanol, methanol, isopropanol, n-propanol, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether; The iron salt is selected from one or more of ferric acetylacetone, ferric chloride, ferric nitrate, ferric sulfate, and ferric stearate.

8. The preparation method according to claim 1 or 7, characterized in that, The mass ratio of the iron salt, the first reactant, and the third reactant is (2~10):(5~30):(80~400). The curing temperature is 20℃~40℃; the curing time is 5 days~10 days.

9. The preparation method according to claim 1, characterized in that, The structural formula of the first reactant is shown below: ; The structural formula of the second reactant is shown below: ; The structural formula of the third reactant is shown below: m is an integer between 20 and 100.

10. A reinforced, toughened, impact-resistant, wear-resistant, and corrosion-resistant integrated coating material, characterized in that, The integrated coating material for enhanced toughness, impact resistance, wear resistance, and corrosion protection is prepared by any of the preparation methods described in claims 1-9.

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