Sulfydryl-containing benzimidazole type hyperbranched organosilicon polymer as well as preparation method and application thereof

Abstract

The invention discloses a sulfydryl-containing benzimidazole type hyperbranched organosilicon polymer as well as a preparation method and application thereof, and belongs to the technical field of antibacterial and antifouling coatings. The sulfydryl benzimidazole type hyperbranched organosilicon polymer with a high branching degree structure is synthesized by utilizing controllable hydrolysis and condensation polymerization of a sulfydryl benzimidazole organosilicon monomer and an organosilicon monomer containing a functional group in an acid environment through a two-step method; the prepared benzimidazolyl hyperbranched organosilicon polymer has the dual advantages of antibiosis and structure, wherein the sulfydryl benzimidazole group realizes efficient broad-spectrum antibiosis on escherichia coli, staphylococcus aureus, aspergillus niger and the like by destroying microbial cell membranes and inhibiting proliferation; the hyperbranched topological structure realizes high crosslinking density while maintaining low viscosity, and terminal siloxy and active functional groups can be crosslinked by themselves or react with other polymer film forming matters to synergistically endow the material with high hydrophobicity, excellent mechanical properties, temperature resistance, water resistance and aging resistance.

Description

Technical Field

[0001] The present invention belongs to the technical field of antibacterial and antifouling coatings, and more specifically, relates to a mercaptobenzimidazole-based hyperbranched organosilicon polymer, a preparation method thereof, and an application thereof. Background Art

[0002] With the development of new-generation aerospace equipment, marine equipment, large buildings, industrial facilities, transportation pipelines and other fields, the performance requirements for anti-corrosion and antifouling coatings are becoming increasingly stringent. In marine engineering, facilities such as cross-sea bridges, deep-sea oil and gas platforms, and ships require coatings to have long-term corrosion resistance (the anti-corrosion performance needs to be 3-6 times higher than that of traditional coatings) and anti-biofouling capabilities to reduce maintenance costs and extend service life; aerospace equipment requires coatings to have lightweight, high-temperature resistance and anti-fatigue characteristics; industrial pipelines and building steel structures require coatings to remain stable under complex chemical corrosion, mechanical wear and temperature and humidity changes, and at the same time meet the environmental protection requirements of green construction and low VOC emissions.

[0003] Existing polymer-based anti-mildew and antifouling coatings generally have significant defects: one is insufficient durability, especially in dynamic scouring or high-stress environments, they are prone to peeling or micro-cracks, resulting in protection failure; the other is poor environmental adaptability, and it is difficult to cope with complex scenarios such as temperature, salinity, and pH value fluctuations. For example, traditional epoxy resin coatings are vulnerable to chloride ion penetration and pitting corrosion in marine environments, and micro-crack propagation is likely to occur under alternating stresses. Polyurethane materials are prone to molecular chain breakage and mechanical property decline under long-term aging in environments such as ultraviolet rays and high temperatures. Organosilicon coatings have high gas permeability and poor solvent resistance, and their adhesion and mechanical strength are insufficient to cope with high-speed air flow impact, etc.; the third is insufficient environmental friendliness. Although release-type antibacterial and anti-mildew agents represented by cuprous oxide can inhibit microbial attachment in the short term, the long-term released copper ions will pollute water bodies, damage the marine ecological balance, and may threaten human health through food chain enrichment. In addition, some coatings rely on toxic solvents (such as carbon tetrachloride, etc.), which exacerbate environmental pollution and operation risks.

[0004] Therefore, developing new high-performance anti-corrosion and antifouling coatings with high-efficiency protection, environmental friendliness and intelligent response characteristics has become the core direction of technological research in this field.

[0005] Chinese Patent No. CN105017830A discloses an antibacterial and antifouling agent and an antibacterial and antifouling coating, which uses a zinc oxide composite powder doped with magnesium oxide loaded on shell powder as a new antibacterial and anti-mildew agent. However, it has no improvement effect on the anti-aging performance, temperature resistance performance and antifouling performance of polymer materials. When actually used, it is still necessary to apply an antifouling coating on the surface of the anti-mildew coating for the second time, with poor construction convenience, and there are also phenomena of low durability and easy damage.

[0006] Chinese Patent No. CN107556856A discloses a nano antibacterial and antifouling coating. By introducing fluorine-modified silica fillers and polydimethylsiloxane into the acrylate material system, the surface energy of the material is reduced, thereby achieving the effects of preventing microbial attachment and antifouling. However, it has no resistance to bacteria, molds, etc., and its mildew and antibacterial properties are poor. Moreover, when polydimethylsiloxane and acrylic resin are used for a long time, phase separation will occur, causing polydimethylsiloxane to migrate to the material surface, resulting in a gradual decline in the antifouling performance of the material system and poor stability of the material system.

[0007] Chinese Patent No. CN118562339A discloses the preparation and application of an antibacterial and antifouling coating based on Cu 2 O blended with PVDF. By using specific solvents and reaction conditions, this coating system combines the excellent antibacterial properties of cuprous oxide and the low surface energy characteristics of polyvinylidene fluoride. However, the cuprous oxide antibacterial and mildew-proof agent used has the problem of copper ion leakage, and a large amount of organic solvents used in the coating construction further aggravates environmental pollution, not meeting the requirements of green environmental protection. At the same time, the inherent problems of poor adhesion and abrasion resistance of polytetrafluoroethylene materials also limit its application in special fields such as aerospace and large ships.

[0008] Existing antibacterial and antifouling coating technologies (such as copper-based antibacterial agents polluting the environment, single-functional coatings requiring multiple coatings, poor aging resistance of matrix materials, insufficient stability, etc.) are difficult to achieve a balance among core properties such as high performance, efficient antibacterial and mildew prevention, long-lasting antifouling, environmental friendliness, durability, and controllable cost, restricting their application in high-end scenarios such as aerospace and ships. Therefore, developing a new type of green and environmentally friendly multifunctional antibacterial and antifouling coating requires breakthroughs in the design of synergistic antibacterial and antifouling mechanisms, optimization of matrix polymer material properties, and low-cost process innovation, which is of great significance for improving equipment reliability, reducing maintenance costs, and promoting sustainable development. Summary of the Invention

[0009] Aiming at the above problems existing in the prior art, the technical problem to be solved by the present invention is to provide a preparation method of a mercaptobenzimidazole-type hyperbranched organosilicon polymer, which is synthesized by a one-pot method, eliminating heavy metal catalysts and highly toxic organic solvents and simplifying the preparation process. The present invention also provides a mercaptobenzimidazole-type hyperbranched organosilicon polymer prepared by the above preparation method, which has the characteristics of environmental friendliness, high-efficiency mildew resistance, low surface energy and functionalization expandability. The present invention also provides the application of the mercaptobenzimidazole-type hyperbranched organosilicon polymer in antibacterial and antifouling coatings.

[0010] To solve the above technical problems, the technical solutions adopted by the present invention are as follows:

[0011] A mercaptobenzimidazole-type hyperbranched organosilicon polymer, the structural formula is:

[0012]

[0013] Among them, R is at least one of vinyl, acryloyloxy, alkyl, phenyl, ureido, mercapto, thio, amino, 3,3,3-trifluoropropyl, perfluorooctyl, chloromethyl, and epoxy group.

[0014] A method for preparing the mercaptobenzimidazole-based hyperbranched organosilicon polymer. Under the protection of an inert gas, a mercaptobenzimidazole-based organosilicon monomer, an organosilicon monomer containing a functional functional group, and water are subjected to a hydrolysis reaction. After the hydrolysis is completed, an acidic catalyst and a solvent are added for a temperature-raising reaction. After rotary evaporation, the mercaptobenzimidazole-based hyperbranched organosilicon polymer is prepared.

[0015] Preferably, the structural formula of the mercaptobenzimidazole-based organosilicon monomer is:

[0016]

[0017] Among them, R 1 is at least one of methyl and ethyl.

[0018] Preferably, the organosilicon monomer containing a functional functional group is selected from one or more of γ-glycidyletheroxypropyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, methacryloyloxypropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, perfluorooctyltrimethoxysilane, 3,3,3-trifluoropropyltrimethoxysilane, mercaptopropyltrimethoxysilane, chloromethyltrimethoxysilane, aminopropyltriethoxysilane, and phenyltriethoxysilane.

[0019] Preferably, the acidic catalyst is selected from one or more of formic acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, trifluoroacetic acid, and oxalic acid.

[0020] Preferably, the solvent is selected from one or more of methanol, ethanol, toluene, xylene, ethyl acetate, methyl acetate, tetrahydrofuran, dioxane, dichloromethane, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetone, and butanone.

[0021] Preferably, the process of the hydrolysis reaction is natural hydrolysis for 1 h.

[0022] Preferably, the process of the temperature-raising reaction is to gradually raise the temperature to 70-90 °C and react for 2-12 h.

[0023] Preferably, the molar ratio of the mercaptobenzimidazole-based organosilicon monomer, the organosilicon monomer containing functional functional groups, and water is 0.1 to 0.9: 0.9 to 0.1: 0.5 to 2. More preferably, the molar ratio of the mercaptobenzimidazole-based organosilicon monomer, the organosilicon monomer containing functional functional groups, and water is 0.3: 0.7: 0.5 to 2.

[0024] Preferably, the amount of the acidic catalyst is 0.3% to 1% of the total mass of the reactants.

[0025] Preferably, the amount of the solvent is 150% to 300% of the total mass of the reactants.

[0026] Preferably, the preparation process of the mercaptobenzimidazole-based organosilicon monomer is as follows: under nitrogen protection, mercaptobenzimidazole and a silane coupling agent containing a glycidyl ether group are mixed at a molar ratio of 1: 3 to 2: 1 to obtain a mixed silane coupling agent; the obtained mixed silane coupling agent, solvent and basic catalyst are reacted, and after cooling and rotary evaporation, a mercaptobenzimidazole-based organosilicon monomer is prepared.

[0027] Preferably, the reaction temperature is 50 to 200 ° C and the reaction time is 0.1 to 24 h.

[0028] Preferably, the silane coupling agent containing a glycidyl ether group is one or more of γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane.

[0029] The structural formula of the silane coupling agent containing a glycidyl ether group is:

[0030]

[0031] Among them, R 1 is at least one of methyl and ethyl.

[0032] Preferably, the basic catalyst is selected from one or more of tertiary amine catalysts such as triethylamine, N, N-diisopropylethylamine, 1,4-diazabicyclo, 4-dimethylaminopyridine, quinuclidine, 1,8-diazabicycloundec-7-ene, 1,5-diazabicyclo [4.3.0] non-5-ene.

[0033] Preferably, the amount of the basic catalyst is 0.01% to 10% of the total mass of the reactants.

[0034] The mercaptobenzimidazole-based hyperbranched organosilicon polymer is prepared by the preparation method of the mercaptobenzimidazole-based hyperbranched organosilicon polymer.

[0035] Application of the mercaptobenzimidazole-based hyperbranched organosilicon polymer in antibacterial and antifouling coatings.

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

[0037] (1) The present invention utilizes the hyperbranched molecular structure to enhance stability and synergy. By introducing a three-dimensional cross-linked network of hyperbranched organosilicon (Si-O-Si skeleton), the high-temperature resistance and anti-ultraviolet aging ability of the material system are significantly enhanced, avoiding the failure caused by the decomposition of traditional mildew inhibitors. At the same time, the presence of abundant active functional groups and mercaptobenzimidazole groups in the molecular structure endows the mercaptobenzimidazole-type hyperbranched organosilicon polymer with high compatibility and high reactivity, greatly improving the stability and durability of the coating;

[0038] (2) The special hyperbranched molecular structure of the present invention enables the formation of antibacterial active sites composed of dense mercaptobenzimidazole groups on the coating surface. By destroying the microbial membrane structure and inhibiting DND / RNA transcription, it avoids the metal pollution of water areas by traditional heavy metal ion-releasing coatings;

[0039] (3) The present invention is synthesized by a one-pot method, eliminating heavy metal catalysts and highly toxic organic solvents, simplifying the preparation process, making the mercaptobenzimidazole-type hyperbranched organosilicon polymer more environmentally friendly in actual production and reducing environmental pollution;

[0040] (4) The construction steps of the high-adhesion antibacterial and antifouling integrated coating of the present invention are simplified. Due to the presence of a large number of silaneoxy active sites in the hyperbranched organosilicon polymer, chemical bonds can be formed with the substrate surface, providing the coating with high adhesion advantages. The Si-O-Si cross-linked network formed by the condensation between silicon-oxygen bonds further reduces the surface energy of the coating and enhances its antifouling performance. In addition, based on the high structural designability of the hyperbranched organosilicon polymer, the introduction of mercaptobenzimidazole groups as antibacterial active sites further endows the material with excellent antibacterial and mildew-proof properties. The combination of primer and topcoat functions can be achieved by single spraying, significantly reducing the number of coating applications and shortening the construction time, thus greatly reducing the construction steps;

[0041] (5) The mercaptobenzimidazole-based hyperbranched organosilicon polymer prepared by the present invention, with its unique molecular structure design, combines the chemical versatility of the hyperbranched structure, the flexible hydrophobicity of organosilicon materials, and the antibacterial activity of the mercaptobenzimidazole unit, showing broad application prospects in the field of polymer functional coatings; through intramolecular synergy, this material can form a dense defense barrier on the coating surface, not only having long-term antibacterial adhesion and killing functions, but also inhibiting the attachment of marine fouling organisms, and at the same time endowing the substrate with self-cleaning, corrosion resistance and other properties, making it have important application potential in the fields of medical devices, aerospace, marine engineering equipment and environmental protection architectural coatings; its characteristics of environmental friendliness, high-efficiency anti-mold, low surface energy and functionalization expansion provide innovative ideas for the development of a new generation of high-performance antibacterial and antifouling materials. BRIEF DESCRIPTION OF THE DRAWINGS

[0042] Figure 1 is the synthetic route diagram for the preparation of the mercaptobenzimidazole-based hyperbranched organosilicon polymer of the present invention;

[0043] Figure 2 are the physical pictures of mercaptobenzimidazole and the mercaptobenzimidazole-based hyperbranched organosilicon polymer; among them, Figure a is the physical picture of mercaptobenzimidazole, and Figure b is the physical picture of the mercaptobenzimidazole-based hyperbranched organosilicon polymer prepared in Example 1;

[0044] Figure 3 is the nuclear magnetic resonance spectrum of the mercaptobenzimidazole-based hyperbranched organosilicon polymer prepared in Example 1;

[0045] Figure 4 is the infrared spectrum of the mercaptobenzimidazole-based hyperbranched organosilicon polymer prepared in Example 1;

[0046] Figure 5 is the physical picture of the cured product of the mercaptobenzimidazole-based hyperbranched organosilicon polymer prepared in Example 2;

[0047] Figure 6 is the thermal stability test diagram of the cured product of the mercaptobenzimidazole-based hyperbranched organosilicon polymer prepared in Example 2;

[0048] Figure 7 is the wear resistance test diagram of the cured product of the mercaptobenzimidazole-based hyperbranched organosilicon polymer prepared in Example 5; among them, Figure A is the surface topography diagram of the coated material after testing, and Figure B is the surface roughness test diagram of the coated material after testing;

[0049] Figure 8 is the contact angle test diagram of the cured product of the mercaptobenzimidazole-based hyperbranched organosilicon polymer prepared in Example 6; among them, Figure A is the water contact angle diagram of the coating, and Figure B is the diiodomethane contact angle diagram of the coating;

[0050] Figure 9 Testing diagram of the anti-graffiti performance of the cured product of the mercaptobenzimidazole-type hyperbranched organosilicon polymer prepared in Example 6;

[0051] Figure 10 Testing diagram of the antibacterial performance of the cured product of the product prepared in Example 8;

[0052] Figure 11 Testing diagram of the antifouling performance of the cured product of the product prepared in Example 8;

[0053] Figure 12 Testing diagram of the anticorrosion performance of the cured product of the product prepared in Example 8;

[0054] Figure 13 Testing diagram of the thermal stability of the cured product of the product prepared in Comparative Example 1;

[0055] Figure 14 Testing diagram of the abrasion resistance of the cured product of the product prepared in Comparative Example 2;

[0056] Figure 15 Testing diagram of the antifouling performance of the cured products of the products prepared in Example 7 and Comparative Example 3;

[0057] Figure 16 Testing diagram of the antibacterial performance of the cured products of the products prepared in Example 7 and Comparative Example 3. Detailed implementation manners

[0058] To make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described below in conjunction with specific embodiments. In the following embodiments, unless otherwise specified, the technical means used are all conventional means well known to those skilled in the art. For those conditions not specified in the embodiments, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. For the reagents or instruments whose manufacturers are not specified, they are all conventional products that can be obtained through commercial purchase.

[0059] In the following embodiments, the mercaptobenzimidazole used is purchased from Guangzhou Weibote Technology Co., Ltd.; the coupling agent monomers are all purchased from Nanjing Nengde New Material Technology Co., Ltd.; the solvents and catalysts used are all purchased from Shanghai Macklin Biochemical Co., Ltd.

[0060] The performance testing methods adopted in the following embodiments are as follows:

[0061] 1. Thermal stability testing: Accurately weigh 5 - 10 mg of the polymer sample and place it in an alumina crucible. Ensure that the sample is evenly spread to avoid agglomeration affecting the test results. Using a thermogravimetric analyzer (TA Instruments Q500) under a nitrogen atmosphere, the gas flow rate is set to 50 mL / min, the heating rate is set to 10 °C / min, and the temperature is raised from room temperature to 1000 °C to record the thermal decomposition process of the polymer.

[0062] 2. Wear resistance test: The wear resistance test of coating is usually carried out using a friction and wear tester. First, prepare the sample with coating, accurately measure and record its initial mass and size, and firmly install the sample on the tester. Set parameters according to the coating characteristics and expected working conditions. During the test, make the sample and the friction pair move relative to each other according to the set parameters to simulate the actual wear condition. After the test, measure the mass and size of the sample again, and evaluate the wear resistance of the coating by the changes in mass and size before and after, combined with the microscopic observation of the wear marks.

[0063] 3. Contact angle test: The coating was evenly applied to the glass substrate and dried at room temperature for 24 hours. The contact angle was recorded using a Krüss DSA25 contact angle meter equipped with a high-speed camera system (500fps) at a constant temperature of 25°C, a relative humidity of 50%±5%, a droplet volume of 2μL ultrapure water / diiodomethane, and a droplet release height of 2mm. Each sample was measured at 5 different positions, and the average value and standard deviation were calculated.

[0064] 4. Anti-graffiti performance test: Use oily and water-based markers to write on the surface of the coating sample, then wipe it with a wet tissue, and judge the anti-graffiti performance of the material by checking the degree of residual writing.

[0065] 5. Antifouling performance test: First, operate in a glass water tank, mix 3000g of artificial seawater, 3g of diatom species and 10-15 drops of diatom culture solution together and stir thoroughly. After that, place the water tank under sunlight for 7 days at room temperature. Until a certain area of ​​diatom growth appears in the glass water tank. Subsequently, immerse the glass sheet coated with the sample coating to be tested in this water tank, and then continue to culture for a period of time under the same conditions as before. After the sample is soaked in the above-mentioned artificial seawater, take the sample to be tested out of the water tank, and then clean the sample surface and the back of the glass sheet with artificial seawater. Finally, use an optical microscope to observe the algae coverage on the sample surface.

[0066] 6. Antibacterial performance test: LB plate counting method and microscope observation are used to detect the antibacterial performance of the sample coating against Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus). The specific steps are as follows: 1) First prepare 20mL of 10 8A colony suspension of CFU / mL was prepared. A glass slide with dimensions of 18 mm × 18 mm and coated with a sample coating was placed into it. Then, it was incubated under constant temperature and shaking at 37 °C for 24 h. 2) After 24 h of incubation, the glass slide coated with the sample coating was taken out, and the side of the glass slide without the sample coating was washed with sterile PBS buffer. The washed glass slide was placed into 20 mL of sterile PBS buffer, and Escherichia coli (E. coli) and Staphylococcus aureus (S. aureus) attached to the coating were dropped off by ultrasonic oscillation for 15 min. 3) Then, the solution after ultrasonic treatment was diluted 1000 times. 20 μL was taken from the diluted solution and inoculated onto the surface of LB medium, and then incubated at 37 °C for 24 h. 4) The LB plate counting method was used to count the number of colonies growing on the surface of LB medium.

[0067] 7. Coating anti-corrosion performance test: Steel plates with and without coatings were immersed in natural seawater. After soaking for more than 7 days, they were taken out, and the anti-corrosion performance of the coating material was judged by visually observing the degree of surface rust.

[0068] The synthetic route diagram of the mercaptobenzimidazole-based hyperbranched organosilicon polymer provided by this application is as Figure 1 shown.

[0069] Based on the synergistic effect of the highly branched structure design of hyperbranched organosilicon polymer and mercaptobenzimidazole functional groups, this application achieves a breakthrough in anti-mildew and anti-fouling performance through innovation at the molecular level. The principle is as follows: The abundant alkoxy groups and active functional groups in the hyperbranched skeleton form strong chemical bonds with the substrate, enhancing the coating adhesion and resistance to environmental erosion; the densely packed silicon-oxygen network formed by self-crosslinking greatly enhances the water resistance and hydrophobicity, reducing the surface energy to achieve physical barrier to prevent pollutant attachment; at the same time, the introduced mercaptobenzimidazole groups achieve excellent broad-spectrum antibacterial and anti-mildew performance without the addition of heavy metal ions through the dual mechanisms of destroying the integrity of microbial cell membranes and interfering with DNA / RNA replication. This structure integrates the triple advantages of chemical anchoring, physical anti-fouling, and biological inhibition, making it have high durability, environmental friendliness, and long-term anti-biofouling ability in practical applications, and is suitable for extremely complex environments such as aerospace, marine equipment, and industrial facilities.

[0070] Example 1

[0071] A preparation method of a mercaptobenzimidazole-based hyperbranched organosilicon polymer, comprising the following steps:

[0072] 1) Under nitrogen protection, 1 mol of mercaptobenzimidazole and 1 mol of γ-glycidoxypropyltrimethoxysilane were added to a three-necked flask equipped with a condenser and a mechanical stirrer and stirred evenly to obtain a mixed silane coupling agent;

[0073] 2) After uniformly mixing 1 mol of the mixed silane coupling agent obtained in step 1) with 3 mol of methanol in a three-necked flask, add a 2 wt% triethylamine catalyst and gradually heat from room temperature to 50 °C at a heating rate of 20 °C / min. React for 1 h, and after the reaction is completed, naturally cool to room temperature. Use a rotary evaporator to remove the solvent and catalyst at 50 °C to obtain a mercaptobenzimidazole-based organosilicon monomer, which is a light yellow transparent liquid;

[0074] 3) Add 0.9 mol of the mercaptobenzimidazole-based organosilicon monomer prepared in step 2), 0.1 mol of phenyltrimethoxysilane monomer, and 1.3 mol of deionized water to a three-necked flask equipped with a condenser and mechanical stirrer, and naturally hydrolyze at room temperature for 1 h to obtain a mixture;

[0075] 4) Uniformly mix 1 mol of the mixture prepared in step 3) with 2 mol of ethanol, add a 0.5 wt% hydrochloric acid catalyst, and gradually heat to 70 °C and react for 6 h at a heating rate of 20 °C / min. After the reaction is completed, naturally cool down. Use a rotary evaporator to remove the solvent, catalyst, and reaction by-products at 60 °C to obtain a mercaptobenzimidazole-containing hyperbranched organosilicon polymer, which is a light yellow transparent liquid with low viscosity and high fluidity.

[0076] As can be seen from Figure 2 it, the obtained mercaptobenzimidazole-containing hyperbranched organosilicon polymer exhibits the characteristics of a low-viscosity liquid. After testing, its room temperature viscosity is only 207 mPa·s.

[0077] As can be seen from Figure 3 it, the calculated degree of branching of the prepared hyperbranched organosilicon polymer exceeds 0.8, which conforms to the general rule that the degree of branching of hyperbranched organosilicon polymers is greater than 0.5, proving the successful synthesis of the hyperbranched organosilicon polymer.

[0078] As can be seen from Figure 4 it, the change of the infrared characteristic peak at 1100 proves the formation of the Si-O-Si bond, which helps to prove the synthesis of the hyperbranched organosilicon polymer.

[0079] Example 2

[0080] A preparation method of a mercaptobenzimidazole-containing hyperbranched organosilicon polymer, comprising the following steps:

[0081] 1) Under nitrogen protection, add 2 mol of mercaptobenzimidazole and 1 mol of γ-glycidyletheroxypropyltriethoxysilane to a three-necked flask equipped with a condenser and mechanical stirrer, and stir evenly to obtain a mixed silane coupling agent;

[0082] 2) After mixing 1 mol of the mixed silane coupling agent obtained in step 1) with 1 mol of ethyl acetate evenly in a three-necked flask, add 10 wt% N,N-diisopropylethylamine catalyst and gradually heat up from room temperature to 200 °C at a heating rate of 20 °C / min, react for 0.1 h, and after the reaction is completed, naturally cool to room temperature. Remove the solvent and catalyst at 55 °C using a rotary evaporator to obtain the mercaptobenzimidazole-based organosilicon monomer, which is a light yellow transparent liquid;

[0083] 3) Add 0.3 mol of the mercaptobenzimidazole-based organosilicon monomer prepared in step 2), 0.7 mol of methyltrimethoxysilane, and 1.5 mol of deionized water to a three-necked flask equipped with a condenser and mechanical stirrer, and naturally hydrolyze at room temperature for 1 h to obtain a mixture;

[0084] 4) Mix 1 mol of the mixture prepared in step 3) with 3 mol of ethyl acetate evenly, add 0.01 wt% sulfuric acid catalyst, and gradually heat up to 90 °C and react for 12 h at a heating rate of 20 °C / min. After the reaction is completed, naturally cool to room temperature. Remove the solvent, catalyst, and reaction by-products at 60 °C using a rotary evaporator to obtain the mercaptobenzimidazole-containing hyperbranched organosilicon polymer, which is a light yellow transparent liquid with low viscosity and high fluidity.

[0085] It can be seen from Figure 5 that after the mercaptobenzimidazole-containing hyperbranched organosilicon polymer prepared above is cured at 100 °C for 24 hours to form a film, the obtained film material presents a light yellow transparent shape, has strong denseness, and good film-forming property.

[0086] It can be seen from Figure 6 that when performing a thermal stability test on the cured product of the mercaptobenzimidazole-containing hyperbranched organosilicon polymer cured into a film, the 95% thermal decomposition temperature of the product prepared in Example 2 exceeds 350 °C, and at the same time, the char residue rate at 1000 °C exceeds 41%, showing excellent heat resistance. Figure 5 Example 3

[0087] A preparation method of a mercaptobenzimidazole-containing hyperbranched organosilicon polymer, comprising the following steps:

[0088] 1) Under nitrogen protection, add 1 mol of mercaptobenzimidazole and 3 mol of γ-glycidoxypropyltrimethoxysilane to a three-necked flask equipped with a condenser and mechanical stirrer, and stir evenly to obtain a mixed silane coupling agent;

[0089]

[0090] ​2) After mixing 1 mol of the mixed silane coupling agent obtained in step 1) with 1.5 mol of acetone evenly in a three-necked flask, add 0.1 wt% of 1,4-diazabicyclo catalyst and gradually heat up from room temperature to 100 °C at a heating rate of 20 °C / min, react for 24 h, and naturally cool to room temperature after the reaction is completed. Remove the solvent and catalyst at 50 °C using a rotary evaporator to obtain a mercaptobenzimidazole-based organosilicon monomer, which is a light yellow transparent liquid;

[0091] 3) Add 0.5 mol of the mercaptobenzimidazole-based organosilicon monomer prepared in step 2), 0.5 mol of phenyltrimethoxysilane, and 0.5 mol of deionized water to a three-necked flask equipped with a condenser and mechanical stirrer, and naturally hydrolyze at room temperature for 1 h to obtain a mixture;

[0092] 4) Mix 1 mol of the mixture prepared in step 3) evenly with 2 mol of ethyl acetate, add 10 wt% of oxalic acid catalyst, and gradually heat up to 70 °C and react for 4 h at a heating rate of 20 °C / min. Naturally cool down after the reaction is completed, and remove the solvent, catalyst, and reaction by-products at 60 °C using a rotary evaporator to obtain a mercaptobenzimidazole-containing hyperbranched organosilicon polymer, which is a light yellow transparent liquid with low viscosity and high fluidity.

[0093] Example 4

[0094] A preparation method of a mercaptobenzimidazole-containing hyperbranched organosilicon polymer, comprising the following steps:

[0095] 1) Under nitrogen protection, add 1 mol of mercaptobenzimidazole and 1.5 mol of γ-glycidoxypropyltrimethoxysilane to a three-necked flask equipped with a condenser and mechanical stirrer, and stir evenly to obtain a mixed silane coupling agent;

[0096] 2) After mixing 1 mol of the mixed silane coupling agent obtained in step 1) with 3 mol of dichloromethane evenly in a three-necked flask, add 3 wt% of 4-dimethylaminopyridine catalyst and gradually heat up from room temperature to 150 °C at a heating rate of 20 °C / min, react for 0.5 h, and naturally cool to room temperature after the reaction is completed. Remove the solvent and catalyst at 60 °C using a rotary evaporator to obtain a mercaptobenzimidazole-based organosilicon monomer, which is a light yellow transparent liquid;

[0097] 3) Add 0.3 mol of the mercaptobenzimidazole-based organosilicon monomer prepared in step 2), 0.5 mol of γ-glycidoxypropyltrimethoxysilane, 0.2 mol of methacryloxypropyltrimethoxysilane, and 2 mol of deionized water to a three-necked flask equipped with a condenser and mechanical stirrer, and naturally hydrolyze at room temperature for 1 h to obtain a mixture;

[0098] 4) Mix 1 mol of the mixture prepared in step 3) evenly with 2 mol of chloroform, add a 2 wt% trifluoroacetic acid catalyst, and gradually heat up to 90 °C for reaction for 2 h with a heating rate of 20 °C / min. After the reaction is completed, cool down naturally. Remove the solvent, catalyst, and reaction by-products at 55 °C using a rotary evaporator to obtain a mercaptobenzimidazole-based hyperbranched organosilicon polymer, which is a light yellow transparent liquid with low viscosity and high fluidity.

[0099] Example 5

[0100] A preparation method of a mercaptobenzimidazole-based hyperbranched organosilicon polymer, comprising the following steps:

[0101] 1) Under nitrogen protection, add 1.5 mol of mercaptobenzimidazole and 1 mol of γ-glycidyletheroxypropyltriethoxysilane into a three-necked flask equipped with a condenser and a mechanical stirrer, and stir evenly to obtain a mixed silane coupling agent;

[0102] 2) After mixing 1 mol of the mixed silane coupling agent obtained in step 1) evenly with 1 mol of N-methylpyrrolidone in a three-necked flask, add a 1 wt% quinuclidine catalyst and gradually heat up from room temperature to 90 °C with a heating rate of 20 °C / min. React for 12 h, and after the reaction is completed, cool down naturally to room temperature. Remove the solvent and catalyst at 60 °C using a rotary evaporator to obtain a mercaptobenzimidazole-based organosilicon monomer, which is a light yellow transparent liquid;

[0103] 3) Add 0.2 mol of the mercaptobenzimidazole-based organosilicon monomer prepared in step 2), 0.8 mol of 3-ureidopropyltrimethoxysilane, and 0.5 mol of deionized water into a three-necked flask equipped with a condenser and a mechanical stirrer, and hydrolyze naturally at room temperature for 1 h to obtain a mixture;

[0104] 4) Mix 1 mol of the mixture prepared in step 3) evenly with 3 mol of dimethyl sulfoxide, add a 0.5 wt% phosphoric acid catalyst, and gradually heat up from room temperature to 70 °C for reaction for 6 h with a heating rate of 20 °C / min. After the reaction is completed, cool down naturally to room temperature. Remove the solvent, catalyst, and reaction by-products at 70 °C using a rotary evaporator to obtain a mercaptobenzimidazole-based hyperbranched organosilicon polymer, which is a light yellow transparent liquid with low viscosity and high fluidity.

[0105] The prepared mercaptobenzimidazole-based hyperbranched organosilicon polymer is cured at 100 °C for 24 hours to form a film and its abrasion resistance is tested. The results are as Figure 7 shown.

[0106] By Figure 7It can be seen that the introduction of the urea group enhances the intermolecular force between materials, so that after the coating material is rubbed 3000 times with a wire brush, only shallow scratches are caused on the surface of the coating. The deepest part of the scratch is less than 1.5 microns, and the scratch range is small, showing excellent wear resistance.

[0107] Example 6

[0108] A preparation method of a mercaptobenzimidazole-based hyperbranched organosilicon polymer, comprising the following steps:

[0109] 1) Under nitrogen protection, 1 mol of mercaptobenzimidazole and 1 mol of γ-glycidyletheroxypropyltrimethoxysilane are added to a three-necked flask equipped with a condenser and a mechanical stirrer and stirred evenly to obtain a mixed silane coupling agent;

[0110] 2) After mixing 1 mol of the mixed silane coupling agent obtained in step 1) with 2 mol of toluene in a three-necked flask, 0.5 wt% of 1,8-diazabicycloundec-7-ene catalyst is added and the temperature is gradually raised from room temperature to 120 °C at a heating rate of 20 °C / min. The reaction is carried out for 1 h, and after the reaction is completed, it is naturally cooled to room temperature. The solvent and the catalyst are removed at 70 °C by a rotary evaporator to obtain a mercaptobenzimidazole-based organosilicon monomer, which is a light yellow transparent liquid;

[0111] 3) 0.3 mol of the mercaptobenzimidazole-based organosilicon monomer prepared in step 2), 0.4 mol of perfluorooctyltrimethoxysilane, 0.3 mol of trifluoropropyltrimethoxysilane and 1.1 mol of deionized water are added to a three-necked flask equipped with a condenser and a mechanical stirrer, and naturally hydrolyzed at room temperature for 1 h to obtain a mixture;

[0112] 4) 1 mol of the mixture prepared in step 3) is mixed evenly with 3 mol of xylene, 0.5 wt% of acetic acid catalyst is added, and the temperature is gradually raised to 70 °C and reacted for 6 h at a heating rate of 20 °C / min. After the reaction is completed, it is naturally cooled to room temperature. The solvent, the catalyst and the reaction by-products are removed at 60 °C by a rotary evaporator to obtain a mercaptobenzimidazole-based hyperbranched organosilicon polymer, which is a light yellow transparent liquid with low viscosity and high fluidity.

[0113] The prepared mercaptobenzimidazole-based hyperbranched organosilicon polymer is cured at 100 °C for 24 hours to form a film and its performance is tested. The results are as Figure 8 and Figure 9 shown.

[0114] From Figure 8It can be seen that due to the introduction of Si-O-Si bonds, the material exhibits excellent resistance to both oil and water. The contact angle of the coating with respect to oily liquids reaches 107°, and the contact angle with respect to aqueous liquids reaches 108°. Its surface energy calculated by the Owens method is only 10.88, showing good hydrophobic and oleophobic properties.

[0115] It is known from Figure 9 that the material exhibits excellent anti-graffiti ability. A water-based pen and an oil-based pen were respectively used to graffiti on the surface of the coating. After wiping with a wet tissue after intervals of 10 min, 20 min, and 30 min, it can be seen that there is no residue of the oil-based pen or water-based pen on the coating surface after wiping at different intervals, demonstrating the excellent anti-graffiti performance of the material against oily or aqueous pollutants.

[0116] Example 7

[0117] A preparation method of a mercaptobenzimidazole-based hyperbranched organosilicon polymer, comprising the following steps:

[0118] 1) Under nitrogen protection, 1 mol of mercaptobenzimidazole and 1 mol of γ-glycidoxypropyltrimethoxysilane were added to a three-necked flask equipped with a condenser and a mechanical stirrer and stirred evenly to obtain a mixed silane coupling agent;

[0119] 2) After mixing 1 mol of the mixed silane coupling agent obtained in step 1) with 3 mol of N,N-dimethylacetamide evenly in a three-necked flask, 1 wt% of 1,5-diazabicyclo[4.3.0]non-5-ene catalyst was added and the temperature was gradually raised from room temperature to 120 °C at a heating rate of 20 °C / min. The reaction was carried out for 0.5 h, and after the reaction was completed, it was naturally cooled to room temperature. The solvent and catalyst were removed at 80 °C using a rotary evaporator to obtain a mercaptobenzimidazole-based organosilicon monomer, which is a pale yellow transparent liquid;

[0120] 3) 0.3 mol of the mercaptobenzimidazole-based organosilicon monomer prepared in step 2), 0.4 mol of mercaptopropyltrimethoxysilane, 0.3 mol of chloromethyltrimethoxysilane, and 0.8 mol of deionized water were added to a three-necked flask equipped with a condenser and a mechanical stirrer, and naturally hydrolyzed at room temperature for 1 h to obtain a mixture;

[0121] 4) After mixing 1 mol of the mixture prepared in step 3) with 2 mol of N,N-dimethylformamide evenly, 1 wt% of nitric acid catalyst was added, and the temperature was gradually raised to 70 °C and reacted for 6 h at a heating rate of 20 °C / min. After the reaction was completed, it was naturally cooled to room temperature. The solvent, catalyst, and reaction by-products were removed at 80 °C using a rotary evaporator to obtain a mercaptobenzimidazole-based hyperbranched organosilicon polymer, which is a pale yellow transparent liquid with low viscosity and high fluidity.

[0122] Example 8

[0123] A preparation method of a mercaptobenzimidazole-based hyperbranched organosilicon polymer, comprising the following steps:

[0124] 1) Under nitrogen protection, 1 mol of mercaptobenzimidazole and 1 mol of γ-glycidoxypropyltrimethoxysilane are added to a three-necked flask equipped with a condenser and a mechanical stirrer and stirred evenly to obtain a mixed silane coupling agent;

[0125] 2) After mixing 1 mol of the mixed silane coupling agent obtained in step 1) with 3 mol of tetrahydrofuran evenly in a three-necked flask, 1 wt% of 1,5-diazabicyclo[4.3.0]non-5-ene catalyst is added and the temperature is gradually raised from room temperature to 120 °C at a heating rate of 20 °C / min, and the reaction is carried out for 0.5 h. After the reaction is completed, it is naturally cooled to room temperature, and the solvent and catalyst are removed at 60 °C by a rotary evaporator to obtain a mercaptobenzimidazole-based organosilicon monomer, which is a pale yellow transparent liquid;

[0126] 3) 0.3 mol of the mercaptobenzimidazole-based organosilicon monomer prepared in step 2), 0.3 mol of aminopropyltriethoxysilane, 0.4 mol of phenyltriethoxysilane and 1.3 mol of deionized water are added to a three-necked flask equipped with a condenser and a mechanical stirrer, and hydrolyzed naturally at room temperature for 1 h to obtain a mixture;

[0127] 4) 1 mol of the mixture prepared in step 3) is mixed evenly with 2 mol of dioxane, 0.3 wt% of formic acid catalyst is added, and the temperature is gradually raised to 70 °C and reacted for 4 h at a heating rate of 20 °C / min. After the reaction is completed, it is naturally cooled to room temperature, and the solvent, catalyst and reaction by-products are removed at 50 °C by a rotary evaporator to obtain a mercaptobenzimidazole-based hyperbranched organosilicon polymer, which is a pale yellow transparent liquid with low viscosity and high fluidity.

[0128] The polymer coatings obtained by curing the above-prepared mercaptobenzimidazole-based hyperbranched organosilicon polymer at 100 °C for 24 hours to form films are respectively subjected to antibacterial performance tests, antifouling performance tests and anti-corrosion performance tests, and the results are as Figures 10 - 12 shown.

[0129] From Figure 10 it can be seen that antibacterial experiments are respectively carried out on a petri dish coated with a hyperbranched organosilicon polymer coating and a petri dish without a coating. It can be seen from the test that fewer colony numbers are shown in the petri dish coated with the coating.

[0130] From Figure 11It can be seen that the anti-microbial adsorption tests were respectively carried out on the steel sheet coated with the hyperbranched organosilicon polymer coating and the uncoated steel sheet. From the tests, it can be seen that there is almost no microbial attachment on the surface of the coated steel sheet, while a large number of microorganisms appear on the surface of the uncoated steel sheet.

[0131] It is Figure 12 known that the seawater corrosion tests were respectively carried out on the steel sheet coated with the hyperbranched organosilicon polymer coating and the uncoated steel sheet. From the tests, it can be seen that after the coated steel sheet is immersed in seawater, only weak rust appears at the scratched area, and there is no obvious rust phenomenon in other areas, while a large area of rust appears on the uncoated steel sheet.

[0132] In summary, it can be seen that the mercaptobenzimidazole-based hyperbranched organosilicon polymer prepared by the above method has both long-term antibacterial properties and surface anti-pollution and anti-corrosion properties.

[0133] Comparative Example 1

[0134] Under nitrogen protection, 2 mol of mercaptobenzimidazole and 1 mol of γ-glycidoxypropyltriethoxysilane were added to a three-necked flask equipped with a condenser and a mechanical stirrer and stirred evenly to obtain a mixed silane coupling agent; after the obtained mixed silane coupling agent was mixed evenly with ethyl acetate in the three-necked flask, 10 wt% of N,N-diisopropylethylamine catalyst was added and the temperature was gradually raised to 200 °C at a heating rate of 20 °C / min, and the reaction was carried out for 0.1 h. After the reaction was completed, the temperature was naturally lowered, and the solvent and the catalyst were removed by a rotary evaporator to obtain a mercaptobenzimidazole-based organosilicon monomer, which was a light yellow transparent liquid.

[0135] The mercaptobenzimidazole-based organosilicon monomer prepared above was cured at 100 °C for 24 h and then subjected to a thermal stability test. The results are as Figure 13 shown.

[0136] It is Figure 13 known that the mercaptobenzimidazole-based silane coupling agent has poor heat resistance, the 95% thermal decomposition temperature is 330 °C, and the char residue rate at 1000 °C is only 2%.

[0137] Comparative Example 2

[0138] Under nitrogen protection, 1.5 mol of mercaptobenzimidazole and 1 mol of γ-glycidoxypropyltriethoxysilane were added to a three-necked flask equipped with a condenser and a mechanical stirrer and stirred evenly to obtain a mixed silane coupling agent; after the obtained mixed silane coupling agent was mixed evenly with N-methylpyrrolidone in the three-necked flask, 1 wt% of quinuclidine catalyst was added and the temperature was gradually raised to 90 °C at a heating rate of 20 °C / min, and the reaction was carried out for 12 h. After the reaction was completed, the temperature was naturally lowered, and the solvent and the catalyst were removed by a rotary evaporator to obtain a mercaptobenzimidazole-based organosilicon monomer, which was a light yellow transparent liquid.

[0139] The prepared mercaptobenzimidazole-based organosilicon monomer was cured at 100 °C for 24 h and then subjected to wear resistance testing. The results are as Figure 14 shown.

[0140] As Figure 14 shown in A, due to the lack of high crosslinking density brought by the hyperbranched structure, the wear resistance of the coating is extremely poor. After 3000 tests, large and obvious scratch areas appeared on the coating surface. As Figure 14 shown in B, the deepest part of the scratch exceeded 4 microns, and compared with the hyperbranched organosilicon polymer coating in Example 5, both the scratch area and the scratch depth increased significantly, indicating poor wear resistance.

[0141] Comparative Example 3

[0142] 0.4 mol of mercaptopropyltrimethoxysilane, 0.3 mol of chloromethyltrimethoxysilane, and 0.8 mol of deionized water were added to a three-necked flask equipped with a condenser and a mechanical stirrer, and naturally hydrolyzed at room temperature for 1 h to obtain a mixture; 1 mol of the prepared mixture was mixed evenly with 2 mol of N,N-dimethylformamide, 1 wt% nitric acid catalyst was added, and the temperature was gradually raised to 70 °C and reacted for 6 h at a heating rate of 20 °C / min. After the reaction was completed, it was naturally cooled to room temperature, and the solvent, catalyst, and reaction by-products were removed at 80 °C using a rotary evaporator to obtain a hyperbranched organosilicon polymer, which was a colorless transparent liquid with low viscosity and high fluidity.

[0143] The products prepared in Example 7 and Comparative Example 3 were respectively cured at 100 °C for 24 hours to form films and their properties were tested. The results are as Figure 15 and Figure 16 shown.

[0144] As Figure 15 shown, the coating prepared in Example 7 showed excellent antibacterial properties against Escherichia coli and Staphylococcus aureus, while the coating prepared in Comparative Example 3 without mercaptobenzimidazole groups had poor inhibitory effects on the proliferation of Staphylococcus aureus and Escherichia coli, indicating insufficient antibacterial and antifouling properties of the material.

[0145] As Figure 16 shown, after the coating prepared in Example 7 was immersed in Chaetoceros muelleri and Nitzschia closterium f. minutissima, there was no obvious algae attachment on the surface, showing high antifouling performance, while after the coating prepared in Comparative Example 3 was immersed in Chaetoceros muelleri and Nitzschia closterium f. minutissima for one week, a large number of algal microorganisms propagated on the surface.

[0146] Example 9

[0147] The products prepared in Examples 1-8 and Comparative Examples 1-3 were subjected to performance testing, and the results are shown in Table 1.

[0148] Table 1 Performance test results of the products prepared in Examples 1-8 and Comparative Examples 1-3

[0149]

[0150]

[0151] As can be seen from Table 1, after introducing the mercaptobenzimidazole group with excellent antibacterial and anti-aging properties, the hyperbranched organosilicon polymer is endowed with excellent antibacterial properties. In the antibacterial test, the number of residual colonies on the coating surface is significantly inhibited. The introduction of the hyperbranched structure endows the coating with more excellent wear resistance. Compared with the coating without the hyperbranched structure, after the wear resistance test, its damage area and maximum damage depth are significantly reduced. The introduction of the siloxane segment and the characteristics of high crosslinking density endow the coating material with the characteristic of low surface energy. In the mold adsorption test, no obvious mold attachment phenomenon appears on the coating surface. The above-mentioned characteristics make the prepared mercaptobenzimidazole-based hyperbranched organosilicon polymer exhibit excellent antibacterial, anti-mold and stain-resistant properties.

[0152] The above are only the preferred embodiments of the present invention. It should be pointed out that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and modifications can be made, and these improvements and modifications should also be regarded as the protection scope of the present invention.

Claims

1. A mercaptobenzimidazole-containing hyperbranched organosilicon polymer, characterized in that: The structural formula is: Wherein, R is at least one of vinyl, acryloxy, alkyl, phenyl, ureido, mercapto, sulfhydryl, amino, trifluoropropyl, perfluorooctyl, chloromethyl, and epoxy.

2. A method for preparing the mercaptobenzimidazole-containing hyperbranched organosilicon polymer according to claim 1, characterized in that: Under the protection of inert gas, a mercaptobenzimidazole-based silicone monomer, a silicone monomer containing a functional group and water are subjected to a hydrolysis reaction. After the hydrolysis is completed, an acidic catalyst and a solvent are added to carry out a temperature-raising reaction. After rotary evaporation, a mercaptobenzimidazole-containing hyperbranched silicone polymer is obtained.

3. The method for preparing the mercaptobenzimidazole-containing hyperbranched organosilicon polymer according to claim 2, characterized in that: The structural formula of the mercaptobenzimidazole-based silicone monomer is: Wherein, R1 is at least one of a methyl group and an ethyl group.

4. The method for preparing the mercaptobenzimidazole-containing hyperbranched organosilicon polymer according to claim 2, characterized in that: The organic silicon monomer containing functional groups is selected from one or more of γ-glycidyloxypropyltrimethoxysilane, methyltrimethoxysilane, phenyltrimethoxysilane, methacryloxypropyltrimethoxysilane, 3-ureidopropyltrimethoxysilane, perfluorooctyltrimethoxysilane, trifluoropropyltrimethoxysilane, mercaptopropyltrimethoxysilane, chloromethyltrimethoxysilane, aminopropyltriethoxysilane and phenyltriethoxysilane.

5. The method for preparing the mercaptobenzimidazole-containing hyperbranched organosilicon polymer according to claim 2, characterized in that: The acidic catalyst is selected from one or more of formic acid, acetic acid, hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, trifluoroacetic acid, and oxalic acid.

6. The method for preparing the mercaptobenzimidazole-containing hyperbranched organosilicon polymer according to claim 2, characterized in that: The solvent is selected from one or more of methanol, ethanol, toluene, xylene, ethyl acetate, methyl acetate, tetrahydrofuran, dioxane, dichloromethane, chloroform, N,N-dimethylformamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetone, and butanone.

7. The method for preparing the mercaptobenzimidazole-containing hyperbranched organosilicon polymer according to claim 3, characterized in that: The preparation process of the mercaptobenzimidazole-based silicone monomer is as follows: under nitrogen protection, mercaptobenzimidazole and a silane coupling agent containing a glycidyl ether group are mixed in a molar ratio of 1:3 to 2:1 to obtain a mixed silane coupling agent; the obtained mixed silane coupling agent, a solvent and an alkaline catalyst are reacted, and the mercaptobenzimidazole-based silicone monomer is obtained by cooling and rotary evaporation.

8. The method for preparing the mercaptobenzimidazole-containing hyperbranched organosilicon polymer according to claim 2, characterized in that: The molar ratio of the mercaptobenzimidazole-based silicone monomer, the silicone monomer containing a functional group and water is 0.1-0.9:0.9-0.1:0.5-2.

9. The method for preparing a mercaptobenzimidazole-containing hyperbranched organosilicon polymer according to any one of claims 2 to 8, wherein the mercaptobenzimidazole-containing hyperbranched organosilicon polymer is prepared.

10. Use of the mercaptobenzimidazole-containing hyperbranched organosilicon polymer according to claim 9 in antibacterial and antifouling coatings.

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