Sulfur-containing onium ionic compound as well as preparation method and application thereof

Abstract

The invention discloses a sulfonium ion-containing compound as well as a preparation method and application thereof. The structural formula of the sulfonium ion-containing compound is as follows: # imgabs0 #, R1 is independently selected from methyl, ethyl or propyl, R2 and R3 are independently selected from C1-C50 linear or branched alkyl, phenyl, alkyl-substituted phenyl or alkyl-substituted naphthenic base, and-R4 is selected from halide ions, CF3SO3 <->, BF4 <-> or HCOO <->. The sulfonium ion-containing compound has efficient antibacterial and anti-algae adhesion capabilities, has the advantages of high antifouling efficiency, good stability, good marine durability, environmental protection and the like when being applied as a marine antifouling agent, and is expected to promote further development of the marine protection field.

Description

Technical Field

[0001] The present application specifically relates to a sulfur-containing onium ion compound, a preparation method thereof, and its application in the fields of marine antifouling. Background Art

[0002] Preventing the adsorption and reproduction of marine organisms on marine equipment is one of the most important technologies that need to be broken through in the development of marine resources and the development of the marine economy. Marine antifouling coatings designed based on functional polymer resins are the most convenient and effective way to prevent marine biofouling. To achieve efficient antifouling, we first need to understand the attachment process of marine organisms. The early stage of marine bioattachment is the formation of biofilms, which are mainly composed of bacteria and diatoms, followed by the secondary attachment of larvae or spores of large organisms on the biofilm. Therefore, inhibiting the formation of biofilms is the key to preventing subsequent large-scale bioattachment. Silicone materials have low surface energy, are affordable, and are easy to modify, which has aroused great research interest among scientists. However, due to the diversity of marine organisms and their size diversity, it is difficult to ensure the broad-spectrum antifouling effect of silicone coatings. Quaternary ammonium salts, as a broad-spectrum, efficient, and simple-to-synthesize bactericide, were once grafted into silicone resins by many researchers for marine antifouling, and achieved good antifouling effects. However, a century of use has led to bacterial resistance to quaternary ammonium salts. In addition, quaternary ammonium salts are easily oxidized and degraded, have poor marine persistence, and after biodegradation, water over-fertilization will occur, polluting the environment. Therefore, there is an urgent need to find a new type of fungicide with good antibacterial properties, stable structure and environmental friendliness.

[0003] Sulfonium ion compounds refer to compounds containing -S + -group substances, sulfur-containing onium ion compounds are widely present in animals and plants in nature. Studies have shown that sulfur-containing onium ion compounds play an extremely important role in the metabolism of animals and plants. With the deepening of people's research on it, sulfur-containing onium ion compounds are widely used in textile printing and dyeing, rust and corrosion prevention, organic synthesis, oil recovery, detergents, cosmetics, medicine, agriculture, papermaking and other industries. Recently, the excellent antibacterial properties of sulfonium ions that destroy negatively charged bacterial cell walls through electrostatic interactions have become a research hotspot in the field of bactericides. Some researchers have proposed an N-chloramine sulfur-containing onium ion compound. Although the compound shows a higher bactericidal efficiency than quaternary ammonium salts of similar structures, it still has the defects of low antifouling efficiency, easy oxidation and degradation, poor marine persistence, and environmental protection when used in marine antifouling. Summary of the invention

[0004] The main purpose of this application is to propose a novel sulfur-containing onium ion compound and a preparation method thereof, which, when used as a marine antifouling agent, has the advantages of high antifouling efficiency, good stability, good marine persistence and environmental protection, thereby overcoming the shortcomings of the prior art.

[0005] In order to achieve the above invention objectives, this application provides the following technical solutions:

[0006] The first aspect of the present application provides a sulfur-containing onium ion compound, the structural formula of which is as follows:

[0007]

[0008] Wherein, R1 is independently selected from methyl, ethyl or propyl, R2 and R3 are independently selected from C1-C50 straight chain or branched chain alkyl, phenyl, alkyl-substituted phenyl or alkyl-substituted cycloalkyl, - R4 is at least selected from halogen ions, CF3SO3 - 、BF4 - or HCOO - .

[0009] In one embodiment, the sulfur-containing onium ion compound has at least one of the following characteristics:

[0010] a) R2 and R3 are independently selected from C n H 2n+1 、Ph、 Where n = 1-50;

[0011] b) The halogen ion is selected from Cl - , Br or I - .

[0012] The second aspect of the present application provides a method for preparing the sulfur-containing onium ion compound, comprising: reacting a sulfur-containing ether compound with an alkylating agent at a molar ratio of 1:0.1-10 at -30°C-100°C to obtain the sulfur-containing onium ion compound;

[0013] Wherein, the structural formula of the sulfide-containing compound is:

[0014]

[0015] The chemical formula of the alkylating agent is R3-R4.

[0016] Furthermore, the reaction formula of the chemical reaction involved in the preparation method is as follows:

[0017]

[0018] In one embodiment, the alkylating agent is at least selected from IC n H 2n+1 BrC n H 2n+1 ,ClC n H 2n+1 , (CF3SO3-Cn H 2n+1 ), AgBF4 or HCOOC2H5 (acetic acid), wherein n=1-50.

[0019] In one embodiment, the preparation method comprises: reacting a vinyl silane coupling agent and a thiol compound at a molar ratio of 1:0.1-10 at -30°C-100°C to form the thioether-containing compound.

[0020] In one embodiment, the preparation method specifically comprises: in the presence of a photoinitiator and under light conditions, reacting a vinyl silane coupling agent and a thiol compound at a molar ratio of 1:0.1-10 at -30°C-100°C to form the thioether-containing compound. The reaction formula of the chemical reaction involved is as follows:

[0021]

[0022] In one embodiment, the vinyl silane coupling agent is at least selected from methylvinyldimethoxysilane, diethoxymethylvinylsilane, triacetoxyvinylsilane, vinyltriisopropoxysilane, vinyldimethylethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane or 1,3-divinyl-1,1,3,3-tetramethoxydisiloxane, and is not limited thereto.

[0023] In one embodiment, the thiol is at least selected from propanethiol, pentanethiol, benzylthiol, cyclohexanethiol, furfurylthiol, 1-octanethiol, poly(ethylene glycol) methyl ether thiol, 1-hexanethiol, 1-tetradecylthiol or 1-hexadecylthiol, and is not limited thereto.

[0024] In one embodiment, the photoinitiator can be selected from 2-hydroxy-methylphenylpropane-1-one, benzoin dimethyl ether or α-aminoalkylphenone, but is not limited thereto.

[0025] In one embodiment, the lighting condition is ultraviolet lighting condition.

[0026] The third aspect of the present application provides the use of the sulfur-containing onium ion compound in the antifouling field, especially in the marine antifouling field.

[0027] The fourth aspect of the present application provides use of the sulfonium ion-containing compound in the preparation of an antifouling agent, an antifouling coating composition or an antifouling coating.

[0028] The fifth aspect of the present application provides a marine antifouling agent comprising the sulfur-containing onium ion compound.

[0029] The sixth aspect of the present application provides an antifouling coating composition, which comprises the sulfonium ion-containing compound. Furthermore, the coating composition may also include components such as resin, pigment, filler, and additives.

[0030] The seventh aspect of the present application provides an antifouling system comprising an antifouling coating formed from the sulfur-containing onium ion compound or the antifouling coating composition.

[0031] The eighth aspect of the present application provides a surface treatment method, which comprises: coating the sulfur-containing onium ion compound or a coating composition comprising the sulfur-containing onium ion compound on the surface of a substrate to form a film layer.

[0032] Furthermore, the material of the substrate includes inorganic materials such as metals, organic materials such as polymers, or composite materials thereof. For example, the substrate may include but is not limited to marine underwater components, such as ships, marine engineering equipment, marine wind power equipment, marine aquaculture equipment, marine construction facilities, underwater cables, underwater monitoring equipment, etc.

[0033] The ninth aspect of the present application provides a surface treatment method, which comprises: contacting the sulfur-containing onium ion compound or the composition containing the sulfur-containing onium ion compound with the surface of a substrate to modify the surface of the substrate. The substrate includes but is not limited to pigments, fillers, fibers, metal substrates, etc.

[0034] Compared with the prior art, the technical solution provided by this application has at least the following beneficial effects:

[0035] (1) The provided sulfur-containing onium ion compound has the advantages of high-efficiency antibacterial performance, excellent stability, good marine durability and environmental protection. It can not only form a film layer with low surface energy and excellent antibacterial and anti-algae adhesion ability, but also when used as a marine antifouling agent, even a very low addition amount can make the marine antifouling coating containing it show high-efficiency antibacterial and anti-algae adhesion ability. Specifically, after adding the sulfur-containing onium ion compound, the marine antifouling coating has the characteristics of low surface energy of organic silicon, making it difficult for marine organisms to attach and can be self-desorbed under the scouring of seawater. On the other hand, it can inhibit and kill marine organisms, bacteria, etc., thereby solving the application problem of poor antifouling effect of existing marine antifouling coatings in static environments through the synergistic effect of two antifouling mechanisms.

[0036] (2) The preparation process of the provided sulfonium ion compound is simple, green and environmentally friendly, and easy to carry out large-scale production.

[0037] (2) The provided sulfur-containing onium ion compound can be used for surface modification of pigments, fillers, fibers, and metal substrates, and can also be used alone to form a film. It can also be combined with resins, pigments, fillers, additives, etc. to form a coating composition and applied to the surface of underwater marine components to prevent the attachment and growth of marine organisms, and has broad application prospects. BRIEF DESCRIPTION OF THE DRAWINGS

[0038] In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings required for use in the embodiments or the prior art descriptions are briefly introduced below. Obviously, the drawings described below are only some embodiments of the present application, and for ordinary technicians in this field, other drawings can be obtained based on these drawings without creative work.

[0039] Figure 1 is the hydrogen nuclear magnetic resonance spectrum of the sulfonium ion-containing compound in Example 1;

[0040] Figure 2 is the hydrogen nuclear magnetic resonance spectrum of the sulfonium ion-containing compound in Example 2;

[0041] Figure 3 is the hydrogen nuclear magnetic resonance spectrum of the sulfonium ion-containing compound in Example 3;

[0042] Figure 4 is the hydrogen nuclear magnetic resonance spectrum of the sulfonium ion-containing compound in Example 4;

[0043] Figure 5 is the hydrogen nuclear magnetic resonance spectrum of the sulfonium ion-containing compound in Example 5;

[0044] Figure 6 is the hydrogen nuclear magnetic resonance spectrum of the sulfonium ion-containing compound in Example 6;

[0045] Figure 7 is the hydrogen nuclear magnetic resonance spectrum of trimethoxysilylethylhexyl sulfide in Comparative Example 1;

[0046] Figure 8 is the H NMR spectrum of trimethoxysilylethyl hexadecyl sulfide in Comparative Example 2;

[0047] Fig. 9 is the hydrogen nuclear magnetic resonance spectrum of trimethoxysilylethylbenzyl sulfide in Comparative Example 3;

[0048] Fig.10 is the hydrogen nuclear magnetic resonance spectrum of trimethoxysilylethyl cyclohexyl sulfide in Comparative Example 4;

[0049] Fig.11 It is a test diagram of the antibacterial performance of the sulfide-containing compounds prepared in Comparative Examples 1-4 and the sulfonium ion-containing compounds prepared in Examples 1-4;

[0050] Fig.12 It is a test graph of water contact angle of the film layer formed by the sulfide-containing compound prepared in Comparative Examples 1-4 and the sulfonium ion-containing compound prepared in Examples 1-4. DETAILED DESCRIPTION

[0051] In order to make the purpose, technical scheme and advantages of the embodiments of the present application clearer, the technical scheme in the embodiments of the present application will be clearly and completely described below in conjunction with the drawings in the embodiments of the present application. Obviously, the described embodiments are part of the embodiments of the present application, not all of the embodiments. Based on the embodiments in the present application, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of this application.

[0052] In addition, unless otherwise specified, the raw materials, reaction equipment, detection equipment, etc. used in the following examples and comparative examples can be obtained through commercial channels.

[0053] In the following examples of the present invention, the purity and sources of the reagents used are as follows: vinyltrimethoxysilane, Aladdin, 98%; hexanethiol, 1-hexadecanethiol, benzyl mercaptan, J&K, 98%; dimethyl benzoate (DMPA), MacLean, 99%; iodomethane, Aladdin, 97%.

[0054] Example 1

[0055] A preparation method of a sulfonium ion compound comprises: adding vinyl trimethoxysilane (10 mmol), hexanethiol (10.1 mmol), dimethyl ether (DMPA) (0.05 mmol) and a solvent into a 50 mL three-necked flask at room temperature, stirring evenly, and irradiating with ultraviolet light at a wavelength of 365 nm for 2 minutes to complete the reaction to obtain a sulfide-containing compound, then adding (10.2 mmol) iodomethane at a temperature of -20°C, and terminating the reaction after 12 hours to obtain a colorless liquid, which is the target product, and contains trimethoxysilylethyl hexasulfonium ion, and its nuclear magnetic resonance hydrogen spectrum is as follows: Figure 1 The reaction route of the above reaction is as follows:

[0056]

[0057] Example 2

[0058] A method for preparing a sulfur-containing onium ion compound: under room temperature, vinyl trimethoxysilane (10 mmol), 1-hexadecene mercaptan (10.1 mmol), dimethyl ether (DMPA) (0.05 mmol) and a solvent are added to a 50 mL three-necked flask, stirred evenly, and irradiated with ultraviolet light at a wavelength of 365 nm for 2 minutes to complete the reaction to obtain a sulfur-containing ether compound, and then (10.2 mmol) of methyl iodide is added at a temperature of -20°C, and the reaction is terminated after 12 hours to obtain a colorless liquid, which is the target product, and contains trimethoxysilylethyl hexadecenesulfonium ion, and its nuclear magnetic resonance hydrogen spectrum is as follows: Figure 2 The reaction route of the above reaction is as follows:

[0059]

[0060] Example 3

[0061] A preparation method of a sulfonium ion compound comprises: adding vinyl trimethoxysilane (10 mmol), benzyl mercaptan (10.1 mmol), dimethyl ether (DMPA) (0.05 mmol) and a solvent into a 50 mL three-necked flask at room temperature, stirring evenly, and reacting under ultraviolet light with a wavelength of 365 nm for 2 min to obtain a sulfide-containing compound, then adding (10.2 mmol) iodomethane at a temperature of -20°C, and terminating the reaction after 12 hours to obtain a colorless liquid, which is the target product, and contains trimethoxysilylethylbenzylsulfonium ions, and its nuclear magnetic resonance hydrogen spectrum is as follows: Figure 3 The reaction route of the above reaction is as follows:

[0062]

[0063] Example 4

[0064] A method for preparing a sulfonium ion compound comprises: adding vinyl trimethoxysilane (10 mmol), cyclohexanethiol (10.1 mmol), dimethyl ether (DMPA) (0.05 mmol) and a solvent into a 50 mL three-necked flask at room temperature, stirring evenly, and reacting under ultraviolet light with a wavelength of 365 nm for 2 min to obtain a sulfide-containing compound, then adding (10.2 mmol) iodomethane at a temperature of -20°C, and terminating the reaction after 12 hours to obtain a colorless liquid, which is the target product, and contains trimethoxysilylethylcyclohexylsulfonium ion, and its nuclear magnetic resonance hydrogen spectrum is as follows: Figure 4 The reaction route of the above reaction is as follows:

[0065]

[0066] Example 5

[0067] A method for preparing a sulfur-containing onium ion compound: under room temperature, vinyl trimethoxysilane (10 mmol), 1-hexadecene mercaptan (10.1 mmol), dimethyl ether (DMPA) (0.05 mmol) and a solvent are added to a 50 mL three-necked flask, stirred evenly, and irradiated with ultraviolet light at a wavelength of 365 nm for 2 minutes to complete the reaction to obtain a sulfur-containing ether compound, and then added (10.2 mmol) of methyl tris mesylate at a temperature of -20°C, and the reaction was terminated after 12 hours to obtain a colorless liquid, which is the target product, and contains trimethoxysilylethyl hexadecene sulfonium ion, and its nuclear magnetic resonance hydrogen spectrum is as follows: Figure 5 The reaction route of the above reaction is as follows:

[0068]

[0069] Example 6

[0070] A method for preparing a sulfur-containing onium ion compound: under room temperature, vinyl trimethoxysilane (10 mmol), 1-hexadecanethiol (10.1 mmol), dimethyl ether of terminal benzoin (DMPA) (0.05 mmol) and a solvent are added to a 50 mL three-necked flask, stirred evenly, and irradiated with ultraviolet light at a wavelength of 365 nm for 2 min to complete the reaction to obtain a sulfur-containing ether compound, and then (10.2 mmol) of methyl iodide is added at a temperature of -20°C, and the reaction is terminated after 12 h to obtain a colorless liquid, and (10.2 mmol) of AgBF4 is further added, reacted for 10 min, and centrifuged to obtain a colorless liquid, which is the target product, and contains trimethoxysilylethyl hexadecylsulfonium ion, and its nuclear magnetic resonance hydrogen spectrum is as follows: Figure 6 The reaction route of the above reaction is as follows:

[0071]

[0072] Comparative Example 1

[0073] The preparation method of trimethoxysilylethyl hexyl sulfide comprises: adding vinyl trimethoxysilane (10 mmol), hexanethiol (10.1 mmol), dimethyl methyl ether (DMPA) (0.05 mmol) and a solvent into a 50 mL three-necked flask at room temperature, stirring evenly, and reacting under ultraviolet light with a wavelength of 365 nm for 2 minutes to obtain a sulfide-containing ether compound, whose nuclear magnetic resonance hydrogen spectrum is as follows: Figure 7 shown.

[0074] The reaction scheme of the above reaction is as follows:

[0075]

[0076] Comparative Example 2

[0077] The preparation method of trimethoxysilylethyl hexadecyl sulfide comprises: adding vinyl trimethoxysilane (10 mmol), 1-hexadecanethiol (10.1 mmol), dimethyl ether (DMPA) (0.05 mmol) and a solvent into a 50 mL three-necked flask at room temperature, stirring evenly, and reacting under ultraviolet light with a wavelength of 365 nm for 2 minutes to obtain a sulfur-containing ether compound, whose nuclear magnetic resonance hydrogen spectrum is as follows: Figure 8 shown.

[0078] The reaction scheme of the above reaction is as follows:

[0079]

[0080] Comparative Example 3

[0081] The preparation method of trimethoxysilylethyl benzyl sulfide comprises: adding vinyl trimethoxysilane (10 mmol), benzyl mercaptan (10.1 mmol), dimethyl methyl ether (DMPA) (0.05 mmol) and a solvent into a 50 mL three-necked flask at room temperature, stirring evenly, and reacting under ultraviolet light with a wavelength of 365 nm for 2 minutes to obtain a sulfide-containing ether compound, whose nuclear magnetic resonance hydrogen spectrum is as follows: Fig. 9 shown.

[0082] The reaction scheme of the above reaction is as follows:

[0083]

[0084] Comparative Example 4

[0085] The preparation method of trimethoxysilylethyl cyclohexyl sulfide comprises: adding vinyl trimethoxysilane (10 mmol), cyclohexyl mercaptan (10.1 mmol), dimethyl benzoate (DMPA) (0.05 mmol) and a solvent into a 50 mL three-necked flask at room temperature, stirring evenly, and reacting under ultraviolet light with a wavelength of 365 nm for 2 minutes to obtain a sulfide-containing ether compound, whose nuclear magnetic resonance hydrogen spectrum is as follows: Fig.10 shown.

[0086] The reaction scheme of the above reaction is as follows:

[0087]

[0088] The antibacterial properties of the sulfide-containing compounds prepared in Examples 1-4 and the sulfonium ion-containing compounds prepared in Examples 1-6 were tested using the method of national standard GB4789.2-2016. The specific testing process includes: after the samples to be tested are steam sterilized using an autoclave (Hirayama HVE-50), they are placed in a 6-well plate according to the grouping and sterilized by ultraviolet irradiation under an ultraviolet lamp. The bacterial solution is diluted to 106CFU / mL with a liquid culture medium, and 7mL of the diluted bacterial solution is added to the corresponding well to ensure that the bacterial solution covers the sample. Oscillating culture is carried out in a constant temperature oscillator (US Crystal IS-RDV1) at 37°C for 6 hours, and the culture process is continuously irradiated with an ultraviolet lamp (peak wavelength 365nm). After the culture is completed, the bacterial solution is diluted 10 times continuously with sterile phosphate buffer. Take 100μL of the dilution and evenly spread it on the solid culture medium, place it in a constant temperature incubator at 37°C for 18 hours, take it out, take pictures and record the number of colonies. See Fig.11 The test results show that the comparative examples 1-4 have almost no antibacterial performance and the antibacterial efficiency is close to 0. However, as these sulfide-containing compounds are ionized to generate sulfonium ions, the antibacterial efficiency is greatly improved, and the antibacterial efficiency of the sulfonium ion-containing compounds of Examples 2, 3 and 5 is as high as 99% or more.

[0089] The sulfur-containing onium ion compound of the present application can be used alone as a film. For example, the sulfur-containing ether compounds of Comparative Examples 1-4 and the sulfur-containing onium ion compounds of Examples 1-6 are coated on a stainless steel plate as a substrate, and cured at room temperature to form a film. The water contact angles of these film layers are tested. Fig.12 The test results show that the hydrophobic angles of the films formed by the sulfide-containing compounds of Comparative Examples 1-4 are all above 110°. Compared with these films, the hydrophobic angles of the films formed by the sulfur-containing onium ion compounds of Examples 1-6 are slightly lower. Among them, the hydrophobic angle of the film formed by the sulfur-containing onium ion compound of Example 3 is about 109°, indicating that the film formed by the sulfur-containing onium ion compound still has excellent hydrophobic properties.

[0090] The bonding strength between the above-mentioned film layer and the substrate, tensile strength, elastic modulus, anti-aging performance, anti-fouling performance, etc. were tested according to the methods of standards ASTM D335909, GB / T 528-2009, GB / T1865, and GB / T5370-2007. The results are shown in Table 1 below.

[0091] Table 1 Performance test results of the film layers formed by the sulfide-containing compounds of Comparative Examples 1-4 and the sulfide-containing onium ion compounds of Examples 1-6

[0092]

[0093]

[0094] The sulfur-containing onium ion compound of the present application can also be used with resins, pigments, fillers, additives, etc. to form a coating composition for application on the surface of underwater components in the ocean to prevent the attachment and growth of marine organisms. Exemplarily, 5 parts by mass of a sulfur-containing onium ion compound in Examples 1-6 are uniformly mixed with 60 parts by mass of hydroxy silicone resin, 23 parts by mass of red iron oxide, 1 part by mass of BYK300 leveling agent, 1 part by mass of BYK085 defoamer, and 10 parts by mass of ethyl orthosilicate curing agent at room temperature to form a coating. In addition, 5 parts by mass of a sulfur-containing ether compound in Comparative Examples 1-4 are uniformly mixed with 60 parts by mass of hydroxy silicone resin, 23 parts by mass of red iron oxide, 1 part by mass of BYK300 leveling agent, 1 part by mass of BYK085 defoamer, and 10 parts by mass of ethyl orthosilicate curing agent at room temperature to form a coating. As a blank control group, 60 parts by mass of hydroxy silicone resin, 23 parts by mass of red iron oxide, 1 part by mass of BYK300 leveling agent, 1 part by mass of BYK085 defoamer and 10 parts by mass of ethyl orthosilicate curing agent were uniformly mixed at room temperature to form a coating.

[0095] Then, the above coatings were applied on the surface of the stainless steel plate to form coatings of the same thickness.

[0096] The bonding strength between the above coating and the substrate, tensile strength, elastic modulus, anti-aging performance, anti-fouling performance, etc. were tested according to the methods of standards ASTM D335909, GB / T 528-2009, GB / T1865, and GB / T5370-2007. The results are shown in Table 2 below.

[0097] Table 2 Performance test results of coatings based on the sulfide-containing compounds of Comparative Examples 1-4 and the sulfonium ion-containing compounds of Examples 1-6

[0098]

[0099]

[0100] Note: The antifouling performance tests in Tables 1 and 2 were conducted in the coastal waters of Taicang City from February 2024 to August 2024.

[0101] In addition, the applicant also referred to the schemes of Examples 1 to 6 and used the other various raw materials listed in this specification to prepare a variety of sulfur-containing onium ion compounds, and tested the performance of these sulfur-containing onium ion compounds when prepared as antifouling coatings. The test results were similar to the coating performance formed by the products of Examples 1 to 6.

[0102] The sulfur-containing onium ion compound of the present application can be used for the protection of ships, marine engineering, marine wind power, marine ranches, and marine facilities below the waterline, and can also be used for the surface antifouling of underwater cables, underwater monitoring equipment, and underwater facilities.

[0103] The above embodiments are only used to illustrate the technical solutions of the present application, rather than to limit them. Although the present application has been described in detail with reference to the aforementioned embodiments, a person skilled in the art should understand that the technical solutions described in the aforementioned embodiments may still be modified, or some of the technical features may be replaced by equivalents. Such modifications or replacements will not cause the essence of the corresponding technical solutions to deviate from the protection scope of the technical solutions of the embodiments of the present application.

Claims

1. A sulfur-containing onium ion compound, characterized in that: The structural formula of the sulfur-containing onium ion compound is as follows: Wherein, R1 is independently selected from methyl, ethyl or propyl, R2 and R3 are independently selected from C1-C50 straight chain or branched chain alkyl, phenyl, alkyl-substituted phenyl or alkyl-substituted cycloalkyl, - R4 is at least selected from halogen ions, CF3SO3 - 、BF4 - or HCOO - .

2. The sulfur-containing onium ion compound according to claim 1, characterized in that The sulfur-containing onium ion compound has at least one of the following characteristics: a) R2 and R3 are independently selected from C n H 2n+1 、Ph、 Where n = 1-50; b) The halogen ion is selected from Cl - Br - or I - .

3. The method for preparing the sulfur-containing onium ion compound according to any one of claims 1 to 2, characterized in that: include: The sulfur-containing onium ion compound is prepared by reacting a sulfur-containing ether compound with an alkylating agent at a molar ratio of 1:0.1-10 at -30°C-100°C; Wherein, the structural formula of the sulfide-containing compound is: The chemical formula of the alkylating agent is R3-R4.

4. The preparation method according to claim 3, characterized in that: The alkylating agent is at least selected from IC n H 2n+1 BrC n H 2n+1 ,ClC n H 2n+1 CF3SO3-C n H 2n+1 , AgBF4 or acetic acid, wherein n=1-50.

5. The preparation method according to claim 3, characterized in that: include: The vinyl silane coupling agent and the thiol compound in a molar ratio of 1:0.1-10 are reacted at -30°C-100°C to form the thioether-containing compound.

6. The preparation method according to claim 5, characterized in that: Specifically include: In the presence of a photoinitiator and under ultraviolet irradiation, a vinyl silane coupling agent and a thiol compound in a molar ratio of 1:0.1-10 are reacted at -30°C-100°C to form the thioether-containing compound.

7. The preparation method according to any one of claims 5-6, characterized in that: The vinyl silane coupling agent is at least selected from methylvinyldimethoxysilane, diethoxymethylvinylsilane, triacetoxyvinylsilane, vinyltriisopropoxysilane, vinyldimethylethoxysilane, vinyltriethoxysilane, vinyltrimethoxysilane or 1,3-divinyl-1,1,3,3-tetramethoxydisiloxane; And / or, the thiol is at least selected from propanethiol, pentanethiol, benzylthiol, cyclohexanethiol, furfurylthiol, 1-octanethiol, poly(ethylene glycol) methyl ether thiol, 1-hexanethiol, 1-tetradecanethiol or 1-hexadecanethiol.

8. Use of the sulfur-containing onium ion compound according to any one of claims 1 to 2 in the preparation of an antifouling agent, an antifouling coating composition or an antifouling coating.

9. Use of the sulfur-containing onium ion compound according to any one of claims 1 to 2 in the field of marine antifouling.

10. A surface treatment method, characterized in that: include: Applying the sulfur-containing onium ion compound according to any one of claims 1 to 2 or a coating composition comprising the sulfur-containing onium ion compound on a surface of a substrate to form a film layer; Alternatively, the sulfonium ion-containing compound or the composition comprising the sulfonium ion-containing compound is brought into contact with a substrate surface to modify the substrate surface.

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