Polymer, super-hydrophobic coating and method for preparing the same

Abstract

The present application relates to polymer, super-hydrophobic coating and its preparation method. The polymer main chain of the present application contains DHPMT derivative structure, and the side chain contains long-chain alkyl, which can give the coating excellent firmness with the base, solvent resistance and durability. The raw materials used in the preparation method of the polymer of the present application are cheap and easy to obtain, the reaction condition is simple, the reaction speed is fast and the efficiency is high.

Description

Technical Field

[0001] This invention relates to polymers, superhydrophobic coatings, and their preparation methods, belonging to the field of polymer chemistry. Background Technology

[0002] With the development of living standards and production levels, traditional polymers can no longer meet application demands. Developing polymers with novel structures and functions has become an important focus in the field of polymer chemistry. 3,4-Dihydropyrimidine-2-thione (DHPMT), a functional heterocycle, can be synthesized in one step via a three-component Biginelli reaction. It exhibits excellent biological activity in antagonizing calcium ion channels, antibacterial activity, anticancer activity, and antioxidant activity. Furthermore, the DHPMT structure possesses high reactivity similar to thiourea, allowing for efficient continuous post-modification. This facilitates the introduction of various functional structures into the molecular structure, endowing molecules with rich functionalities. Therefore, polymers with DHPMT (derived) structures have potential applications in multiple fields, and developing new polymers containing DHPMT (derived) structures and corresponding synthetic methods is of great significance.

[0003] For example, Non-Patent Literature 1 synthesized a polymer with a DHPMT structure in the main chain or side chain and chemically modified it by an addition reaction of acrylate-DHPMT, thereby greatly improving the polymer's solubility in water.

[0004] Superhydrophobic surfaces possess excellent properties such as anti-sticking, anti-fouling, anti-icing, and self-cleaning, and have important applications in aerospace, construction, and electronics industries. Modifying material surfaces with superhydrophobic coatings is one of the important ways to achieve superhydrophobicity in materials. However, due to the very low surface energy of superhydrophobic coatings, the bond between the coating and the substrate is often not strong, resulting in poor environmental resistance and durability.

[0005] In response, some efforts have been made in the prior art. For example, Patent Document 1 discloses a high weather-resistant superhydrophobic polymer and a coating composition containing the same. By including specific superhydrophobic segments, compatibility-modifying segments, and end-capping segments in the high weather-resistant superhydrophobic polymer, it achieves superhydrophobic properties while also providing excellent weather resistance and good compatibility, thereby giving the coating a long-lasting superhydrophobic effect.

[0006] References:

[0007] Non-patent literature 1: Polym. Chem., 2022, 13, 6322

[0008] Patent Document 1: CN116217935A Summary of the Invention

[0009] The problem the invention aims to solve

[0010] Existing superhydrophobic coatings still have significant room for improvement in terms of adhesion strength, resistance, and durability to the substrate. The present invention aims to provide a polymer that imparts excellent adhesion strength, resistance, and durability to the substrate, a method for preparing the polymer, and a superhydrophobic coating composition comprising the polymer.

[0011] Solution for solving the problem

[0012] To address the aforementioned problems, the inventors conducted long-term and in-depth research and proposed a polymer whose main chain contains a DHPMT-derived structure and whose side chain contains long-chain alkyl groups. They proposed first synthesizing a precursor polymer by reacting DHPMT with acrylates, and then modifying the precursor polymer by reacting DHPMT with halogenated hydrocarbons to obtain the polymer. The polymer is then used to formulate a superhydrophobic coating, which is then used to modify a copper mesh by dip coating to construct a superhydrophobic filter.

[0013] Specifically, the present invention solves the problems of the present invention through the following solutions.

[0014] [1] A polymer comprising repeating units as shown in formula (1):

[0015]

[0016] in,

[0017] R1 and R2 may represent alkylene groups having 1 to 30 carbon atoms, wherein one or more non-adjacent -CH2- groups are optionally represented by -O-, -S-, -CO-, or -NR in such a manner that the O and / or S atoms are not directly connected to each other. 0 -, -C(=O)NH-, -C(=O)O-, -OC(=O)-, -C=C- are substituted, and one or more of the hydrogen atoms are optionally substituted with halogens;

[0018] Ar represents phenylene, which is optionally mono- or poly-substituted with an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, or a halogen.

[0019] R3 and R4 may be the same or different and represent alkyl groups having 5 to 50 carbon atoms, wherein the alkyl group may be mono- or poly-substituted with fluorine.

[0020] * indicates a connection point.

[0021] [2] According to the polymer described in [1], wherein R1 in formula (1) represents the group -OZO-, where Z represents an alkylene group having 1 to 20 carbon atoms, wherein one or more non-adjacent -CH2- groups in the alkylene group are optionally replaced by -O-, -S-, -CO-, -C(=O)O-, -OC(=O)- in such a way that O and / or S atoms are not directly connected to each other, and wherein one or more hydrogen atoms are optionally replaced by halogens; R2 represents an alkylene group having 2 to 20 carbon atoms, wherein one or more non-adjacent -CH2- groups in the alkylene group are... The group is optionally replaced by -O-, -S-, -CO-, -C(=O)O-, -OC(=O)- in such a way that the O and / or S atoms are not directly connected to each other, and one or more of the hydrogen atoms are optionally substituted with a halogen; Ar represents a phenylene, which is optionally monosubstituted or polysubstituted with an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, or a halogen; R3 represents an alkyl group having 5 to 20 carbon atoms, which is polysubstituted with fluorine; R4 represents an alkyl group having 12 to 30 carbon atoms, which is optionally monosubstituted or polysubstituted with fluorine.

[0022] [3] According to the polymer of [2], wherein Z represents an alkylene group having 4 to 12 carbon atoms; R2 represents an alkylene group having 4 to 12 carbon atoms; Ar represents a phenylene group, wherein the phenylene group is optionally mono- or poly-substituted by an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen; R3 represents an alkyl group having 6 to 16 carbon atoms, wherein the alkyl group is poly-substituted by fluorine; and R4 represents an alkyl group having 15 to 25 carbon atoms, wherein the alkyl group is optionally mono- or poly-substituted by fluorine.

[0023] [4] A method for preparing the polymer according to any one of [1] to [3], comprising the following steps:

[0024] Step a): React the compound shown in formula (2) and the compound shown in formula (3) with thiourea to obtain monomer B shown in formula (4);

[0025]

[0026] Step b): The monomer A shown in formula (5) is subjected to an addition polymerization reaction with monomer B to obtain the precursor polymer shown in formula (6);

[0027]

[0028] Step c): The precursor polymer shown in formula (6) is subjected to a substitution reaction with the compound shown in formula (7) to obtain the polymer;

[0029] R3-I Equation (7)

[0030] Wherein, each group in formulas (2) to (7) has the definition given in any one of claims 1 to 3; n represents the number of repeating units in the precursor polymer, which is an integer from 1 to 50.

[0031] [5] According to the preparation method described in [4], wherein,

[0032] The reaction in step a) is carried out in a solvent in the presence of a catalyst, the catalyst being one or more selected from Brønsted acids and Lewis acids, preferably one or more selected from magnesium chloride, p-toluenesulfonic acid, hydrochloric acid, zinc chloride, cerium ammonium nitrate, ytterbium trifluoromethanesulfonate, and trimethylchlorosilane; the solvent is a polar solvent, preferably one or more selected from acetic acid, N,N-dimethylformamide, methanol, ethanol, and acetonitrile; the ratio of the compound shown in formula (2) to the compound shown in formula (3) is thiourea = 1:(1.8-2.2):(2.5-3.5) in molar proportions; the reaction temperature is 25-100°C; and the reaction time is 2-24 hours.

[0033] The addition polymerization reaction in step b) is carried out in a solvent in the presence of a catalyst, wherein the catalyst is a base, preferably an inorganic base, more preferably one or more selected from sodium carbonate, potassium carbonate, potassium hydroxide, and sodium hydroxide; the solvent is a polar aprotic solvent; in molar terms, monomer A: monomer B: catalyst = 1:(0.9-1.1):(0.05-0.20); the reaction temperature is 80-120°C; the reaction time is 4-12 hours;

[0034] The substitution reaction in step c) is carried out under the catalysis of a base and an iodide, wherein the base is preferably an inorganic base, more preferably potassium carbonate and / or sodium carbonate; the iodide is preferably sodium iodide and / or potassium iodide; the precursor polymer: the compound shown in formula (7): base: iodide = 1:(3.5-4.5):(2.5-4.5):(0.05-0.5) on a molar basis; the reaction temperature is 80-120°C; and the reaction time is 12-36 hours.

[0035] [6] A superhydrophobic coating comprising a polymer and a solvent according to any one of [1] to [3].

[0036] [7] A superhydrophobic coating comprising the polymer according to any one of [1] to [3].

[0037] [8] A superhydrophobic copper mesh, comprising a copper mesh substrate and a polymer layer located on the surface of the copper mesh substrate, the polymer layer comprising a polymer according to any one of [1] to [3].

[0038] [9] The method for preparing the superhydrophobic copper mesh according to any one of [8] includes the following steps:

[0039] The superhydrophobic coating described in [6] is applied to the surface of the copper mesh substrate and optionally dried.

[0040]

[10] The use of superhydrophobic copper mesh for oil-water separation as described in [8].

[0041] The effects of the invention

[0042] The polymers of this invention can impart excellent adhesion to the substrate, solvent resistance and durability to the coating.

[0043] The polymer preparation method of the present invention uses inexpensive and readily available raw materials, has simple reaction conditions, and is fast and efficient.

[0044] The superhydrophobic coating of the present invention can achieve a superhydrophobic coating with excellent adhesion to the substrate, resistance and durability.

[0045] The superhydrophobic copper mesh of the present invention has excellent superhydrophobicity, tolerance and durability, and can be used for the separation of various oil-water mixtures, with high separation throughput and high separation efficiency. Attached Figure Description

[0046] Figure 1 a) is the synthesis route diagram of polymer P2 in Example 1;

[0047] Figure 1 b) is the precursor polymer P1 in Example 1. 1 H NMR spectrum;

[0048] Figure 1 c) refers to polymer P2 in Example 1. 1 H NMR spectrum;

[0049] Figure 2 a) represents the contact angle test results of the copper mesh in Example 2 before and after the surface was modified with a superhydrophobic coating;

[0050] Figure 2 b) is a scanning electron microscope image of the copper mesh in Example 2 before and after the surface is modified with a superhydrophobic coating;

[0051] Figure 3 a) is a photograph of the self-cleaning test experiment process of Example 3;

[0052] Figure 3 b) shows the contact angle test results of each sample in the solvent resistance test of Example 3;

[0053] Figure 4 a) is a photograph of the oil separation experiment process in Example 4;

[0054] Figure 4 b) represents the test results of oil-water separation efficiency and throughput in Example 4;

[0055] Figure 5 The results are from the durability test in Example 5. Detailed Implementation

[0056] The present invention will now be described in detail. The description of the technical features described below is based on representative embodiments and specific examples of the present invention, but the present invention is not limited to these embodiments and specific examples.

[0057] <Terminology and Definitions>

[0058] In this specification, the terms "alkyl" and "alkylene" include straight-chain, branched, or cyclic alkyl or alkylene groups, unless otherwise expressly stated.

[0059] In this specification, halogens include fluorine, chlorine, bromine, and iodine.

[0060] In this specification, “O” in the structural formula represents an oxygen atom, “N” represents a nitrogen atom, and “S” represents a sulfur atom.

[0061] In this specification, the term "superhydrophobic" refers to a surface with a static water contact angle of 150° or more, which can be measured using a contact angle tester.

[0062] In this specification, the range of values ​​referred to as "value A to value B" refers to the range including the endpoint values ​​A and B.

[0063] In this specification, the numerical range indicated by "above" or "below" refers to the numerical range that includes the stated number.

[0064] In this specification, the word "may" has two meanings: to perform a certain process and not to perform a certain process.

[0065] In this specification, the terms "optionally" or "optionally" are used to indicate the use or non-use of certain substances, components, procedures, application conditions, etc.

[0066] All unit names used in this manual are international standard unit names, and unless otherwise stated, the "%" used refers to weight or mass percentage content.

[0067] In this specification, references to "preferred embodiments," "implementation methods," etc., mean that a specific element (e.g., feature, structure, property, and / or characteristic) related to that embodiment is included in at least one of the embodiments described herein, and may or may not be present in other embodiments. Furthermore, it should be understood that the elements may be combined in any suitable manner in various embodiments.

[0068] <Polymer>

[0069] One object of the present invention is to provide a polymer whose main chain comprises repeating units as shown in formula (1):

[0070]

[0071] In equation (1), "*" indicates the connection site with other repeating units or end capping groups, and each group represented by a letter has the meaning given below.

[0072] R1 and R2 may represent alkylene groups having 1 to 30 carbon atoms, wherein one or more non-adjacent -CH2- groups are optionally represented by -O-, -S-, -CO-, or -NR in such a manner that the O and / or S atoms are not directly connected to each other. 0 -, -C(=O)NH-, -C(=O)O-, -OC(=O)-, -C=C- are substituted, and one or more of the hydrogen atoms are optionally substituted with halogens.

[0073] Preferably, R1 represents the group -OZO-, where Z represents an alkylene group with 1 to 20 carbon atoms, preferably 4 to 18, more preferably 6 to 16 (e.g., 7, 8, 9, 10, 11, 12, 13, 14, 15, etc.), wherein one or more non-adjacent -CH2- groups in the alkylene group are optionally replaced by -O-, -S-, -CO-, -C(=O)O-, -OC(=O)- in such a manner that the O and / or S atoms are not directly connected to each other, and wherein one or more hydrogen atoms are optionally replaced by a halogen. Z preferably represents butylene, pentylene, hexylene, heptylene, octylene, nonylene, decylene, undecylene, or dodecylene.

[0074] The chain length of the group represented by R1 affects the thermodynamic properties of the polymer. When the alkyl chain length in the R1 group is relatively long (e.g., greater than or equal to 6 carbons), the polymer chain segments are relatively long, and the main and side chain groups move more freely, which is more conducive to the arrangement of hydrophobic groups on the material surface in a thermodynamically stable manner (i.e., the manner with the lowest surface energy). Therefore, from the perspective of obtaining a superhydrophobic surface (e.g., used in the superhydrophobic coating of the present invention), R1 is further preferably represented by the group -OZO-, where Z represents hexane, heptane, octane, nonane, decane, undecylene, or dodecylene.

[0075] Preferably, R2 represents an alkylene group having 2 to 20 carbon atoms, more preferably 4 to 18, and more preferably 6 to 16 (e.g., 7, 8, 9, 10, 11, 12, 13, 14, 15, etc.), wherein one or more non-adjacent -CH2- groups in the alkylene group are optionally replaced by -O-, -S-, -CO-, -C(=O)O-, or -OC(=O)- in such a manner that the O and / or S atoms are not directly connected to each other, and wherein one or more hydrogen atoms are optionally substituted with a halogen. R2 more preferably represents an ethylene, propylene, butylene, pentylene, hexylene, heptylene, or octylene group optionally mono- or poly-substituted with a fluorine atom.

[0076] The chain length of the group represented by R2, as well as the type and number of substituents, especially the number of fluorine substituents, will affect the thermodynamic properties, hydrophobicity, and solubility of the polymer. From the perspective of obtaining a superhydrophobic surface, the more fluorine substituents in the group represented by R2 and the longer its carbon chain, the better the hydrophobicity and the more favorable the arrangement of hydrophobic groups on the material surface. However, at the same time, its solubility in various solvents will decrease, making it difficult to formulate hydrophobic coatings by simply dissolving the polymer in organic solvents. Therefore, in practical applications, it is necessary to select an appropriate chain length and the number of fluorine substituents according to specific requirements. From the perspective of the superhydrophobic coating of the present invention, R2 preferably represents ethylene, propylene, butylene, pentylene, or hexylene.

[0077] Ar represents phenylene, which is optionally mono- or poly-substituted with an alkyl group having 1 to 10 carbon atoms (preferably 1 to 5, more preferably 1 to 3), an alkoxy group having 1 to 10 carbon atoms (preferably 1 to 5, more preferably 1 to 3), or a halogen.

[0078] R3 and R4 represent, respectively, alkyl groups having 5 to 50 carbon atoms, which are optionally mono- or poly-substituted with fluorine.

[0079] Preferably, R3 represents an alkyl group having 5 to 20 carbon atoms, more preferably 6 to 16, wherein the alkyl group is substituted with fluorine, more preferably more preferably more than 1 / 2 of the hydrogen atoms in the alkyl group are substituted with fluorine, and more preferably more than 2 / 3 of the hydrogen atoms are substituted with fluorine.

[0080] Preferably, R4 represents an alkyl group having 12 to 30 carbon atoms, more preferably 15 to 25, wherein the alkyl group is optionally mono- or poly-substituted with fluorine.

[0081] Hydrophobicity can be imparted to the polymer by making R3 and R4 long alkyl chains, and the hydrophobicity can be further enhanced by giving R3 and / or R4 fluorine substituents.

[0082] In one specific embodiment, the polymer of the present invention has repeating units as shown in formula (1-1):

[0083]

[0084] Each letter represents a group that has one of the meanings given in the context.

[0085] In one specific embodiment, the polymer of the present invention has repeating units as shown in formula (1-2):

[0086]

[0087] Each letter represents a group that has one of the meanings given in the context.

[0088] In one specific embodiment, the polymer of the present invention has repeating units as shown in formulas (1-3):

[0089]

[0090] Each letter represents a group that has one of the meanings given in the context. p and q represent integers between 2 and 20, preferably between 2 and 12, and more preferably 2, 3, 4, 5, 6, 7, 8, 9, and 10.

[0091] In one embodiment, the number average molecular weight (Mn) of the polymer of the present invention is 2,000 to 100,000, preferably 4,000 to 80,000, more preferably 6,000 to 50,000, even more preferably 8,000 to 40,000, and even more preferably 10,000 to 30,000.

[0092] In one embodiment, the polymer of the present invention has a molecular weight distribution (PDI) of 1.5 to 3, preferably 1.7 to 2.5, and more preferably 1.8 to 2.3.

[0093] <Polymer Preparation Methods>

[0094] One object of the present invention is to provide a method for preparing the polymer of the present invention, which includes the following steps:

[0095] Step a): React the compound shown in formula (2) and the compound shown in formula (3) with thiourea to obtain monomer B shown in formula (4);

[0096]

[0097] Step b): The monomer A shown in formula (5) is subjected to an addition polymerization reaction with monomer B to obtain the precursor polymer shown in formula (6);

[0098]

[0099] Step c): The precursor polymer shown in formula (6) is subjected to a substitution reaction with the compound shown in formula (7) to obtain the polymer;

[0100] R3-I Equation (7)

[0101] In which each group in formulas (2) to (7) has one of the definitions given in the context, and n represents the number of repeating units in the precursor polymer, which is an integer from 1 to 50, preferably 2 to 40, more preferably 3 to 25, further preferably 4 to 20, and particularly preferably 5 to 15.

[0102] The following describes in detail each step of the preparation method of the present invention.

[0103] Step a)

[0104] In step a), the compound containing two terminal aldehyde groups shown in formula (2), the β-keto ester compound shown in formula (3), and thiourea are subjected to the Biginelli reaction to obtain monomer B containing two terminal DHPMT structures shown in formula (4).

[0105] The Biginelli reaction can be carried out under suitable conditions known in the art.

[0106] In one embodiment, the reaction temperature in step a) is 25–150°C, preferably 50–130°C, and more preferably 80–120°C.

[0107] In one embodiment, the reaction time in step a) is 2 to 24 hours, preferably 4 to 12 hours.

[0108] In one embodiment, the reaction in step a) is carried out in the presence of a catalyst, which may be one or more selected from Brønsted acids and Lewis acids, preferably one or more selected from magnesium chloride, p-toluenesulfonic acid, hydrochloric acid, zinc chloride, cerium ammonium nitrate, ytterbium trifluoromethanesulfonate, and trimethylchlorosilane.

[0109] In one embodiment, the amount of catalyst used is 10–30 mol% based on the compound shown in formula (2), preferably 15–25 mol%.

[0110] In one embodiment, the reaction in step a) is carried out in a solvent, which is a polar solvent, preferably one or more selected from acetic acid, N,N-dimethylformamide, methanol, ethanol, and acetonitrile.

[0111] In one embodiment, the ratio of the compound represented by formula (2) to the compound represented by formula (3) to thiourea is 1:(1.8-2.2):(2.5-3.5), preferably 1:(1.9-2.1):(2.8-3.2), in molar quantities.

[0112] In a particularly preferred embodiment, the β-keto ester compound represented by formula (3) is one or more selected from ethyl acetoacetate, propyl acetoacetate, butyl acetoacetate, hexyl acetoacetate, octyl acetoacetate, decyl acetoacetate, dodecyl acetoacetate, tetradecyl acetoacetate, hexadecyl acetoacetate, and octadecyl acetoacetate.

[0113] In one embodiment, after the reaction is complete, the solid product, namely monomer B, is collected by water precipitation. Specifically, the reaction solution is dropped into cold water to precipitate, and the solvent is washed away.

[0114] Step b)

[0115] In step b), monomer B, which contains two terminal DHPMT structures as shown in formula (4), is added to monomer A, which contains two terminal acrylate structures as shown in formula (5), to obtain the precursor polymer containing the DHPMT structure as shown in formula (6).

[0116] In one embodiment, the addition polymerization reaction is carried out in the presence of a catalyst, which is a base, preferably an inorganic base, and more preferably one or more selected from sodium carbonate, potassium carbonate, potassium hydroxide, and sodium hydroxide.

[0117] In one embodiment, the addition polymerization reaction is carried out in a solvent, which is a polar aprotic solvent, preferably one or more selected from acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone, more preferably N,N-dimethylformamide.

[0118] In one embodiment, monomer A: monomer B = 1:(0.9 to 1.1), preferably 1:(0.95 to 1.05, in molar terms.

[0119] In one embodiment, monomer A: monomer B: catalyst, in molar ratio, is 1:(0.9-1.1):(0.05-0.20), preferably 1:(0.95-1.05):(0.08-0.15).

[0120] In one embodiment, the reaction temperature is 80–120°C, preferably 90–110°C.

[0121] In one implementation, the reaction time is 4 to 12 hours.

[0122] In a particularly preferred embodiment, the monomer A containing two terminal acrylate structures shown in formula (5) is a diol diacrylate, specifically one or more selected from 1,2-ethylene glycol diacrylate, 1,3-propanediol diacrylate, 1,4-butanediol diacrylate, 1,6-hexanediol diacrylate, and 2,2,3,3,4,4-hexafluoro-1,6-hexanediol diacrylate, with 1,6-hexanediol diacrylate being particularly preferred.

[0123] In one implementation, the polymerization process is monitored. Specifically, the molecular weight of the polymer in the polymerization system is detected at certain time intervals (e.g., using gel permeation chromatography (GPC)), and the reaction is stopped when the molecular weight of the polymer in the polymerization system stops increasing.

[0124] In one embodiment, step b) further includes post-processing of the polymerization product (i.e., the precursor polymer). For example, the polymerization product may be separated and purified by precipitation or dialysis using unsuitable solvents (e.g., water, ether).

[0125] Preferably, the post-treatment is performed using a precipitation method with a poor solvent, wherein the poor solvent used is preferably diethyl ether. Specifically, the reaction solution is poured into diethyl ether, the precipitate is filtered and optionally washed with water and / or diethyl ether, and then optionally dried.

[0126] Step c)

[0127] In step c), the precursor polymer shown in formula (6) is subjected to a substitution reaction with the halogenated compound shown in formula (7), thereby introducing a long alkyl side chain into the side chain of the precursor polymer.

[0128] In one embodiment, the substitution reaction in step c) is carried out in the presence of a base and an iodide salt. The base is preferably an inorganic base, more preferably potassium carbonate and / or sodium carbonate. The iodide salt is preferably sodium iodide and / or potassium iodide.

[0129] In one embodiment, the substitution reaction in step c) is carried out in a solvent, which is a polar aprotic solvent, preferably one or more selected from acetonitrile, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone, more preferably N,N-dimethylformamide.

[0130] In a specific implementation, the ratio of precursor polymer to compound of formula (7) to base to iodide salt is 1:(3.5-4.5):(2.5-4.5):(0.05-0.5), preferably 1:(3.8-4.2):(2.8-4.0):(0.1-0.3), for example 1:4:3:0.2.

[0131] In one embodiment, the reaction temperature is 80–120°C, preferably 90–110°C.

[0132] In one embodiment, the reaction time is 12 to 36 hours, preferably 18 to 30 hours.

[0133] In a particularly preferred embodiment, the halogenated compound represented by formula (7) is a halogenated alkane, specifically an iodoalkane, more specifically a perfluoroalkyl-substituted iodoethane, such as one or more selected from 2-(perfluorooctyl)iodoethane, 2-(perfluorohexyl)iodoethane, and 2-(perfluorobutyl)iodoethane.

[0134] In one implementation scheme, the substitution reaction process is monitored. Specifically, proton nuclear magnetic resonance (NMR) spectroscopy is used. 1 H NMR can be used to monitor the extent of the substitution reaction, allowing the reaction to be stopped at an appropriate degree of substitution based on the specific requirements for the hydrophobic properties of the polymer.

[0135] In one embodiment, the product can be separated and purified by dialysis or ether precipitation. Dialysis is preferred; specifically, the reaction solution can be filtered, and the filtrate can be purified by dialysis in methanol solution using a dialysis bag with a molecular weight cutoff of 3500 Da.

[0136] Other steps

[0137] Step a')

[0138] In one embodiment, the preparation method of the present invention further includes step a' of preparing the compound represented by formula (2). The specific preparation method of the compound represented by formula (2) can be a preparation method known in the art.

[0139] For example, in an embodiment where R1 represents the group -OZO-, the compound represented by formula (2) can be prepared by the following method:

[0140] Reacting the compound shown in formula (8) with the compound shown in formula (9) yields the compound shown in formula (2') containing two terminal aldehyde groups:

[0141]

[0142] Where X represents a halogen, preferably Br; Ar and Z have one of the meanings given in the context.

[0143] In one embodiment, the reaction is carried out under base catalysis, wherein the base is preferably an inorganic base, and may be one or more selected from potassium carbonate, sodium carbonate, potassium hydroxide, and sodium hydroxide.

[0144] In one embodiment, the reaction is carried out in a solvent, which may be a polar aprotic solvent, such as one or more selected from acetonitrile, dioxane, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, and N-methylpyrrolidone.

[0145] In one embodiment, the ratio of the compound represented by formula (8) to the compound represented by formula (9) to the base, in molar amounts, is (1.7–2.5):1:(2.5–3.5), preferably (2–2.2):1:(2.8–3.2), for example, 2.1:1:3.

[0146] In one embodiment, the reaction temperature is 80°C to 120°C, preferably 90°C to 110°C.

[0147] In one embodiment, the reaction time is 6 to 24 hours, preferably 12 to 18 hours.

[0148] In one implementation, the solid product, namely the compound shown in formula (2'), can be collected by precipitation of an alkaline aqueous solution after the reaction is complete.

[0149] In a particularly preferred embodiment, the compound represented by formula (8) represents p-hydroxybenzaldehyde, and the dihalogenated compound represented by formula (9) is one or more selected from 1,4-dibromobutane, 1,6-dibromohexane, and 1,8-dibromooctane.

[0150] Step a)

[0151] In one embodiment, the preparation method of the present invention further includes the step of preparing the β-keto ester compound represented by formula (3).

[0152] In one embodiment, the compound represented by formula (3) can also be prepared by the following method:

[0153] React tert-butyl acetoacetate with the alcohol shown in formula (10):

[0154] R4-OH formula (10)

[0155] In one embodiment, the reaction is carried out in a solvent, which may be an aprotic solvent, preferably a high-boiling-point (boiling point above 100°C) aprotic solvent, such as one or more selected from toluene, xylene, dimethyl sulfoxide, pyridine, N-methylpyrrolidone, diphenyl ether, and dodecane, with toluene and xylene being the most preferred.

[0156] In one embodiment, the molar ratio of tert-butyl acetoacetate to the alcohol represented by formula (10) is 1:(1 to 1.5), preferably 1:(1.1 to 1.3), for example 1:1.2.

[0157] In one embodiment, the reaction temperature is 90–120°C.

[0158] In one implementation, the reaction time is 6 to 20 hours.

[0159] <Superhydrophobic coatings and coatings>

[0160] One object of the present invention is to provide a superhydrophobic coating comprising the polymer and solvent of the present invention.

[0161] In one embodiment, the content of the polymer of the present invention in the superhydrophobic coating is 0.001 to 1 mol / L, preferably 0.005 to 0.1 mol / L, more preferably 0.008 to 0.05 mol / L, for example 0.01 mol / L, based on repeating units.

[0162] In one embodiment, the polymer of the present invention is present in a superhydrophobic coating at a content of 1 to 30 wt% by mass, preferably 2 to 20 wt%, more preferably 3 to 15 wt%, and even more preferably 5 to 10 wt%.

[0163] The present invention does not impose any particular limitation on the solvent, which can be any suitable solvent known in the field of coatings, including water and organic solvents.

[0164] In one embodiment, the solvent is one or more selected from hydrocarbons, chlorinated hydrocarbons, esters, ethers, ketones, nitriles, sulfoxides, and amides. Specifically, the solvent may be one or more selected from ethyl acetate, butyl acetate, propylene glycol methyl ether, propylene glycol methyl ether acetate, propylene glycol butyl ether, ethylene glycol methyl ether, ethylene glycol butyl ether, methanol, ethanol, propanol, isopropanol, n-butanol, isobutanol, acetone, methyl ethyl ketone, cyclohexanone, methyl isobutyl ketone, methyl n-butyl ketone, methyl pentylenetone, 3-pentanone, dioxane, dichloromethane, acetonitrile, dimethyl sulfoxide, N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. From the perspective of easy solvent removal to form a coating, low-boiling-point solvents are preferred, such as solvents with a boiling point below 100°C. From the perspective of improving the dispersion and solubility of polymers, halogenated hydrocarbons, tetrahydrofurans, amides (such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc.), and dimethyl sulfoxides are preferred.

[0165] In the superhydrophobic coating of the present invention, the solvent content can be 70-99 wt%, preferably 80-98 wt%, more preferably 85-97 wt%, and even more preferably 90-95 wt%.

[0166] In one embodiment, the superhydrophobic coating of the present invention further comprises other polymers or polymer precursors. Other polymers may be basic polymers known in the coatings industry, including but not limited to (meth)acrylic polymers, epoxy, polyester, polyurethane, etc. Polymer precursors refer to substances that can form part of the polymer molecular chain during the coating curing process, such as monomers that form the various polymers described above.

[0167] In one embodiment, the superhydrophobic coating of the present invention optionally includes an additive, which can be any suitable additive known in the coatings field, and those skilled in the art can select one according to specific needs.

[0168] In a specific implementation plan, the additive is one or more selected from pigments, dyes, nanoparticles, leveling agents, dispersing agents, and wetting agents.

[0169] The content of additives in superhydrophobic coatings can be 0–30 wt%, for example 1–25 wt%, or 2–20 wt%.

[0170] One object of the present invention is to provide a superhydrophobic coating comprising the polymers of the present invention. In one embodiment, it may also optionally comprise other polymers and / or additives described above.

[0171] In one embodiment, the polymer of the present invention is present in a content of 10 wt% or more in the superhydrophobic coating, preferably 30 wt% or more, more preferably 50 wt% or more, further preferably 70 wt%, and even more preferably 90 wt% or more. There is no particular limitation on the upper limit of the content of the polymer of the present invention in the superhydrophobic coating; it can be 100 wt%, or less than 95 wt%, or less than 85 wt%, or less than 75 wt%.

[0172] In one embodiment, the superhydrophobic coating of the present invention is formed by curing the superhydrophobic coating of the present invention. Therefore, the superhydrophobic coating of the present invention may also include other non-volatile components (other polymers, additives) of the superhydrophobic coating described above.

[0173] <Superhydrophobic Copper Mesh and its Preparation Method>

[0174] One object of the present invention is to provide a superhydrophobic copper mesh comprising a copper mesh substrate and a polymer layer located on the surface of the copper mesh substrate, the polymer layer comprising the polymer of the present invention.

[0175] In one embodiment, the polymer layer is composed of the polymer of the present invention.

[0176] In the polymer of this invention, sulfur in the DHPMT-derived structure can coordinate with divalent copper, which makes the polymer layer and the copper oxide mesh substrate of this invention firmly bonded and not easy to fall off, thus having excellent durability and solvent resistance.

[0177] This invention does not impose any particular restrictions on the copper mesh substrate, which can have any shape and size, and those skilled in the art can choose according to specific needs.

[0178] In one embodiment, the mesh size of the copper mesh substrate is 10–500 μm.

[0179] In one embodiment, the shape of the copper mesh substrate is circular, rectangular, square, triangular, trapezoidal, or polygonal. For the above shapes, the longest diameter in its area can be 1 cm or more, 10 cm or more, or 1 m or less, or less than 100 m, less than 10 m, or less than 5 m.

[0180] In one embodiment, the thickness of the polymer layer is 50 nm to 50 μm.

[0181] In one embodiment, the water contact angle of the superhydrophobic copper mesh is 150° or higher, for example, 151° or higher, 152° or higher, 153° or higher, or 154° or higher.

[0182] One object of the present invention is to provide a method for preparing the superhydrophobic copper mesh of the present invention, which includes the following steps:

[0183] The superhydrophobic coating of the present invention is applied to the surface of a copper mesh substrate and optionally dried.

[0184] Coating can be performed using any suitable method known in the art, including but not limited to spin coating, brush coating, dip coating, roll coating, and spray coating. Dip coating is preferred from the perspective of facilitating polymer layer formation. Specifically, coating can be performed by immersing a copper mesh substrate in the superhydrophobic coating of the present invention and then removing it.

[0185] In one embodiment, after coating is completed, the coated copper mesh substrate is dried. Drying can be carried out by suitable methods known in the art, including but not limited to air drying (20-30°C), oven drying (40-80°C), baking, hot air drying, etc.

[0186] In one embodiment, the method for preparing the superhydrophobic copper mesh of the present invention further includes a pretreatment step of the copper mesh substrate. Specifically, an alkaline oxidizing etching solution can be used for treatment to remove oxides from the surface of the copper mesh substrate. More specifically, the copper mesh substrate can be immersed in an alkaline oxidizing etching solution for a preferred immersion time of 1 to 30 minutes.

[0187] In one embodiment, the alkaline oxidizing corrosion solution can be a mixed aqueous solution of an alkali (e.g., sodium hydroxide, potassium hydroxide) and an oxidizing agent. The oxidizing agent can be a peroxide (e.g., hydrogen peroxide) and / or a persulfate (e.g., potassium persulfate, sodium persulfate). The concentration of the alkali can be 0.5–1.5 mol / L, and the concentration of the oxidizing agent can be 0.05–0.15 mol / L.

[0188] Oil-water separation

[0189] The present invention also relates to the use of the superhydrophobic copper mesh of the present invention for oil-water separation.

[0190] The present invention also relates to an oil-water separation method, which includes the following steps: filtering an oil-water mixture using the superhydrophobic copper mesh of the present invention.

[0191] Due to the superhydrophobicity of the superhydrophobic copper mesh of this invention, during the filtration process, the water in the oil-water mixture will be retained, while the oil can pass smoothly through the copper mesh, thereby achieving oil-water separation.

[0192] Example

[0193] The following specific embodiments further illustrate the present invention. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Furthermore, it should be understood that after reading the contents of this invention, those skilled in the art can make various alterations or modifications to the invention, and these equivalent forms also fall within the scope defined by this invention.

[0194] Example 1: Preparation of polymer P2

[0195] The synthetic route of polymer P2 is as follows Figure 1 As shown in a).

[0196] 1. Preparation of precursor polymer P1

[0197] In the first step, p-hydroxybenzaldehyde, 1,6-dibromohexane, and potassium carbonate were added to dioxane in a molar ratio of 2.1:1:3, with the dibromohexane concentration being 1 mol / L. The mixture was heated to 100°C and refluxed for 12 hours. After the reaction was complete, the reaction solution was dropped into cold water to precipitate the product, which was then washed with petroleum ether to obtain the precursor diCHO, containing two terminal aldehyde groups, as a yellow solid powder with a yield of approximately 90%.

[0198] In the second step, tert-butyl acetoacetate and octadecyl alcohol were dissolved in toluene at a molar ratio of 1:1.2, with the concentration of tert-butyl acetoacetate being 1 mol / L. The mixture was then heated to 110 °C and refluxed for 12 hours. After the reaction was completed, the reaction solvent was removed by rotary evaporation, and the mixture was purified by rapid column chromatography using petroleum ether as the eluent to obtain octadecyl acetoacetate as a white solid powder, with a yield of approximately 95%.

[0199] In the third step, diCHO, octadecyl acetoacetate, and thiourea were dissolved in acetic acid at a molar ratio of 1:2:3, with the concentration of diCHO being approximately 2 mol / L. Magnesium chloride (10 mol% relative to diCHO) was added as a catalyst, and the mixture was heated to 100°C and reacted for 6 hours. After the reaction was complete, the reaction solution was dropped into cold water to precipitate the product, and the acetic acid was washed away with sodium bicarbonate solution to obtain monomer B2, a yellow solid powder with a yield of approximately 80%.

[0200] The commercial monomer 1,6-hexanediol diacrylate was purified by silica gel column chromatography (eluent: petroleum ether: ethyl acetate = 20:1) to obtain purified monomer A2. The purified monomer A2 and monomer B2 were dissolved in N,N-dimethylformamide at a molar ratio of 1:1, with both monomers at a concentration of 1 mol / L. After the system was heated to 100°C, potassium carbonate (10 mol% relative to monomer A2) was added as a catalyst for the polymerization reaction. The polymerization process was monitored using gel permeation chromatography. When the molecular weight of the system stopped increasing (generally after 4 hours of polymerization), the reaction solution was precipitated in cold diethyl ether and washed with cold water and cold diethyl ether to obtain the precursor polymer P1, a yellow-brown solid.

[0201] Depend on Figure 1 b) shows 1 The 1H NMR spectrum showed that the precursor polymer P1 with a clear structural characterization was successfully obtained, and its Mn value was determined to be 7.0 × 10⁻⁶ using GPC. 3 g / mol, PDI = 2.1.

[0202] 2. Preparation of polymer P2

[0203] Precursor polymer P1 (based on repeating units), 2-perfluorooctyl iodoethane, potassium carbonate, and sodium iodide were added to N,N-dimethylformamide in a molar ratio of 1:4:3:0.2, with the concentration of precursor polymer P1 being 1 mol / L (based on repeating units). The mixture was heated to 100 °C and reacted for 18 hours. The inorganic salts in the reaction solution were filtered and purified by dialysis (dialysis solution methanol, molecular weight cutoff 3500 Da) to obtain polymer P2.

[0204] Depend on Figure 1 c) 1 The 1H NMR spectrum showed that the target polymer P2 was successfully synthesized, and its Mn value was determined to be 9.9 × 10⁻⁶ using GPC. 3 g / mol, PDI = 2.0.

[0205] Example 2: Preparation of superhydrophobic copper mesh

[0206] A mixed aqueous solution of 1 mol / L sodium hydroxide and 0.1 mol / L potassium persulfate was prepared as an alkaline oxidizing etching solution. A 400-mesh commercial phosphor bronze mesh was cut into 4 cm × 4 cm pieces and ultrasonically cleaned with 75% ethanol. The cleaned copper mesh was immersed in the etching solution for 10 minutes, then removed, rinsed with deionized water, and dried. The polymer P2 obtained in Example 1 was dissolved in dichloromethane at a concentration of 0.01 mol / L (based on repeating units) to prepare a superhydrophobic coating. The dried copper mesh was then dipped into the prepared superhydrophobic coating, removed, and directly dried in a 50°C oven to obtain the superhydrophobic copper mesh.

[0207] The copper mesh before and after surface modification with a superhydrophobic coating was characterized using a contact angle meter and a scanning electron microscope.

[0208] Depend on Figure 2 The contact angle test results of a) show that the water contact angle of the copper mesh before modification is 0°, which shows superhydrophilicity, while after the surface is modified with a superhydrophobic coating, the water contact angle is 150.8°, which shows superhydrophobicity.

[0209] Depend on Figure 2 As shown in the scanning electron microscope image (b), there are more particles and mucus-like structures on the modified copper substrate, indicating that polymer P2 was successfully modified onto the copper mesh by dip coating.

[0210] Example 3: Self-cleaning properties of superhydrophobic copper mesh and its stability in different liquid environments

[0211] 3-1: Self-cleaning test experiment

[0212] The superhydrophobic copper mesh prepared in Example 2 was cut into 2cm × 4cm pieces and flatly attached to the surface of a glass slide. A suitable amount of copper powder was sprinkled on the surface to simulate solid contaminants during the use of the copper mesh. The mesh was then rinsed with deionized water to simulate the rinsing process of rainwater. The residue of copper powder after washing was observed to evaluate the self-cleaning property of the superhydrophobic copper mesh. Photos of the experimental process are shown below. Figure 3 As shown in a).

[0213] Depend on Figure 3 As shown in a), the copper powder on the superhydrophobic copper mesh can be cleaned by simple rinsing, and its surface will be clean again, which indicates that the superhydrophobic copper mesh has self-cleaning properties.

[0214] 3-2: Solvent resistance test

[0215] The superhydrophobic copper mesh prepared in Example 2 was cut into strips of similar size (approximately 1 cm × 4 cm) and immersed in different liquid environments, including three aqueous solutions with different pH values ​​(hydrochloric acid at pH = 1, sodium chloride solution at pH = 7 with a mass fraction of 3%, and sodium hydroxide solution at pH = 13) and four different organic solvents (petroleum ether (PE), dichloromethane (DCM), tetrahydrofuran (THF), and ethanol (EtOH)). In the experiments using aqueous solutions, the superhydrophobic copper mesh was immersed in the aqueous environment for 48 hours. In the experiments using organic solvents, the superhydrophobic copper mesh was immersed in the organic solvent and ultrasonically treated for 15 minutes. After immersion, the superhydrophobic copper mesh was removed and dried, and its surface water contact angle was measured again to evaluate the stability of the superhydrophobic properties of the superhydrophobic copper mesh in different liquid environments. The contact angle test results are as follows: Figure 3 As shown in b).

[0216] Depend on Figure 3 The contact angle data in b) show that the superhydrophobic copper mesh still has good hydrophobicity after being immersed in different liquid environments, indicating that the superhydrophobic copper mesh has good solvent resistance and environmental stability.

[0217] Example 4: Oil-water separation performance test of superhydrophobic copper mesh

[0218] according to Figure 4 As shown in a), the superhydrophobic copper mesh obtained in Example 2 was fixed between two glass tubes using a polytetrafluoroethylene clamp, and the outlet of the lower tube was collected by a beaker, serving as an oil-water separation device. An equal volume of the organic solvent dichloromethane (DCM) was mixed with water to form a model oil-water mixture. To facilitate observation, Oil Red O was added as a dye to color the oil layer, making the interface between it and the water layer clearer.

[0219] 20 mL of the model oil-water mixture was poured into the oil-water separator. The throughput of the superhydrophobic copper mesh for separating this oil-water mixture was evaluated by measuring the time it took for all the oil in the mixture to pass through the superhydrophobic copper mesh. The efficiency of the superhydrophobic copper mesh for oil-water separation was evaluated by measuring the water content in the liquid passing through the superhydrophobic copper mesh using a Karl Fischer micro-water analyzer.

[0220] The other three organic solvents, petroleum ether (PE), toluene, and cyclohexane (CYH), were mixed with water in equal volumes to form model oil-water mixtures, and their oil-water separation performance was tested in the same manner as described above.

[0221] The oil-water separation performance test results of the superhydrophobic copper mesh obtained in Example 2 for four model oil-water mixtures are as follows: Figure 4 As shown in b).

[0222] pass Figure 4 As shown in b), for the four model oil-water mixtures, the superhydrophobic copper mesh of the present invention exhibits a large separation flux and high separation efficiency, indicating that the superhydrophobic copper mesh of the present invention can be used for oil-water separation and has satisfactory separation flux and separation efficiency.

[0223] Example 5: Durability Test of Superhydrophobic Copper Mesh

[0224] Using the oil-water separation apparatus from Example 4, and with a dichloromethane / water mixture as the model oil-water mixture, ten consecutive oil-water separation experiments were conducted on the same superhydrophobic copper mesh sample. The throughput and efficiency of each separation were evaluated according to the method described in Example 4. The results are as follows: Figure 5 As shown.

[0225] pass Figure 5It can be seen that the superhydrophobic copper mesh of the present invention can maintain a high level of separation efficiency and separation flux when performing multiple oil-water separations continuously, which indicates that the superhydrophobic copper mesh of the present invention has good durability.

[0226] Industrial availability

[0227] The polymer and superhydrophobic coating of the present invention can be widely used to prepare superhydrophobic coatings and have broad application prospects in the field of oil-water separation.

Claims

1. A superhydrophobic copper mesh, characterized in that, The system includes a copper mesh substrate and a polymer layer located on the surface of the copper mesh substrate, the polymer layer comprising a polymer containing repeating units as shown in formula (1): Equation (1) in, R1 represents the group -OZO-, where Z represents an alkylene group with 1 to 20 carbon atoms; R2 indicates an alkylene group having 4 to 12 carbon atoms; Ar represents phenylene, which is optionally mono- or poly-substituted with an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, or a halogen. R3 represents an alkyl group having 6 to 16 carbon atoms, wherein more than 2 / 3 of the hydrogen atoms in the alkyl group are replaced by fluorine. R4 represents an alkyl group having 15 to 25 carbon atoms, wherein the alkyl group is optionally mono- or poly-substituted with fluorine; * indicates a connection point.

2. The superhydrophobic copper mesh according to claim 1, characterized in that, The polymer has repeating units as shown in formula (1-1): Equation (1-1) Among them, R 2 R 3 and R 4 With the meaning of claim 1, Z represents an alkylene group having 4 to 12 carbon atoms.

3. The superhydrophobic copper mesh according to claim 1, characterized in that, The polymer has repeating units as shown in formula (1-2): Equation (1-2) Among them, R 2 R 3 R 4 Z has the meaning as in claim 1.

4. The superhydrophobic copper mesh according to claim 1, characterized in that, The polymer has repeating units as shown in formula (1-3): Equation (1-3) Among them, R 3 and R 4 Having the meaning of claim 1, p and q represent integers between 4 and 10, either the same or different.

5. The method for preparing the superhydrophobic copper mesh according to any one of claims 1 to 4, characterized in that, Includes the following steps: A superhydrophobic coating is applied to the surface of the copper mesh substrate and optionally dried. The superhydrophobic coating mentioned above includes the polymer and solvent.

6. The preparation method according to claim 5, characterized in that, It also includes the following steps: Step a): React the compound shown in formula (2) and the compound shown in formula (3) with thiourea to obtain monomer B shown in formula (4); ， Step b): The monomer A shown in formula (5) is subjected to an addition polymerization reaction with monomer B to obtain the precursor polymer shown in formula (6); ， Step c): The precursor polymer shown in formula (6) is subjected to a substitution reaction with the compound shown in formula (7) to obtain the polymer; Equation (7) Wherein, each group in formulas (2) to (7) has the definition given in any one of claims 1 to 4; n represents the number of repeating units in the precursor polymer, which is an integer from 1 to 50.

7. The preparation method according to claim 6, characterized in that, The reaction in step a) is carried out in a solvent in the presence of a catalyst, which is one or more selected from Brønsted acid and Lewis acid; the solvent is a polar solvent; the ratio of the compound shown in formula (2) to the compound shown in formula (3) to thiourea is 1:(1.8~2.2):(2.5~3.5) in molar proportions; the reaction temperature is 25~100℃; the reaction time is 2~24 hours; The addition polymerization reaction in step b) is carried out in a solvent in the presence of a catalyst, wherein the catalyst is a base; the solvent is a polar aprotic solvent; the molar ratio of monomer A: monomer B: catalyst is 1:(0.9~1.1):(0.05~0.20); the reaction temperature is 80~120℃; and the reaction time is 4~12 hours. The substitution reaction in step c) is carried out under the catalysis of base and iodide; the ratio of precursor polymer to compound shown in formula (7) is 1: (3.5~4.5): (2.5~4.5): (0.05~0.5) in molar proportions; the reaction temperature is 80~120℃; and the reaction time is 12~36 hours.

8. The preparation method according to claim 7, characterized in that, In step a), the catalyst is selected from one or more of magnesium chloride, p-toluenesulfonic acid, hydrochloric acid, zinc chloride, cerium ammonium nitrate, ytterbium trifluoromethanesulfonate, and trimethylchlorosilane; the solvent is selected from one or more of acetic acid, N,N-dimethylformamide, methanol, ethanol, and acetonitrile. In step b), the base is an inorganic base; In step c), the alkali is an inorganic alkali; the iodized salt is sodium iodide and / or potassium iodide.

9. The preparation method according to claim 7, characterized in that, In step b), the alkali is selected from one or more of sodium carbonate, potassium carbonate, potassium hydroxide, and sodium hydroxide. In step c), the alkali is potassium carbonate and / or sodium carbonate.

10. The use of the superhydrophobic copper mesh according to any one of claims 1 to 4 for oil-water separation.

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