An oxidation-resistant, antibacterial, large-flux reverse osmosis membrane and a preparation method and application thereof

Abstract

The application discloses an oxidation-resistant, antibacterial and large-flux reverse osmosis membrane and a preparation method and application thereof. The reverse osmosis membrane comprises a polymer base film and a polyamide functional layer formed on the polymer base film, and is characterized in that the surface of the polyamide functional layer comprises a blend of benzene series containing a mercapto group and a carboxylic acid group, benzene series containing a triazole group, a sulfonate group and a hydroxyl group, and benzene series containing a sulfide bond, a sulfonate group and a triazole group. The reverse osmosis membrane provided by the application has the advantages of high oxidation resistance, high antibacterial property and the like on the basis of maintaining a high desalination rate and water flux, and has a wide application prospect in the water treatment field such as wastewater reuse and industrial water supply.

Description

Technical Field

[0001] This invention belongs to the field of water treatment materials technology, specifically relating to an oxidation-resistant, antibacterial, high-flux reverse osmosis membrane, its preparation method, and its application. Background Technology

[0002] With the rapid development of global urbanization and industrialization, existing freshwater resources can no longer meet the needs of social and economic development, and the global water scarcity problem has attracted much attention. Compared with traditional methods, reverse osmosis has irreplaceable advantages such as no phase change, small footprint, low cost, and no secondary pollution, and has been widely used in various fields such as pharmaceuticals, medicine, food, beverages, wine, chemicals, electronics, semiconductors, and environmental protection.

[0003] Currently, most reverse osmosis membranes on the market are aromatic polyamide composite membranes. A functional layer is formed on the surface of a polysulfone-based membrane through an interfacial condensation reaction between m-phenylenediamine and trimesoyl chloride. However, in practical applications, they are still limited by a series of problems. Due to varying water quality conditions, microbial fouling is extremely common, severely hindering the development of the membrane-based water treatment industry. The most common method to inhibit membrane biofouling is to pretreat the feed water by adding an appropriate amount of active chlorine to kill bacteria. However, the polyamide structure itself is not resistant to oxidation and is easily attacked and degraded by active chlorine. Although there are measures to reduce oxidizing chlorine, the removal rate cannot reach 100%, and the risk of irreversible damage to the membrane by residual chlorine still exists, seriously affecting the stability and lifespan of membrane operation and increasing operating costs. Therefore, improving the membrane's oxidation resistance while effectively controlling biofouling is extremely important.

[0004] To address the aforementioned issues, various methods have been disclosed for preparing oxidation-resistant and antibacterial reverse osmosis membranes. Patent CN115463552A improves the chlorine resistance of the membrane by setting a sulfonated polyethersulfone chlorine-resistant layer on the separation layer surface and reduces the membrane roughness and increases its hydrophilicity by polyvinyl alcohol hybrid crosslinking, thereby enhancing the membrane's antifouling ability. CN115430300 discloses a method for modifying a polyamide membrane with GO graphene oxide, which reduces the pore size, porosity, hydrophilicity, and surface roughness of the GO-modified polyamide membrane, decreasing the active sites in contact with chlorine and thus enhancing the chlorine resistance and antifouling performance of the reverse osmosis composite membrane. While the above patents have achieved some research results in oxidation resistance and antibacterial properties, they still fail to simultaneously achieve both without sacrificing basic membrane performance such as flux. However, in the field application environment of membranes, microbial contamination and residual chlorine are unavoidable. Therefore, there is an urgent need to develop an oxidation-resistant, antibacterial, high-flux reverse osmosis membrane. Summary of the Invention

[0005] To address the aforementioned problems in the existing technology, the present invention aims to provide an oxidation-resistant, antibacterial, and high-flux reverse osmosis membrane that can simultaneously achieve oxidation resistance and antibacterial properties without sacrificing flux and desalination rate.

[0006] Another object of the present invention is to provide a method for preparing such an oxidation-resistant, antibacterial, high-flux reverse osmosis membrane.

[0007] Another object of the present invention is to provide applications for this oxidation-resistant, antibacterial, high-flux reverse osmosis membrane.

[0008] To achieve the above-mentioned objectives, the present invention adopts the following technical solution:

[0009] On one hand, the present invention provides an oxidation-resistant, antibacterial, high-flux reverse osmosis membrane, comprising a polymer base membrane and a polyamide functional layer formed on the polymer base membrane, characterized in that the surface of the polyamide functional layer comprises a blend of benzene compounds containing thiol groups and carboxylic acid groups, and benzene compounds containing triazole groups, sulfonate groups and hydroxyl groups;

[0010] Preferably, the blend on the surface of the polyamide functional layer further contains benzene compounds containing sulfide bonds, sulfonate groups, and triazole groups.

[0011] In one specific embodiment, the benzene compound containing a thiol group and a carboxylic acid group is a benzene compound containing at least one thiol group and at least one carboxyl group, preferably a benzene compound containing one thiol group and one carboxyl group;

[0012] Preferably, the benzene compound containing thiol and carboxylic acid groups is selected from one or more of 3-mercaptobenzoic acid, 4-mercaptobiphenyl-4-carboxylic acid, 4-amino-3-mercaptobenzoic acid, and 5-fluoro-2-mercaptobenzoic acid.

[0013] In one specific embodiment, the benzene compound containing a triazole group, a sulfonate group, and a hydroxyl group is a benzene compound containing at least one triazole group, at least one sulfonate group, and at least one hydroxyl group, preferably a benzene compound containing one triazole group, one sulfonate group, and one hydroxyl group;

[0014] Preferably, the benzene compound containing a triazole group, a sulfonate group, and a hydroxyl group is selected from one or more of 2-(1H-1,2,4-triazol-1-yl)-4-sulfonylbenzyl alcohol, 3-(1H-1,2,4-triazol-1-yl)-5-sulfonylbenzyl alcohol, and 4-(1H-1,2,4-triazol-1-yl)-6-sulfonylbenzyl alcohol.

[0015] In one specific embodiment, the benzene compound containing thioether bonds, sulfonate groups, and triazole groups is a product obtained by reacting a benzene compound containing thiol groups and carboxylic acid groups with a benzene compound containing triazole groups, sulfonate groups, and hydroxyl groups. In this embodiment, the surface of the polyamide functional layer includes benzene compounds containing thiol groups and carboxylic acid groups, benzene compounds containing triazole groups, sulfonate groups, and hydroxyl groups, and blends of benzene compounds containing thioether bonds, sulfonate groups, and triazole groups.

[0016] In one specific embodiment, the polyamide functional layer is an aromatic polyamide with a three-dimensional network structure, which is formed by interfacial polymerization of an aqueous solution with m-phenylenediamine as the monomer and an organic solution with trimesoyl chloride as the monomer.

[0017] In one specific embodiment, the polymer base film is selected from any one of polysulfone base film, polyethersulfone base film, and polyethylene base film, and is preferably a polysulfone base film supported by polyester nonwoven fabric.

[0018] On the other hand, the present invention provides a method for preparing the aforementioned oxidation-resistant, antibacterial, high-flux reverse osmosis membrane, comprising the following steps:

[0019] 1) Contact the polymer-based membrane with an aqueous solution containing m-phenylenediamine monomer, and then remove excess aqueous solution from the surface of the polymer-based membrane;

[0020] 2) Then, the polymer base membrane treated in step 1) is brought into contact with an oil phase organic solution containing trimesoyl chloride monomer, so that m-phenylenediamine and trimesoyl chloride undergo interfacial polymerization on the surface of the polymer base membrane. The excess organic solution is poured off and the residual organic solution on the surface of the polymer base membrane is removed. Then, after washing with water and drying, a polyamide reverse osmosis membrane is formed on the surface of the polymer base membrane.

[0021] 3) The prepared solution containing benzene compounds with thiol and carboxylic acid groups and a carboxylic acid crosslinking agent is brought into contact with the polyamide reverse osmosis membrane formed in step 2), and then the excess solution on the surface is removed. Then, heat treatment, water washing, and secondary heat treatment are performed to graft benzene compounds with thiol and carboxylic acid groups onto the surface of the polyamide reverse osmosis membrane.

[0022] 4) The prepared solution of benzene compounds containing triazole groups, sulfonate groups, and hydroxyl groups and a ruthenium (Ru) chelate catalyst is brought into contact with the polyamide reverse osmosis membrane treated in step 3), so that the benzene compounds containing thiol groups and carboxylic acid groups react with the benzene compounds containing triazole groups, sulfonate groups, and hydroxyl groups. Then, excess solution on the surface is removed, followed by heat treatment, water washing, and a second heat treatment. The benzene compounds containing triazole groups, sulfonate groups, and hydroxyl groups are grafted onto the surface of the polyamide reverse osmosis membrane, while simultaneously generating benzene compounds containing sulfide bonds, sulfonate groups, and triazole groups, to obtain the oxidation-resistant, antibacterial, high-flux reverse osmosis membrane.

[0023] In one specific implementation, the aqueous solution containing m-phenylenediamine monomer in step 1) is an aqueous solution of m-phenylenediamine, wherein the concentration of m-phenylenediamine is 1.5 to 3.5 wt%.

[0024] In one specific implementation, the oil-phase organic solution containing trimesoyl chloride monomer in step 2) is a mixed solution of trimesoyl chloride and an organic solvent, wherein the concentration of trimesoyl chloride is 0.08 to 0.2 wt%.

[0025] Preferably, the organic solvent is one or more of aliphatic alkanes, aromatic alkanes, and haloalkanes, preferably aliphatic alkanes, and more preferably one or more of n-decane, isopar G, isopar L, and isopar H isoalkanes.

[0026] In one specific embodiment, the solution containing the benzene compound with thiol and carboxylic acid groups and the carboxylic acid crosslinking agent in step 3) is an aqueous solution of the benzene compound with thiol and carboxylic acid groups and the carboxylic acid crosslinking agent, wherein the concentration of the benzene compound with thiol and carboxylic acid groups is 0.01-1 wt%, preferably 0.1-0.5 wt%, and the concentration of the carboxylic acid crosslinking agent is 0.01-1%.

[0027] Preferably, the carboxylic acid crosslinking agent is selected from one or more of BOP carter condensing agent, AOP condensing agent, and HBTU peptide synthesis condensing agent.

[0028] In one specific embodiment, the solution of the benzene series containing triazole groups, sulfonate groups, and hydroxyl groups and the ruthenium-containing chelate catalyst in step 4) is an aqueous solution of the benzene series containing triazole groups, sulfonate groups, and hydroxyl groups and the ruthenium-containing chelate catalyst in an organic solvent, wherein the concentration of the benzene series containing triazole groups, sulfonate groups, and hydroxyl groups is 0.05–2 wt%, preferably 0.1–1.0 wt%; and the concentration of the ruthenium-containing chelate catalyst is 0.5–1 wt%.

[0029] Preferably, the ruthenium-containing chelate catalyst is selected from one or more of xanthracene-Ru, PNP-Ru, and PNNH-Ru.

[0030] In one specific embodiment, the contact time between the polymer base film and the aqueous solution containing m-phenylenediamine monomer in step 1), and the contact time between the polymer base film and the oil-phase organic solution containing trimesoyl chloride monomer in step 2), are both 10 to 300 s, preferably 30 to 60 s.

[0031] In one specific embodiment, the contact time between the polyamide reverse osmosis membrane and the solution containing benzene compounds with thiol and carboxylic acid groups and a carboxylic acid crosslinking agent in step 3) is 10–1200 s, preferably 30–300 s; and the contact time between the polyamide reverse osmosis membrane and the solution containing benzene compounds with triazole groups, sulfonate groups and hydroxyl groups and a ruthenium-containing chelate catalyst in step 4) is 10–1200 s, preferably 30–300 s.

[0032] In one specific implementation, in steps 3) and 4), the heat treatment is performed at a temperature of 60–100°C, preferably 80–90°C, for a time of 0.5–10 min, preferably 1–3 min.

[0033] The secondary heat treatment is performed at a temperature of 60–100°C, preferably 80–90°C, for a time of 0.5–10 min, preferably 3–6 min.

[0034] In one specific implementation, the water washing in step 2) is at a temperature of 60–90°C; the water washing in step 3) is at a temperature of 60–90°C; and the water washing in step 4) is at a temperature of 60–90°C.

[0035] In another aspect, the present invention provides the application of the aforementioned oxidation-resistant, antibacterial, high-flux reverse osmosis membrane or the oxidation-resistant, antibacterial, high-flux reverse osmosis membrane prepared by the aforementioned preparation method in water treatment components or water treatment methods.

[0036] Compared with the prior art, the beneficial effects of the present invention are reflected in:

[0037] 1) Based on polymer-based membranes and polyamide reverse osmosis membranes, this invention modifies the membrane surface with benzene compounds containing thiol and carboxylic acid groups, and benzene compounds containing triazole groups, sulfonate groups and hydroxyl groups, to obtain a reverse osmosis membrane that combines oxidation resistance and antibacterial properties without sacrificing flux and desalination rate.

[0038] 2) This invention employs a multi-step post-processing procedure to chemically graft benzene compounds containing thiol and carboxylic acid groups, as well as benzene compounds containing triazole, sulfonate, and hydroxyl groups, onto the surface of a polyamide layer, partially forming a benzene compound structure containing thioether bonds, sulfonate groups, and triazole groups. The triazole structure possesses unique antibacterial properties, the sulfonate groups exhibit strong hydrophilicity, and the thioether bonds obtained through the reaction effectively improve the chlorine resistance of the polyamide membrane. Due to the low bond energy of the thioether bonds, the antioxidant active groups preferentially react with oxidizing agents after the membrane is attacked, thereby protecting the amide bonds of the main structure of the polyamide layer and enhancing the antioxidant properties of the polyamide reverse osmosis membrane layer.

[0039] 3) The oxidation-resistant, antibacterial, and high-flux reverse osmosis membrane of the present invention can extend the service life of the membrane to a certain extent and reduce the membrane wear cost. The method is simple to operate, can be industrialized, and is easy to widely apply. Detailed Implementation

[0040] The technical solution of the present invention will be further described in detail below with reference to specific embodiments. The scope of protection of the present invention is not limited to the specific embodiments described below. All other embodiments obtained by those skilled in the art without creative effort should fall within the scope of protection of the present invention.

[0041] An oxidation-resistant, antibacterial, high-flux reverse osmosis membrane includes a polymer base membrane and a polyamide functional layer formed on the polymer base membrane. The polyamide functional layer of the reverse osmosis membrane of the present invention is a blend of benzene compounds containing thiol groups and hydroxyl groups, benzene compounds containing triazole groups, sulfonate groups and hydroxyl groups, and benzene compounds containing thioether bonds, sulfonate groups and triazole groups grafted onto the surface of a conventional polyamide functional layer in the art.

[0042] The polyamide functional layer is an aromatic polyamide with a three-dimensional network structure, which is formed by interfacial polymerization of an aqueous solution with m-phenylenediamine as the monomer and an organic solution with trimesoyl chloride as the monomer.

[0043] The polymer-based film is selected from any one of polysulfone-based film, polyethersulfone-based film, and polyethylene-based film. It can be a polymer-based film supported by non-woven fabric, including non-woven fabric and a polymer support film on its surface, preferably a polysulfone-based film supported by polyester non-woven fabric.

[0044] The polyamide functional layer is formed on one side of the polymer support film of the polymer base film; the polymer base film is an existing product that can be purchased or prepared by a technician using conventional methods well known in the art, and will not be described in detail here.

[0045] The greatest innovation of this invention lies in grafting benzene compounds containing thiol and carboxylic acid groups, benzene compounds containing triazole, sulfonate, and hydroxyl groups, and blends of benzene compounds containing thioether bonds, sulfonate groups, and triazole groups onto the surface of the polyamide functional layer. This results in reverse osmosis membranes possessing properties such as oxidation resistance, antibacterial properties, and high flux.

[0046] The method for preparing the oxidation-resistant, antibacterial, and high-flux reverse osmosis membrane includes the following steps:

[0047] 1) Immerse the polymer base film in an aqueous solution containing m-phenylenediamine monomer, and after removing it, use a squeeze roller to remove excess aqueous solution from the surface of the base film;

[0048] 2) Then, the base membrane treated in step 1) is brought into contact with the prepared oil phase organic solution containing trimesoyl chloride monomer, so that m-phenylenediamine and trimesoyl chloride undergo interfacial polymerization reaction on the surface of the polymer base membrane. The excess organic solution is poured off and the residual organic solution on the surface of the polymer base membrane is removed. Then, it is rinsed with deionized water and placed in an oven to dry, forming a polyamide reverse osmosis membrane on the surface of the polymer base membrane.

[0049] 3) The prepared solution containing benzene compounds with thiol and carboxylic acid groups and carboxylic acid crosslinking agent is brought into contact with the polyamide reverse osmosis membrane formed in step 2), and then the excess solution on the surface is removed. The membrane is then placed in an oven for heat treatment. After the membrane is removed and washed with water, it is placed in an oven again for secondary heat treatment to graft benzene compounds with thiol and carboxylic acid groups onto the surface of the polyamide reverse osmosis membrane.

[0050] 4) The prepared solution of benzene compounds containing triazole groups, sulfonate groups, and hydroxyl groups and Ru-containing chelate catalyst is brought into contact with the polyamide reverse osmosis membrane treated in step 3), so that some of the benzene compounds containing thiol groups and carboxylic acid groups react with some of the benzene compounds containing triazole groups, sulfonate groups, and hydroxyl groups. Then, the excess solution on the surface is removed, and the membrane is placed in an oven for heat treatment. After the membrane is removed, it is rinsed with deionized water and placed in the oven again for secondary heat treatment. Benzene compounds containing triazole groups, sulfonate groups, and hydroxyl groups are grafted onto the surface of the polyamide reverse osmosis membrane, and at the same time, some benzene compounds containing sulfide bonds, sulfonate groups, and triazole groups are generated, thus obtaining the oxidation-resistant, antibacterial, high-flux reverse osmosis membrane.

[0051] It should be noted that the "contact" in this invention can refer to immersing the surface of the polymer support film layer of the polymer base film in a corresponding solution and then removing it, or it can refer to pouring or applying the corresponding solution onto the surface of the polymer support film layer, or a combination of both, as well as other common "contact" methods in the art. The key is to coat the surface of the polymer support film layer with the corresponding reactive material to prepare for subsequent polycondensation or grafting reactions. This invention preferably uses interfacial contact, making it preferable for interfacial polymerization reactions to occur at the interface. These "contact" methods are all understandable to those skilled in the art and should all be within the scope of protection of this invention.

[0052] In this invention, the aqueous solution containing m-phenylenediamine monomer in step 1) is an aqueous solution of m-phenylenediamine, and the mass concentration of m-phenylenediamine in the aqueous solution is usually 1.5 to 3.5 wt%, for example, including but not limited to 1.5 wt%, 2.0 wt%, 2.5 wt%, 3.0 wt%, and 3.5 wt%.

[0053] Step 2) The oil phase organic solution containing trimesoyl chloride monomer is a mixed solution of trimesoyl chloride and organic solvent, wherein the mass concentration of trimesoyl chloride in the oil phase organic solution is usually 0.08 to 0.2 wt%, for example, including but not limited to 0.08 wt%, 0.15 wt%, and 0.2 wt%; the organic solvent is one or more of aliphatic alkanes, aromatic alkanes, and haloalkanes, preferably aliphatic alkanes, for example, one or more of n-decane, isopar G, isopar L, and isopar H isoalkanes.

[0054] Step 3) The solution containing the benzene compound with thiol and carboxylic acid groups and the carboxylic acid crosslinking agent is an aqueous solution of the benzene compound with thiol and carboxylic acid groups and the carboxylic acid crosslinking agent. The mass concentration of the benzene compound with thiol and carboxylic acid groups is 0.01-1 wt%, for example, including but not limited to 0.01 wt%, 0.02 wt%, 0.04 wt%, 0.05 wt%, 0.08 wt%, 0.1 wt%, 0.2 wt%, 0.3 wt%, 0.4 wt%, 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, and 0.9 wt%, preferably 0.1-0.5 wt%. The mass concentration of the carboxylic acid crosslinking agent is 0.01-1%, for example, including but not limited to 0.01 wt%, 0.05 wt%, 0.1 wt%, 0.3 wt%, 0.5 wt%, 0.7 wt%, and 0.9 wt%.

[0055] The benzene compounds containing thiol and carboxylic acid groups are benzene compounds containing at least one thiol group and at least one carboxyl group, preferably benzene compounds containing one thiol group and one carboxyl group, more preferably selected from one or more of 3-mercaptobenzoic acid and 4-mercaptobiphenyl-4-carboxylic acid (e.g., 4'-mercaptobiphenyl-4-carboxylic acid); the carboxylic acid crosslinking agent is selected from one or more of BOP Carter condensing agent, AOP condensing agent, and HBTU peptide synthesis condensing agent. Those skilled in the art will understand that other benzene compounds containing at least one thiol group and at least one carboxyl group can also achieve the effects of the present invention and should all be within the scope of protection of the present invention.

[0056] Step 4) The solution of the benzene series containing triazole groups, sulfonate groups, and hydroxyl groups and the ruthenium-containing chelate catalyst is an aqueous solution of the benzene series containing triazole groups, sulfonate groups, and hydroxyl groups and the ruthenium-containing chelate catalyst. The mass concentration of the benzene series containing triazole groups, sulfonate groups, and hydroxyl groups is 0.05-2 wt%, for example, including but not limited to 0.05 wt%, 0.08 wt%, 0.2 wt%, 0.4 wt%, 0.6 wt%, 0.8 wt%, 1.0 wt%, 1.2 wt%, 1.4 wt%, 1.6 wt%, 1.8 wt%, and 1.9 wt%, preferably 0.1-1.0 wt%. The mass concentration of the ruthenium-containing chelate catalyst is 0.5-1 wt%, for example, including but not limited to 0.5 wt%, 0.6 wt%, 0.7 wt%, 0.8 wt%, 0.9 wt%, and 1.0 wt%.

[0057] The benzene derivative containing a triazole group, a sulfonate group, and a hydroxyl group is a benzene derivative containing at least one triazole group, at least one sulfonate group, and at least one hydroxyl group, preferably a benzene derivative containing one triazole group, one sulfonate group, and one hydroxyl group, more preferably selected from one or more of 2-(1H-1,2,4-triazol-1-yl)-4-sulfonylbenzyl alcohol, 3-(1H-1,2,4-triazol-1-yl)-5-sulfonylbenzyl alcohol, and 4-(1H-1,2,4-triazol-1-yl)-6-sulfonylbenzyl alcohol, and even more preferably 2-(1H-1,2,4-triazol-1-yl)-4-sulfonylbenzyl alcohol; the ruthenium-containing chelate catalyst is selected from one or more of aziran-Ru, PNP-Ru, and PNNH-Ru.

[0058] The aforementioned 2-(1H-1,2,4-triazol-1-yl)-4-sulfonic acid benzyl alcohol, 3-(1H-1,2,4-triazol-1-yl)-5-sulfonic acid benzyl alcohol, and 4-(1H-1,2,4-triazol-1-yl)-6-sulfonic acid benzyl alcohol are existing products that can be purchased or prepared by conventional methods well known in the art. However, since they are generally not very stable in their form containing sulfonic acid groups, they are often prepared in-house. For example, they can be obtained by reacting the raw materials 2-(1H-1,2,4-triazol-1-yl)benzyl alcohol, 3-(1H-1,2,4-triazol-1-yl)benzyl alcohol, and 4-(1H-1,2,4-triazol-1-yl)benzyl alcohol with concentrated sulfuric acid. The specific reaction conditions can be referred to in the prior art, and will not be elaborated here.

[0059] In this invention, the contact time between the polymer base film and the aqueous solution containing m-phenylenediamine monomer in step 1), and between the polymer base film and the oil-phase organic solution containing trimesoyl chloride monomer in step 2), is 10-300 s, for example, including but not limited to 20 s, 30 s, 40 s, 50 s, 60 s, 70 s, 80 s, 90 s, 100 s, 110 s, 130 s, 150 s, 170 s, 200 s, 220 s, 250 s, 280 s, and 300 s, preferably 30-60 s.

[0060] In this invention, the contact time between the polyamide reverse osmosis membrane and the solution containing benzene compounds with thiol groups and carboxylic acid groups and a carboxylic acid crosslinking agent in step 3) is 10-1200 s, for example, including but not limited to 10 s, 60 s, 120 s, 180 s, 240 s, 300 s, 600 s, and 1200 s, preferably 30-300 s; the contact time between the polyamide reverse osmosis membrane and the solution containing benzene compounds with triazole groups, sulfonate groups, and hydroxyl groups and a ruthenium-containing chelate catalyst in step 4) is 10-1200 s, for example, including but not limited to 10 s, 60 s, 120 s, 180 s, 240 s, 300 s, 600 s, and 1200 s, preferably 30-300 s. In step 4), some benzene compounds containing thiol groups and carboxylic acid groups undergo a dehydration reaction with some benzene compounds containing triazole groups, sulfonate groups and hydroxyl groups through contact, forming a benzene compound structure containing thioether bonds, sulfonate groups and triazole groups.

[0061] In this invention, in steps 3) and 4), the heat treatment temperature is 60-100℃, including but not limited to 60℃, 70℃, 80℃, 90℃, and 100℃, preferably 80-90℃, and the time is 0.5-10min, including but not limited to 0.5min, 1min, 2min, 3min, 4min, 5min, 6min, 7min, 8min, 9min, and 10min, preferably 1-3min;

[0062] The secondary heat treatment is performed at temperatures of 60–100°C, including but not limited to 60°C, 70°C, 80°C, 90°C, and 100°C, preferably 80–90°C, for a time of 0.5–10 min, including but not limited to 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, and 10 min, preferably 3–6 min.

[0063] In this invention, steps 3) and 4) both employ a two-stage heat treatment method. The first heat treatment provides a suitable environment for the grafting reaction, allowing benzene compounds to be grafted onto the base film. The purpose of the second heat treatment after water washing is to remove residual moisture on the surface and achieve conventional drying. In step 4), benzene compounds containing thiol and carboxylic acid groups react with benzene compounds containing triazole, sulfonate, and hydroxyl groups under the action of a catalyst to form a benzene compound structure containing thioether bonds, sulfonate groups, and triazole groups.

[0064] In this invention, step 2) involves washing with water at a temperature of 60–90°C, including but not limited to 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, and 90°C; step 3) involves washing with water at a temperature of 60–90°C, including but not limited to 60°C, 65°C, 70°C, 75°C, 80°C, 85°C, and 90°C; and step 4) involves washing with water at a temperature of 60–90°C, including but not limited to 60°C, 70°C, 80°C, and 90°C. After rinsing with hot water in steps 3) and 4), the product is then dried.

[0065] In this invention, the preparation process of the oxidation-resistant, antibacterial, and high-flux reverse osmosis membrane involves contacting a porous polymer support layer with an aqueous solution of m-phenylenediamine, followed by contacting it with an oil-phase organic solution of trimesoyl chloride to obtain a polyamide composite membrane. The inventors of this application unexpectedly discovered that after the initial interfacial polymerization reaction of m-phenylenediamine and trimesoyl chloride, the residual acyl chloride on the membrane surface is hydrolyzed into carboxyl groups by water washing. This is followed by sequentially passing the membrane through an organic solution containing benzene compounds with thiol and carboxylic acid groups and a carboxylic acid crosslinking agent, then through an organic solution containing triazole, sulfonate, and hydroxyl groups, and finally through a grafting reaction in the presence of a ruthenium-containing chelate catalyst. This significantly improves the oxidation resistance and antibacterial properties of the polyamide composite membrane while maintaining high flux and desalination rate.

[0066] The possible mechanism is speculated as follows: When the polyamide membrane is washed with water, especially hot water, the unreacted acyl chloride groups on the membrane surface can be hydrolyzed into carboxyl groups. When it passes through a solution containing benzene compounds with thiol and carboxylic acid groups and a carboxylic acid crosslinking agent, the carboxyl groups in the substance can react with the amino groups remaining on the membrane surface under the action of the carboxylic acid crosslinking agent to form amide bonds, thereby being chemically grafted and fixed to the membrane surface. At the same time, there are some free thiol groups. When the membrane passes through a solution of benzene compounds containing triazole groups, sulfonate groups and hydroxyl groups again, the free thiol groups can react with hydroxyl groups under the action of a catalyst to form a benzene compound structure containing thioether bonds, sulfonate groups and triazole groups.

[0067] On the one hand, triazole structures possess unique antibacterial properties, significantly enhancing the antibacterial performance of the membrane surface and effectively preventing biofouling deposition. On the other hand, the resulting thioether bonds effectively improve the chlorine resistance of the polyamide membrane. The low bond energy of thioether bonds allows the antioxidant active groups to preferentially react with oxidizing agents after the membrane is attacked, thus protecting the amide bonds of the main polyamide layer structure and enhancing the antioxidant properties of the polyamide desalination layer. Furthermore, the introduction of sulfonate groups to the membrane surface provides strong hydrophilicity, increasing membrane flux to some extent. Two-step post-treatment grafting after interfacial polymerization ensures that the degree of crosslinking remains unaffected during the initial interfacial polymerization. The newly formed amide bonds further increase the membrane's density, ensuring that the desalination rate remains unaffected.

[0068] The present invention will be further explained and illustrated below through more specific embodiments, but these do not constitute any limitation.

[0069] The following describes the methods used or that may be used in the embodiments of the present invention:

[0070] 1) Evaluation of desalination rate and permeability

[0071] Permeation flux and desalination rate are two important parameters for evaluating the separation performance of reverse osmosis membranes.

[0072] This invention evaluates the separation performance of reverse osmosis membranes according to GB / T 32373-2015 "Test Methods for Reverse Osmosis Membranes".

[0073] Desalination rate (R) is defined as: under certain operating conditions, the salt concentration (C) of the feed solution... f ) and the salt concentration in the permeate (C p The difference between the two is then divided by the feed solution salt concentration (C). f ), as in formula (1).

[0074]

[0075] Permeation flux is defined as the volume of water that permeates through a unit membrane area per unit time under certain operating conditions, and its unit is L / (m²). 2 ·h).

[0076] The operating conditions used for the reverse osmosis membrane performance determination in this invention are as follows: the feed solution is a 2000ppm sodium chloride aqueous solution, the solution pH is 7.0±0.5, the operating pressure is 1.55MPa, and the operating temperature is 25±0.5℃.

[0077] 2) Evaluation of oxidation resistance

[0078] The oxidation resistance of the reverse osmosis membrane was characterized by the changes in permeate flux and desalination rate before and after the sodium hypochlorite solution immersion test. The main steps were as follows: Prepare a sodium hypochlorite solution with a concentration of 1000 ppm, adjust its pH to 7.0 with 1 mol / L hydrochloric acid, immerse the reverse osmosis membrane in the sodium hypochlorite solution for 20 h, then remove the membrane and rinse the membrane surface repeatedly with deionized water. Subsequently, immerse the membrane in a 0.1 wt% sodium bisulfite solution to remove residual active chlorine, rinse the membrane surface with deionized water, and then immerse the membrane in deionized water for 2 h before testing its desalination rate and permeate flux. The test method is as described in 1).

[0079] Record the permeate flux and desalination rate of the reverse osmosis membrane before and after the sodium hypochlorite solution immersion test, and calculate the membrane desalination rate decay rate:

[0080] Desalination rate decay rate = (Desalination rate before chlorination resistance - Desalination rate after chlorination resistance) / Desalination rate before chlorination resistance × 100%.

[0081] 3) Evaluation of antibacterial properties

[0082] Antibacterial performance tests were conducted using Escherichia coli and yeast as inoculum, respectively, in accordance with GB / T37206-2018.

[0083] Number A represents the blank reverse osmosis membrane prepared in Comparative Example 3 for blank reference; B1-B13 correspond to the reverse osmosis membranes prepared in Examples 1-13; B14-B15 correspond to the reverse osmosis membranes in Examples 1 and 2; and B16-B17 correspond to the reverse osmosis membranes prepared in Examples 4-5.

[0084] Cut the membrane to be tested into a circle with a diameter of (20±1) mm, and sterilize it after washing it several times. Take 20 sterile petri dishes, numbered A and B1-B17, and drop 0.4 mL of the test bacterial suspension onto the petri dishes. Make the corresponding numbered membranes evenly contact the bacterial suspension, and place them in a constant temperature and humidity incubator at 37℃ and 90% humidity for 2 hours. Take out the reverse osmosis membrane and rinse the membrane and petri dishes with phosphate buffer. Take 1 mL and dilute it 10 times stepwise and mix it thoroughly. Take 1 mL of the diluted solution and spread it evenly on plate counting agar. Incubate it again at 37℃ and humidity for 24 hours. After taking it out, count the colonies.

[0085] The formula for calculating the antibacterial rate (K) is as follows:

[0086] K(%) = ((AB) / A) × 100%

[0087] In the formula:

[0088] K—Inhibition rate, %;

[0089] A—Count of colonies after blank culture, CFU;

[0090] B—The number of bacterial colonies (CFU) in the reverse osmosis membranes of Examples 1-13, Comparative Examples 1-2, and 4-5.

[0091] 4) Zeta potential at the membrane surface

[0092] The zeta potential of a reverse osmosis membrane reflects the surface charge distribution to some extent and has a significant impact on membrane performance.

[0093] This invention uses a Surpass3 Zeta potential meter to measure the zeta potential of a membrane. The test conditions are as follows: gap height is 100±5μm, temperature is 20±3℃, solution is 1mM KCl solution, test pH is 6.7±0.2. Before each test, the membrane is cleaned with pure water and then rinsed with the test solution 2-4 times. Each membrane is tested 4 times, and the average value is taken.

[0094] 5) Elemental analysis of membrane surface (XPS)

[0095] X-ray photoelectron spectroscopy (XPS) is a highly sensitive surface analysis method. The detection signal originates from 2-5 nm on the material surface and can characterize the types and percentage content of various elements on the surface.

[0096] This invention uses XPS to characterize the types and percentage content of elements on the surface of reverse osmosis membranes. Before testing, the reverse osmosis membranes are dried in a vacuum oven at 40°C for 24 hours. Three points are tested for each sample, and the average value of the test results is taken.

[0097] The main sources of raw materials in the following embodiments are shown in Table 1 below. Unless otherwise specified, all other raw materials were obtained through ordinary commercial channels.

[0098] Table 1 Information on Main Raw Materials

[0099]

[0100]

[0101] Preparation of 2-(1H-1,2,4-triazol-1-yl)-4-sulfonic acid benzyl alcohol: It is prepared by sulfonation reaction of 2-(1H-1,2,4-triazol-1-yl)benzyl alcohol with concentrated sulfuric acid. The specific process is as follows: 2-(1H-1,2,4-triazol-1-yl)-4-sulfonic acid benzyl alcohol is placed in a flask, and 98% concentrated sulfuric acid is slowly added while stirring continuously. The temperature is controlled at 70-75℃. The molar ratio of concentrated sulfuric acid to 2-(1H-1,2,4-triazol-1-yl)-4-sulfonic acid benzyl alcohol is 1:1. After the addition is complete, stirring is maintained for 60 min. After the reaction is complete, excess NaCl is added to remove water, and filtration yields 2-(1H-1,2,4-triazol-1-yl)-4-sulfonic acid benzyl alcohol.

[0102] 3-(1H-1,2,4-triazol-1-yl)-5-sulfonic acid benzyl alcohol and 4-(1H-1,2,4-triazol-1-yl)-6-sulfonic acid benzyl alcohol were prepared by the above method, with the raw materials replaced by 3-(1H-1,2,4-triazol-1-yl)benzyl alcohol and 4-(1H-1,2,4-triazol-1-yl)benzyl alcohol, respectively.

[0103] The embodiments and comparative examples of this invention all use polymer-based films prepared by the conventional methods described below, and will not be described separately.

[0104] Preparation of polysulfone-based membrane: 16.5 wt% of polysulfone resin was dissolved in dimethylformamide to obtain polysulfone casting solution; then the filtered and degassed polysulfone casting solution was uniformly coated onto polyester nonwoven fabric; subsequently, it was introduced into water for phase inversion to form a membrane, and after washing, a polysulfone supported membrane was obtained. The pore size of the prepared polysulfone-based membrane is between 30 and 50 nm.

[0105] Preparation of polyethersulfone-based membrane: 16 wt% polyethersulfone resin was dissolved in dimethylformamide to obtain polysulfone casting solution; then the filtered and degassed polysulfone casting solution was uniformly coated onto polyester nonwoven fabric; subsequently, it was introduced into water for phase inversion to form a membrane, and after washing, a polysulfone supported membrane was obtained. The pore size of the prepared polysulfone-based membrane is between 30 and 50 nm.

[0106] Polyethylene-based film: Purchased lithium battery separator film.

[0107] Example 1

[0108] The polysulfone-based membrane prepared by the above method was then used to prepare a reverse osmosis membrane using the following method:

[0109] 1) Mix m-phenylenediamine with water to prepare an aqueous solution of m-phenylenediamine with a mass concentration of 2.5 wt%, and stir at room temperature until it is completely dissolved;

[0110] 2) Prepare an oil-phase organic solution of pyromellitic trimethylol chloride with a mass concentration of 0.12 wt% by mixing it with isopar G isoparaffin as the organic solvent, and stir at room temperature until it is completely dissolved;

[0111] 3) Prepare an aqueous solution with a 3-mercaptobenzoic acid concentration of 0.2 wt% and a BOP Carter condensing agent concentration of 0.05 wt% by mixing 3-mercaptobenzoic acid, BOP Carter condensing agent and water, and stir at room temperature until completely dissolved;

[0112] 4) Prepare an aqueous solution of 2-(1H-1,2,4-triazol-1-yl)-4-sulfonic acid benzyl alcohol and azathane-Ru by mixing 2-(1H-1,2,4-triazol-1-yl)-4-sulfonic acid benzyl alcohol with a mass concentration of 0.5 wt% and azathane-Ru with a mass concentration of 0.75 wt% by mixing with water, and stir at room temperature until completely dissolved;

[0113] 5) Immerse one side of the polysulfone support layer of the polysulfone-based membrane in the aqueous solution containing m-phenylenediamine prepared in step 1) for 30 seconds. After removing it, use a squeeze roller to remove excess aqueous solution from the surface of the polysulfone-based membrane.

[0114] 6) Pour the oil-phase organic solution containing trimesoyl chloride prepared in step 2) onto the surface of the polysulfone support layer and contact it for 30 seconds to allow the m-phenylenediamine and trimesoyl chloride to undergo interfacial polymerization on the surface of the polysulfone support layer. Pour off the excess organic solution and use an air knife to evenly blow the membrane until there is no residual solvent on the membrane surface. Then rinse it with 60°C deionized water and put it in an oven to dry. At this point, a polyamide reverse osmosis membrane is formed on the surface of the polysulfone ultrafiltration support layer.

[0115] 7) Pour the aqueous solution of 3-mercaptobenzoic acid and BOP Carter condensing agent prepared in step 3) onto the surface of the polyamide reverse osmosis membrane formed in step 6). After contacting for 60 seconds, pour off the excess solution and place it in an oven for heat treatment at 85°C for 1 minute. After taking out the membrane, rinse it with deionized water at 80°C and perform a second heat treatment at 85°C for 3 minutes to graft 3-mercaptobenzoic acid onto the surface of the polyamide reverse osmosis membrane.

[0116] 8) Pour the aqueous solution of 2-(1H-1,2,4-triazol-1-yl)-4-sulfonic acid benzyl alcohol and azirthracene-Ru prepared in step 4) onto the surface of the polyamide reverse osmosis membrane treated in step 7), and allow it to contact for 60 seconds to allow some of the 3-mercaptobenzoic acid to react with some of the 2-(1H-1,2,4-triazol-1-yl)-4-sulfonic acid benzyl alcohol. After discarding the excess solution, place the membrane in an oven and heat-treat it again at 85°C for 1 minute. After removing the membrane, rinse it with deionized water at 80°C and heat-treat it again at 85°C for 3 minutes to obtain the reverse osmosis membrane.

[0117] Example 2-11

[0118] The reverse osmosis membranes in Examples 2-11 were prepared using essentially the same method as in Example 1, with the only difference being that the types and proportions of raw materials were adjusted according to Table 2, while other parameters and operating conditions remained unchanged.

[0119] Table 2 Raw material information for each embodiment

[0120]

[0121]

[0122] Examples 12-13

[0123] The reverse osmosis membranes in Examples 12 and 13 were prepared using essentially the same method as in Example 2, with the only difference being that: Example 12 used the polyethersulfone-based membrane prepared above, and Example 13 used a polyethylene-based membrane. The other raw materials and their proportions were the same as in Example 2. In addition, the reaction conditions were different as shown in Table 3, while other parameters and operating conditions remained unchanged.

[0124] Table 3 Reaction conditions for Examples 2, 12, and 13

[0125]

[0126] Comparative Example 1

[0127] The reverse osmosis membrane was prepared using a method essentially the same as in Example 2, except that steps 4) and 8) were omitted, and 2-(1H-1,2,4-triazol-1-yl)-4-sulfonic acid benzyl alcohol was not added.

[0128] Comparative Example 2

[0129] The reverse osmosis membrane was prepared using a method essentially the same as that in Example 2, except that steps 3) and 7) were omitted and 3-mercaptobenzoic acid was not added.

[0130] Comparative Example 3

[0131] The reverse osmosis membrane was prepared using a method essentially the same as in Example 2, except that steps 3), 4), 7), and 8) were omitted, and 2-(1H-1,2,4-triazol-1-yl)-4-sulfonic acid benzyl alcohol and 3-mercaptobenzoic acid were not added.

[0132] Comparative Example 4

[0133] The reverse osmosis membrane was prepared using essentially the same method as in Example 2, except that the catalyst nitrogen-anthracene-Ru was not added in step 4).

[0134] The reverse osmosis membranes prepared in Examples 1-13 and Comparative Examples 1-4 were tested for desalination rate, permeate flux, chlorine resistance (oxidation resistance) and Zeta potential. The results are recorded in Table 4, Reverse Osmosis Membrane Permeation Performance.

[0135] Table 4. Membrane performance of examples and comparative examples

[0136]

[0137] Elemental analysis was performed on the membrane surfaces prepared in Example 2 and Comparative Examples 2 and 3. The relevant results are shown in Table 5. It can be seen that the surface elemental composition and ratio have changed. Sulfur was detected in Example 2, which proves that the thioether bond was successfully grafted onto the surface. The decrease in the C / N ratio proves that there are triazole groups on the surface.

[0138] Table 5. Elemental analysis results of the membrane surface

[0139]

[0140] Based on the experimental results in Tables 3 and 4, when the polyamide membrane is treated with a solution containing benzene compounds with thiol and carboxylic acid groups and a solution containing benzene compounds with triazole, sulfonate and hydroxyl groups, a reverse osmosis membrane is obtained that maintains high flux and desalination rate while also having good oxidation resistance and effective antibacterial properties.

[0141] Obviously, the above embodiments are merely illustrative examples for clear explanation and are not intended to limit the implementation. Those skilled in the art will recognize that other variations or modifications can be made based on the above description. It is neither necessary nor possible to exhaustively list all possible implementations here. However, obvious variations or modifications derived therefrom are still within the scope of protection of this invention.

Claims

1. A high-flux reverse osmosis membrane with oxidation resistance, antibacterial properties, and high throughput, characterized in that: The invention includes a polymer base film and a polyamide functional layer formed on the polymer base film. The surface of the polyamide functional layer includes a blend of benzene compounds containing thiol groups and carboxylic acid groups, and benzene compounds containing triazole groups, sulfonate groups and hydroxyl groups. The blend of the polyamide functional layer surface also contains benzene compounds containing thioether bonds, sulfonate groups and triazole groups.

2. The reverse osmosis membrane according to claim 1, characterized in that, The benzene compounds containing thiol and carboxylic acid groups are benzene compounds containing at least one thiol group and at least one carboxyl group.

3. The reverse osmosis membrane according to claim 2, characterized in that, The benzene series containing thiol and carboxylic acid groups is a benzene series containing one thiol group and one carboxyl group.

4. The reverse osmosis membrane according to claim 2, characterized in that, The benzene compounds containing thiol and carboxylic acid groups are selected from one or more of 3-mercaptobenzoic acid, 4-mercaptobiphenyl-4-carboxylic acid, 4-amino-3-mercaptobenzoic acid, and 5-fluoro-2-mercaptobenzoic acid.

5. The reverse osmosis membrane according to claim 1, characterized in that, The benzene series containing triazole groups, sulfonate groups, and hydroxyl groups is a benzene series containing at least one triazole group, at least one sulfonate group, and at least one hydroxyl group.

6. The reverse osmosis membrane according to claim 5, characterized in that, The benzene series containing triazole group, sulfonate group and hydroxyl group is a benzene series containing one triazole group, one sulfonate group and one hydroxyl group.

7. The reverse osmosis membrane according to claim 5, characterized in that, The benzene compounds containing triazole groups, sulfonate groups, and hydroxyl groups are selected from one or more of 2-(1H-1,2,4-triazol-1-yl)-4-sulfonylbenzyl alcohol, 3-(1H-1,2,4-triazol-1-yl)-5-sulfonylbenzyl alcohol, and 4-(1H-1,2,4-triazol-1-yl)-6-sulfonylbenzyl alcohol.

8. The reverse osmosis membrane according to claim 1, characterized in that, The benzene compounds containing thioether bonds, sulfonate groups, and triazole groups are products obtained by reacting benzene compounds containing thiol groups and carboxylic acid groups with benzene compounds containing triazole groups, sulfonate groups, and hydroxyl groups.

9. The reverse osmosis membrane according to claim 1, characterized in that, The polyamide functional layer is an aromatic polyamide with a three-dimensional network structure, formed by interfacial polymerization of an aqueous solution with m-phenylenediamine as the monomer and an organic solution with trimesoyl chloride as the monomer; and / or The polymer-based film is selected from any one of polysulfone-based film, polyethersulfone-based film, and polyethylene-based film.

10. The reverse osmosis membrane according to claim 9, characterized in that, The polymer-based membrane is a polysulfone-based membrane supported by polyester nonwoven fabric.

11. A method for preparing an oxidation-resistant, antibacterial, high-flux reverse osmosis membrane according to any one of claims 1-10, characterized in that the step... include: 1) Contact the polymer-based membrane with an aqueous solution containing m-phenylenediamine monomer, and then remove excess aqueous solution from the surface of the polymer-based membrane; 2) Then, the polymer base membrane treated in step 1) is brought into contact with an oil phase organic solution containing trimesoyl chloride monomer, so that m-phenylenediamine and trimesoyl chloride undergo interfacial polymerization on the surface of the polymer base membrane. The excess organic solution is poured off and the residual organic solution on the surface of the polymer base membrane is removed. Then, after washing with water and drying, a polyamide reverse osmosis membrane is formed on the surface of the polymer base membrane. 3) The prepared solution containing benzene compounds with thiol and carboxylic acid groups and a carboxylic acid crosslinking agent is brought into contact with the polyamide reverse osmosis membrane formed in step 2), and then the excess solution on the surface is removed. Then, heat treatment, water washing, and secondary heat treatment are performed to graft benzene compounds with thiol and carboxylic acid groups onto the surface of the polyamide reverse osmosis membrane. 4) The prepared solution of benzene compounds containing triazole groups, sulfonate groups, and hydroxyl groups and ruthenium-containing chelate catalyst is brought into contact with the polyamide reverse osmosis membrane treated in step 3), so that the benzene compounds containing thiol groups and carboxylic acid groups react with the benzene compounds containing triazole groups, sulfonate groups, and hydroxyl groups. Then, excess solution on the surface is removed, followed by heat treatment, water washing, and a second heat treatment. The benzene compounds containing triazole groups, sulfonate groups, and hydroxyl groups are grafted onto the surface of the polyamide reverse osmosis membrane, while simultaneously generating benzene compounds containing sulfide bonds, sulfonate groups, and triazole groups, to obtain the oxidation-resistant, antibacterial, high-flux reverse osmosis membrane.

12. The preparation method according to claim 11, characterized in that, Step 1) The aqueous solution containing m-phenylenediamine monomer is an aqueous solution of m-phenylenediamine, wherein the concentration of m-phenylenediamine is 1.5–3.5 wt%; and / or Step 2) The oil-phase organic solution containing trimesoyl chloride monomer is a mixed solution of trimesoyl chloride and an organic solvent, wherein the concentration of trimesoyl chloride is 0.08–0.2 wt%; and / or Step 3) The solution containing the benzene compound with thiol and carboxylic acid groups and the carboxylic acid crosslinking agent is an aqueous solution of the benzene compound with thiol and carboxylic acid groups and the carboxylic acid crosslinking agent, wherein the concentration of the benzene compound with thiol and carboxylic acid groups is 0.01-1 wt%, and the concentration of the carboxylic acid crosslinking agent is 0.01-1 wt%; and / or Step 4) The solution of the benzene series containing triazole groups, sulfonate groups and hydroxyl groups and the ruthenium-containing chelate catalyst is an aqueous solution of the benzene series containing triazole groups, sulfonate groups and hydroxyl groups and the ruthenium-containing chelate catalyst, wherein the concentration of the benzene series containing triazole groups, sulfonate groups and hydroxyl groups is 0.05-2 wt%; and the concentration of the ruthenium-containing chelate catalyst is 0.5-1 wt%.

13. The preparation method according to claim 12, characterized in that, The organic solvent is one or more of aliphatic alkanes, aromatic alkanes, and haloalkanes.

14. The preparation method according to claim 13, characterized in that, The organic solvent is an aliphatic alkane.

15. The preparation method according to claim 14, characterized in that, The organic solvent is selected from one or more isoparaffins selected from n-decane, isoparG, isoparL, and isoparH.

16. The preparation method according to claim 12, characterized in that, The concentration of the benzene series containing thiol and carboxylic acid groups is 0.1 to 0.5 wt%.

17. The preparation method according to claim 12, characterized in that, The carboxylic acid crosslinking agent is selected from one or more of BOP carter condensing agent, AOP condensing agent, and HBTU peptide synthesis condensing agent.

18. The preparation method according to claim 12, characterized in that, The concentration of the benzene series containing triazole groups, sulfonate groups and hydroxyl groups is 0.1 to 1.0 wt%.

19. The preparation method according to claim 12, characterized in that, The ruthenium-containing chelate catalyst is selected from one or more of the following: anthracene-Ru, PNP-Ru, and PNNH-Ru.

20. The preparation method according to claim 11, characterized in that, The contact time between the polymer base film and the aqueous solution containing m-phenylenediamine monomer in step 1), and the oil-phase organic solution containing trimesoyl chloride monomer in step 2), is 10–300 s; and / or The contact time between the polyamide reverse osmosis membrane and the solution containing benzene compounds with thiol and carboxylic acid groups and carboxylic acid crosslinking agent in step 3) is 10-1200 s; the contact time between the polyamide reverse osmosis membrane and the solution containing benzene compounds with triazole groups, sulfonate groups and hydroxyl groups and ruthenium-containing chelate catalyst in step 4) is 10-1200 s.

21. The preparation method according to claim 20, characterized in that, The contact time between the polymer base film and the aqueous solution containing m-phenylenediamine monomer in step 1), and the oil-phase organic solution containing trimesoyl chloride monomer in step 2), is 30–60 s.

22. The preparation method according to claim 20, characterized in that, The contact time between the polyamide reverse osmosis membrane and the solution containing benzene compounds with thiol and carboxylic acid groups and carboxylic acid crosslinking agent in step 3) is 30 to 300 seconds.

23. The preparation method according to claim 20, characterized in that, The contact time between the benzene series compounds containing triazole groups, sulfonate groups and hydroxyl groups in step 4) and the ruthenium-containing chelate catalyst solution is 30 to 300 s.

24. The preparation method according to claim 11, characterized in that, In steps 3) and 4), the heat treatment is performed at a temperature of 60–100°C for a time of 0.5–10 min. The secondary heat treatment is performed at a temperature of 60–100°C for a time of 0.5–10 min; and / or The water washing in step 2) is at a temperature of 60-90℃; the water washing in step 3) is at a temperature of 60-90℃; the water washing in step 4) is at a temperature of 60-90℃.

25. The preparation method according to claim 24, characterized in that, The heat treatments were all performed at temperatures of 80–90°C for 1–3 minutes.

26. The preparation method according to claim 24, characterized in that, The secondary heat treatment was performed at a temperature of 80–90°C for a time of 3–6 minutes.

27. The use of the oxidation-resistant, antibacterial, high-flux reverse osmosis membrane according to any one of claims 1-10, or the oxidation-resistant, antibacterial, high-flux reverse osmosis membrane prepared by the method according to any one of claims 11-26, in a water treatment component or water treatment method.

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