Wear-resistant and antibacterial composite material for rubber stopper and preparation method thereof

Abstract

The present invention provides a wear-resistant and antibacterial composite material for rubber stoppers and a preparation method thereof, which belongs to the technical field of rubber preparation; the preparation process thereof comprises the following steps: preparation of surface-modified carbon-coated silver particles; preparation of a composite antibacterial agent; intercalation modification of zirconium phosphate; preparation of a hydrophobic antibacterial rubber stopper wear-resistant coating; and preparation of a wear-resistant and antibacterial composite material. The N-substituted benzisothiazolinone compound synthesized by the present invention has good antibacterial activity, and the N-substituted benzisothiazolinone compound reacts chemically with active groups such as amino groups of 3-aminopropyltriethoxysilane on the surface-modified carbon-coated silver particles to achieve grafting to prepare a composite antibacterial agent, the composite antibacterial agent is used to prepare a rubber stopper, and the surface of the rubber stopper is sprayed with a hydrophobic antibacterial and wear-resistant coating, and the prepared composite material has good wear-resistant and antibacterial effects.

Description

Technical Field

[0001] The present invention relates to the technical field of rubber preparation, and in particular to a wear-resistant and antibacterial composite material for rubber stoppers and a preparation method thereof. Background Art

[0002] As a key component for sealing various containers, rubber stoppers play an indispensable role in numerous industries, including the chemical and cosmetics industries. Whether it's a glass bottle containing corrosive chemicals or a delicate container for high-end skincare products, rubber stoppers shoulder the important task of isolating the internal and external environments and maintaining the stability of the contents. Their performance is closely linked to product quality, safety, and shelf life, making the research and development of rubber stopper materials a highly sought-after topic in related fields.

[0003] Traditional rubber stoppers are often made from mainstream materials such as natural rubber, nitrile rubber, and silicone rubber. Natural rubber, with its excellent elasticity and flexibility, adapts well to various container openings, creating a tight seal. Nitrile rubber, with its oil and solvent resistance, performs well in the chemical industry against various chemical corrosion. Silicone rubber, with its high and low temperature resistance and good biocompatibility, has a certain market share in pharmaceutical and food packaging. However, rubber stoppers made from these traditional materials have significant shortcomings in terms of wear resistance and antibacterial properties.

[0004] In actual working conditions, frequent plugging and unplugging and friction are common. For example, in chemical experiments, reagent bottle stoppers are frequently used to take out reagents, or cosmetic samples are frequently opened and tried, resulting in stopper wear, and pressure fluctuations inside high-pressure containers frequently impacting rubber stoppers. These situations will make ordinary rubber stoppers overwhelmed, and wear marks will easily appear on the surface. In severe cases, they may even tear and deform, causing the sealing performance to plummet, resulting in leakage of substances in the container, bringing safety hazards and product losses.

[0005] At the same time, microbial contamination is like a hidden "time bomb" that constantly threatens product quality. During long-term storage, especially in a humid environment with high humidity, rubber stoppers are prone to absorbing water vapor due to their inherent hydrophilicity. In addition, the extremely small amount of nutrient-rich organic matter remaining on the rubber surface during the production and processing process together constitutes a "habitable paradise" in the eyes of microorganisms. Bacteria, fungi and other microorganisms rapidly multiply here. They not only erode the rubber stopper itself, damaging its structural strength and accelerating aging, but also penetrate the tiny pores of the rubber stopper over time, invading the interior of the container, contaminating the contents, significantly shortening the shelf life of the product, and causing a devastating blow to product quality.

[0006] While existing rubber stopper materials have made numerous attempts to address these issues, success has been limited. Conventional rubber formulation improvements often focus on improving a single property. For example, simply adding fillers like carbon black to enhance wear resistance sacrifices rubber flexibility, compromising sealing effectiveness. Adding antimicrobial agents often results in poor compatibility with the rubber matrix, leading to precipitation and agglomeration, weakening the antimicrobial's durability.

[0007] Therefore, we proposed a wear-resistant and antibacterial composite material for rubber stoppers that has both excellent wear resistance and high-efficiency antibacterial properties and a preparation method thereof. Summary of the Invention

[0008] In view of the shortcomings of the prior art, the object of the present invention is to provide a wear-resistant and antibacterial composite material for rubber stoppers and a preparation method thereof.

[0009] A method for preparing a wear-resistant and antibacterial composite material for a rubber stopper comprises the following steps:

[0010] S1: Preparation of surface-modified carbon-coated silver particles, using silver nitrate and glucose as raw materials to prepare carbon-coated silver particles, and then using 3-aminopropyltriethoxysilane to modify the surface of the carbon-coated silver particles to obtain a dispersion of surface-modified carbon-coated silver particles;

[0011] S2: Preparation of a composite antibacterial agent, comprising reacting benzisothiazolinone, potassium carbonate, N,N-dimethylformamide, and 1,3-dibromo-2-propanol, followed by purification to prepare an N-substituted benzisothiazolinone compound, and grafting the N-substituted benzisothiazolinone compound onto surface-modified carbon-coated silver particles to obtain a composite antibacterial agent;

[0012] S3: Intercalation modification of zirconium phosphate, using tetrabutyl titanate and polyethyleneimine to intercalate zirconium phosphate to obtain intercalation-modified zirconium phosphate;

[0013] S4: Preparation of a hydrophobic, antibacterial, and wear-resistant coating: polydimethylsiloxane, dilute sulfuric acid, ethyl orthosilicate, and silica nanoparticles are mixed, vinyl-substituted polysilsesquioxane and intercalated modified zirconium phosphate are added, and ultrasonic dispersion is performed to obtain a hydrophobic, antibacterial, and wear-resistant coating;

[0014] S5: Preparation of wear-resistant and antibacterial composite materials. Bromobutyl rubber, ethylene-ethyl acrylate copolymer, polyisobutylene, stearic acid, zinc oxide, sulfur, calcined kaolin, 2,2'-dibenzothiazole disulfide, 2,6-di-tert-butyl-p-cresol and composite antibacterial agent are added to an internal mixer for mixing, and then vulcanized to prepare a rubber stopper material. The rubber stopper material is plasma treated to obtain a pretreated rubber stopper material, and a hydrophobic, antibacterial and wear-resistant coating is sprayed on the surface of the pretreated rubber stopper material. After curing, a wear-resistant and antibacterial composite material is obtained.

[0015] Furthermore, the preparation of the surface-modified carbon-coated silver particles in step S1 specifically includes the following steps:

[0016] S1.1: Add 4-5 parts by weight of a 0.3-0.5 mol / L silver nitrate solution to 80-90 parts by weight of a 0.5 mol / L glucose aqueous solution. Transfer the solution into a polytetrafluoroethylene liner and ultrasonically disperse for 10-20 minutes. Place the solution in a sealed reactor and react at 200-300°C for 5-6 hours. Cool to room temperature, centrifuge, wash, and then dry at 40-50°C for 10-12 hours to obtain carbon-encapsulated silver particles.

[0017] S1.4: Disperse 3-5 parts by weight of carbon-wrapped silver particles in 10-15 parts by weight of ethanol, and ultrasonically disperse for 30-60 minutes to obtain a carbon-wrapped silver particle dispersion. Add 0.3-0.5 parts by weight of 3-aminopropyltriethoxysilane to the carbon-wrapped silver particle dispersion, and stir and react at 60-80°C under nitrogen protection for 4-6 hours. After the reaction is completed, wash the product with anhydrous ethanol 2-3 times and centrifuge to obtain surface-modified carbon-wrapped silver particles. Re-disperse the obtained surface-modified carbon-wrapped silver particles in 10-15 parts by weight of ethanol, and ultrasonically disperse for 30-60 minutes to obtain a surface-modified carbon-wrapped silver particle dispersion.

[0018] Furthermore, step S2 of preparing the composite antibacterial agent specifically includes the following steps:

[0019] S2.1: 3-5 parts by weight of benzisothiazolinone and 2-3 parts by weight of potassium carbonate were mixed, 20-30 parts by weight of N,N-dimethylformamide were added, and the mixture was stirred at 400-500 r / min for 20-30 min. Then, 2-2.3 parts by weight of 1,3-dibromo-2-propanol were added, and the mixture was reacted at 70-73°C for 14-15 h to obtain a reaction solution;

[0020] S2.2: Cool the reaction solution to room temperature, then add 40-50 parts by weight of deionized water, and extract with ethyl acetate to obtain an organic solution. Dry the organic solution over anhydrous sodium sulfate, and then filter and collect the filtrate. Rotary evaporate the filtrate and purify it using a chromatography column with a dichloromethane:ethyl acetate ratio of 1:1 to obtain an N-substituted benzisothiazolinone compound.

[0021] S2.3: Add 2-3 parts by weight of an N-substituted benzisothiazolinone compound to 10-12 parts by weight of tetrahydrofuran, stir and mix for 20-30 minutes, then add 0.3-0.5 parts by weight of triethylamine, and stir and react at room temperature for 30-60 minutes to obtain a mixed solution;

[0022] S2.4: Add 3-5 parts by weight of the mixed liquid to 10-12 parts by weight of a dispersion of surface-modified carbon-coated silver particles, and stir the reaction at 50-70°C under nitrogen protection for 12-24 hours. After the reaction is completed, wash the product with anhydrous ethanol 2-3 times, centrifuge it, and place it in a vacuum drying oven at 60-80°C for 12-24 hours to obtain a composite antibacterial agent.

[0023] Furthermore, the structure of the N-substituted benzisothiazolinone compound in step S2.2 is:

[0024]

[0025] Furthermore, step S3 of intercalation modification of zirconium phosphate specifically includes the following steps:

[0026] S3.1: Add 4-5 parts by weight of zirconium oxychloride to 6-8 parts by weight of deionized water, and stir for 3-5 minutes to obtain a zirconium oxychloride aqueous solution. Add 8-10 parts by weight of phosphoric acid to 17-20 parts by weight of deionized water, and stir for 5-10 minutes to obtain a phosphoric acid solution. Add 2-3 parts by weight of polyethyleneimine to 10-12 parts by weight of deionized water, and stir for 3-5 minutes to obtain a polyethyleneimine aqueous solution.

[0027] S3.2: Add 0.06-0.08 parts by weight of tetrabutyl titanate to 5-8 parts by weight of deionized water, stir and mix, then add polyethyleneimine aqueous solution, stir for 3-5 minutes to obtain a mixed solution, then mix the zirconium oxychloride aqueous solution and the phosphoric acid solution and add them to the mixed solution, stir and mix at 700-800 r / min for 20-30 minutes, place the obtained solution in a reactor and place it in an oven at 180-200°C to react for 24-25 hours, then wash the product with distilled water 2-3 times and with anhydrous ethanol 2-3 times, and obtain intercalated modified zirconium phosphate after centrifugal drying.

[0028] Furthermore, step S5 of preparing the wear-resistant and antibacterial rubber stopper composite material specifically includes the following steps:

[0029] S5.1: Prepare the following raw materials: 100-120 parts by weight of brominated butyl rubber, 20-30 parts by weight of ethylene-ethyl acrylate copolymer, 2-3 parts by weight of polyisobutylene, 2-3 parts by weight of stearic acid, 3-5 parts by weight of zinc oxide, 0.2-0.3 parts by weight of sulfur, 20-30 parts by weight of calcined kaolin, 1-2 parts by weight of 2,2'-dibenzothiazole disulfide, and 1-2 parts by weight of 2,6-di-tert-butyl-p-cresol;

[0030] S5.2: Add the above raw materials and 4-8 parts by weight of the composite antibacterial agent to an internal mixer and mix at 100-110°C for 10-12 minutes to obtain a rubber compound. Cool the rubber compound to below 50-60°C, then roll it and store it for 24-48 hours. Sheet it using an open mixer at 75-80°C, then cool it to 20-25°C and slice it to obtain a rubber sheet. Place the rubber sheet in the cavity of a vulcanization mold and vulcanize it at 170-180°C and 15-18 MPa for 3-5 minutes to produce a rubber stopper material.

[0031] S5.3: Place the rubber stopper material in a plasma treatment device for plasma treatment to obtain a pretreated rubber stopper material, spray a hydrophobic, antibacterial, and wear-resistant coating on the surface of the pretreated rubber stopper material, and then cure it at room temperature for 10-12 minutes to obtain a wear-resistant and antibacterial rubber stopper composite material after curing.

[0032] Furthermore, nitrogen gas is used for plasma treatment in S5.3.

[0033] A wear-resistant and antibacterial composite material for rubber stoppers is prepared by any of the methods for preparing a wear-resistant and antibacterial composite material for rubber stoppers.

[0034] Compared with the prior art, the present invention has at least the following beneficial effects:

[0035] 1. The N-substituted benzisothiazolinone compound synthesized in the present invention has good antibacterial activity. The isothiazolinone ring in its molecular structure is the key part of the antibacterial activity and can inhibit the growth and reproduction of microorganisms by interacting with microbial cells. In addition, the N-substituted benzisothiazolinone compound chemically reacts with active groups such as amino groups of 3-aminopropyltriethoxysilane on the surface-modified carbon-coated silver particles to achieve grafting. After grafting modification, the carbon-coated silver particles themselves also have certain antibacterial properties. Silver ions can combine with biomacromolecules such as proteins and nucleic acids of microorganisms to destroy the normal physiological functions of microorganisms. Therefore, the combination of the two can produce a synergistic antibacterial effect, so that the composite antibacterial agent has a stronger inhibitory and killing ability against a variety of bacteria, fungi and other microorganisms. At the same time, the carbon-coated silver particles themselves have high strength and hardness. When the composite antibacterial agent is dispersed in the rubber stopper composite material, the carbon-coated silver particles can withstand part of the external force, reduce the deformation and damage of the rubber stopper composite material, and make it difficult to wear the surface during repeated plugging or friction, thereby maintaining the sealing and integrity of the rubber stopper composite material. The 3-aminopropyltriethoxysilane on the surface-modified carbon-coated silver particles can improve the compatibility with the rubber matrix. At the same time, the silane molecules on the surface of the carbon-coated silver particles can increase the steric hindrance between the particles and prevent excessive aggregation between the particles, so that they are evenly dispersed in the rubber matrix, thereby achieving antibacterial persistence.

[0036] 2. The present invention forms titanium dioxide nanoparticles during the hydrolysis of tetrabutyl titanate. These nanoparticles can be inserted into the interlayer of zirconium phosphate to increase the interlayer spacing. Polyethyleneimine is a high molecular weight cationic polymer with good hydrophilicity and adsorption properties. The larger interlayer spacing is conducive to the interaction between polyethyleneimine and the anion layer of zirconium phosphate, thereby realizing the intercalation modification of titanium dioxide and polyethyleneimine into zirconium phosphate. Titanium dioxide has photocatalytic antibacterial properties. Under light conditions, its surface will produce active oxygen species such as hydroxyl radicals and superoxide anion radicals with strong oxidizing properties. These active oxygen species can destroy the cell membranes and cells of bacteria. The cell wall and the internal biological macromolecules, thereby playing a bactericidal role. Polyethyleneimine has certain antibacterial properties. The amino group in its molecular structure can interact with the cell membrane of microorganisms and destroy the normal physiological functions of microorganisms. When polyethyleneimine and titanium dioxide are modified by intercalation into the zirconium phosphate structure, they can give zirconium phosphate antibacterial activity, and polyethyleneimine can form strong interactions with zirconium phosphate and titanium dioxide, such as hydrogen bonds, electrostatic effects, etc., further enhancing the stability of the intercalation structure, making it difficult for the composite material to slip between layers and structural damage when subjected to external friction, thereby improving the wear resistance of the composite material.

[0037] 3. The present invention uses dilute sulfuric acid as a catalyst to prepare an organosilicon polymer through the co-hydrolysis and condensation reaction of polydimethylsiloxane and ethyl orthosilicate, and then adds silica nanoparticles, intercalation-modified zirconium phosphate and vinyl-substituted polysilsesquioxane. The prepared hydrophobic, antibacterial and wear-resistant coating has good antibacterial, hydrophobic and wear-resistant effects. The silica nanoparticles added to the coating have a large specific surface area and can adsorb bacteria and restrict their activity. The intercalation-modified zirconium phosphate itself has antibacterial activity and can inhibit and kill adsorbed bacteria. The presence of silica nanoparticles can increase the contact opportunity between bacteria and zirconium phosphate, effectively reducing the risk of bacterial infection during use, and the organosilicon polymer has low surface energy. The characteristics of the coating, as one of the main ingredients in the coating, can significantly reduce the surface energy of the rubber stopper composite material. When the rubber stopper composite material is coated with the coating, it is difficult for water molecules to spread and adhere to its surface, so that the rubber stopper composite material has good hydrophobicity, effectively preventing the penetration and adsorption of liquids such as water and blood, and reducing the bacterial growth and corrosion problems caused by liquid residue. The silica nanoparticles have high hardness and rigidity, and the intercalated modified zirconium phosphate has high hardness and strength. When the rubber stopper composite material rubs against other objects during use, the coating can better resist wear, reduce scratches and wear on the surface of the rubber stopper composite material, and extend the service life of the rubber stopper composite material.

[0038] 4. The present invention introduces vinyl-substituted polysilsesquioxane into the hydrophobic, antibacterial, and wear-resistant coating as a highly active component that enhances structural stability and adhesion. The vinyl-substituted polysilsesquioxane can undergo a cross-linking reaction with the active groups on the surface of the intercalated modified zirconium phosphate, thereby better fixing the zirconium phosphate in the coating network structure and enhancing its bonding with the coating system. At the same time, the cross-linked structure also makes the coating less likely to suffer internal structural damage when subjected to friction, thereby improving wear resistance. In addition, the vinyl-substituted polysilsesquioxane can also enhance the adhesion between the hydrophobic, antibacterial, and wear-resistant coating and the substrate surface and its own physicochemical stability, thereby achieving a long-lasting hydrophobic, antibacterial, and wear-resistant effect. BRIEF DESCRIPTION OF THE DRAWINGS

[0039] The accompanying drawings, which are incorporated herein and constitute a part of the specification, illustrate embodiments of the invention and, together with the description, further serve to explain the principles of the invention and to enable one skilled in the art to make and use the invention.

[0040] Figure 1 This is a flow chart of a method for preparing a wear-resistant and antibacterial composite material for rubber stoppers used in an embodiment of the present invention. DETAILED DESCRIPTION

[0041] The following is a detailed description of the preparation method of a wear-resistant and antibacterial composite material for rubber stoppers provided by the present invention, in conjunction with the accompanying drawings and specific embodiments. It is also noted that, in order to make the embodiments more detailed, the following embodiments are the best and preferred embodiments, and those skilled in the art may also adopt other alternative methods for implementing some known technologies; and the accompanying drawings are only for more specific description of the embodiments, and are not intended to specifically limit the present invention.

[0042] N-substituted benzisothiazolinone compound structure:

[0043]

[0044] Example 1

[0045] A method for preparing a wear-resistant and antibacterial composite material for a rubber stopper, such as Figure 1 As shown, the following steps are included:

[0046] S1: Preparation of surface-modified carbon-coated silver particles

[0047] S1.1: 4 parts by weight of a 0.3 mol / L silver nitrate solution was added to 80 parts by weight of a 0.5 mol / L glucose aqueous solution. The solution was then transferred to a polytetrafluoroethylene liner and ultrasonically dispersed for 10 minutes. The mixture was then placed in a sealed reactor and reacted at 200°C for 5 hours. After cooling to room temperature, the mixture was centrifuged, washed, and dried at 40°C for 10 hours to obtain carbon-encapsulated silver particles.

[0048] S1.4: 3 parts by weight of carbon-coated silver particles were dispersed in 10 parts by weight of ethanol, and ultrasonically dispersed for 30 minutes to obtain a carbon-coated silver particle dispersion. 0.3 parts by weight of 3-aminopropyltriethoxysilane was added to the carbon-coated silver particle dispersion, and the mixture was stirred at 60° C. for 4 hours under nitrogen protection. After the reaction, the product was washed twice with anhydrous ethanol and centrifuged to obtain surface-modified carbon-coated silver particles. The obtained surface-modified carbon-coated silver particles were redispersed in 10 parts by weight of ethanol and ultrasonically dispersed for 30 minutes to obtain a surface-modified carbon-coated silver particle dispersion.

[0049] S2: Preparation of composite antimicrobial agents

[0050] S2.1: 3 parts by weight of benzisothiazolinone and 2 parts by weight of potassium carbonate were mixed, 20 parts by weight of N,N-dimethylformamide were added, and the mixture was stirred at 400 r / min for 20 minutes. Then, 2 parts by weight of 1,3-dibromo-2-propanol was added, and the mixture was reacted at 70°C for 14 hours to obtain a reaction solution;

[0051] S2.2: The reaction solution is cooled to room temperature, and then 40 parts by weight of deionized water is added, followed by extraction with ethyl acetate to obtain an organic solution. The organic solution is dried over anhydrous sodium sulfate, and the filtrate is collected by filtration. The filtrate is rotary evaporated and purified using a chromatography column with a dichloromethane:ethyl acetate ratio of 1:1 to obtain an N-substituted benzisothiazolinone compound;

[0052] S2.3: Add 2 parts by weight of an N-substituted benzisothiazolinone compound to 10 parts by weight of tetrahydrofuran, stir and mix for 20 minutes, then add 0.3 parts by weight of triethylamine, and stir and react at room temperature for 30 minutes to obtain a mixed solution;

[0053] S2.4: Add 3 parts by weight of the mixed solution to 10 parts by weight of a dispersion of surface-modified carbon-coated silver particles, and stir the mixture at 50°C for 12 hours under nitrogen. After the reaction, wash the product twice with anhydrous ethanol, centrifuge it, and dry it in a vacuum drying oven at 60°C for 12 hours to obtain a composite antibacterial agent;

[0054] S3: Intercalation modification of zirconium phosphate

[0055] S3.1: 4 parts by weight of zirconium oxychloride were added to 6 parts by weight of deionized water, and the mixture was stirred for 3 minutes to obtain a zirconium oxychloride aqueous solution. 8 parts by weight of phosphoric acid were added to 17 parts by weight of deionized water, and the mixture was stirred for 5 minutes to obtain a phosphoric acid solution. 2 parts by weight of polyethyleneimine were added to 10 parts by weight of deionized water, and the mixture was stirred for 3 minutes to obtain a polyethyleneimine aqueous solution.

[0056] S3.2: Add 0.06 parts by weight of tetrabutyl titanate to 5 parts by weight of deionized water, stir and mix, then add polyethyleneimine aqueous solution, stir for 3 minutes to obtain a mixed solution, then mix zirconium oxychloride aqueous solution and phosphoric acid solution and add them to the mixed solution, stir and mix at 700 rpm for 20 minutes, place the obtained solution in a reactor and place it in an oven at 180°C to react for 24 hours, then wash the product twice with distilled water and twice with anhydrous ethanol, and centrifuge and dry to obtain intercalated modified zirconium phosphate;

[0057] S4: Preparation of hydrophobic, antibacterial and wear-resistant coatings

[0058] S4.1: 5 parts by weight of polydimethylsiloxane was added to 20 parts by weight of ethanol, followed by the addition of 2% dilute sulfuric acid, and the reaction was allowed to proceed for 3 hours. Then, 1 part by weight of ethyl orthosilicate was added, and the reaction was allowed to proceed for 3 hours. After the reaction, 1 part by weight of silica nanoparticles was added, and the mixture was stirred for 20 minutes to obtain a composite organosiloxane suspension.

[0059] S4.2: Add 1 part by weight of vinyl-substituted polysilsesquioxane to the composite organosiloxane suspension, ultrasonically disperse for 20 minutes, then add 0.2 parts by weight of intercalated modified zirconium phosphate and ultrasonically disperse for 10 hours to obtain a hydrophobic, antibacterial, and wear-resistant coating;

[0060] S5: Preparation of wear-resistant and antibacterial rubber stopper composite materials

[0061] S5.1: Prepare the following raw materials: 100 parts by weight of brominated butyl rubber, 20 parts by weight of ethylene-ethyl acrylate copolymer, 2 parts by weight of polyisobutylene, 2 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 0.2 parts by weight of sulfur, 20 parts by weight of calcined kaolin, 1 part by weight of 2,2'-dibenzothiazole disulfide, and 1 part by weight of 2,6-di-tert-butyl-p-cresol;

[0062] S5.2: The above raw materials and 4 parts by weight of the composite antimicrobial agent are added to an internal mixer and mixed at 100°C for 10 minutes to obtain a rubber compound. The rubber compound is cooled to below 50°C, rolled, stored for 24 hours, and sheeted using an open mixer at 75°C. The rubber compound is then cooled to 20°C and sliced ​​to obtain a rubber sheet. The rubber sheet is placed in the cavity of a vulcanization mold and vulcanized at 170°C and 15 MPa for 3 minutes to produce a rubber stopper material.

[0063] S5.3: Place the rubber stopper material in a plasma treatment device and perform plasma treatment with nitrogen to obtain a pretreated rubber stopper material. Spray a hydrophobic, antibacterial, and wear-resistant coating on the surface of the pretreated rubber stopper material, and then cure it at room temperature for 10 minutes to obtain a wear-resistant and antibacterial rubber stopper composite material.

[0064] Example 2

[0065] A method for preparing a wear-resistant and antibacterial composite material for a rubber stopper, such as Figure 1 As shown, the following steps are included:

[0066] S1: Preparation of surface-modified carbon-coated silver particles

[0067] S1.1: 4 parts by weight of a 0.3 mol / L silver nitrate solution was added to 80 parts by weight of a 0.5 mol / L glucose aqueous solution. The solution was then transferred to a polytetrafluoroethylene liner and ultrasonically dispersed for 20 minutes. The mixture was then placed in a sealed reactor and reacted at 300°C for 6 hours. After cooling to room temperature, the mixture was centrifuged, washed, and dried at 50°C for 12 hours to obtain carbon-encapsulated silver particles.

[0068] S1.4: 3 parts by weight of carbon-coated silver particles were dispersed in 10 parts by weight of ethanol and ultrasonically dispersed for 60 minutes to obtain a carbon-coated silver particle dispersion. 0.3 parts by weight of 3-aminopropyltriethoxysilane was added to the carbon-coated silver particle dispersion. The mixture was stirred and reacted at 80° C. under nitrogen for 6 hours. After the reaction, the product was washed three times with anhydrous ethanol and centrifuged to obtain surface-modified carbon-coated silver particles. The surface-modified carbon-coated silver particles were redispersed in 10 parts by weight of ethanol and ultrasonically dispersed for 60 minutes to obtain a surface-modified carbon-coated silver particle dispersion.

[0069] S2: Preparation of composite antimicrobial agents

[0070] S2.1: 3 parts by weight of benzisothiazolinone and 2 parts by weight of potassium carbonate were mixed, 20 parts by weight of N,N-dimethylformamide were added, and the mixture was stirred at 500 r / min for 30 minutes. Then, 2 parts by weight of 1,3-dibromo-2-propanol was added, and the mixture was reacted at 73°C for 15 hours to obtain a reaction solution;

[0071] S2.2: The reaction solution is cooled to room temperature, and then 40 parts by weight of deionized water is added, followed by extraction with ethyl acetate to obtain an organic solution. The organic solution is dried over anhydrous sodium sulfate, and the filtrate is collected by filtration. The filtrate is rotary evaporated and purified using a chromatography column with a dichloromethane:ethyl acetate ratio of 1:1 to obtain an N-substituted benzisothiazolinone compound;

[0072] S2.3: Add 2 parts by weight of an N-substituted benzisothiazolinone compound to 10 parts by weight of tetrahydrofuran, stir and mix for 30 minutes, then add 0.3 parts by weight of triethylamine, and stir and react at room temperature for 60 minutes to obtain a mixed solution;

[0073] S2.4: Add 3 parts by weight of the mixed solution to 10 parts by weight of a dispersion of surface-modified carbon-coated silver particles, and stir under nitrogen at 70°C for 24 hours. After the reaction, wash the product three times with anhydrous ethanol, centrifuge, and dry it in a vacuum drying oven at 80°C for 24 hours to obtain a composite antibacterial agent;

[0074] S3: Intercalation modification of zirconium phosphate

[0075] S3.1: 4 parts by weight of zirconium oxychloride were added to 6 parts by weight of deionized water, and the mixture was stirred for 5 minutes to obtain a zirconium oxychloride aqueous solution. 8 parts by weight of phosphoric acid were added to 17 parts by weight of deionized water, and the mixture was stirred for 10 minutes to obtain a phosphoric acid solution. 2 parts by weight of polyethyleneimine were added to 10 parts by weight of deionized water, and the mixture was stirred for 5 minutes to obtain a polyethyleneimine aqueous solution.

[0076] S3.2: Add 0.06 parts by weight of tetrabutyl titanate to 5 parts by weight of deionized water, stir and mix, then add polyethyleneimine aqueous solution, stir for 5 minutes to obtain a mixed solution, then mix zirconium oxychloride aqueous solution and phosphoric acid solution and add them to the mixed solution, stir and mix at 800 rpm for 30 minutes, place the obtained solution in a reactor and place it in an oven at 200°C to react for 25 hours, then wash the product with distilled water three times and anhydrous ethanol three times, and centrifuge and dry to obtain intercalated modified zirconium phosphate;

[0077] S4: Preparation of hydrophobic, antibacterial and wear-resistant coatings

[0078] S4.1: 5 parts by weight of polydimethylsiloxane was added to 20 parts by weight of ethanol, followed by the addition of 2% dilute sulfuric acid, and the reaction was allowed to proceed for 5 hours. Then, 1 part by weight of ethyl orthosilicate was added, and the reaction was allowed to proceed for 5 hours. After the reaction, 1 part by weight of silica nanoparticles was added, and the mixture was stirred for 30 minutes to obtain a composite organosiloxane suspension.

[0079] S4.2: Add 1 part by weight of vinyl-substituted polysilsesquioxane to the composite organosiloxane suspension, ultrasonically disperse for 30 minutes, then add 0.2 parts by weight of intercalated modified zirconium phosphate and ultrasonically disperse for 12 hours to obtain a hydrophobic, antibacterial, and wear-resistant coating;

[0080] S5: Preparation of wear-resistant and antibacterial rubber stopper composite materials

[0081] S5.1: Prepare the following raw materials: 100 parts by weight of brominated butyl rubber, 20 parts by weight of ethylene-ethyl acrylate copolymer, 2 parts by weight of polyisobutylene, 2 parts by weight of stearic acid, 3 parts by weight of zinc oxide, 0.2 parts by weight of sulfur, 20 parts by weight of calcined kaolin, 1 part by weight of 2,2'-dibenzothiazole disulfide, and 1 part by weight of 2,6-di-tert-butyl-p-cresol;

[0082] S5.2: The above raw materials and 4 parts by weight of the composite antimicrobial agent are added to an internal mixer and mixed at 110°C for 12 minutes to obtain a rubber compound. The rubber compound is cooled to below 60°C, rolled, stored for 48 hours, and sheeted using an open mixer at 80°C. The rubber compound is then cooled to 25°C and sliced ​​to obtain a rubber sheet. The rubber sheet is placed in the cavity of a vulcanization mold and vulcanized at 180°C and 18 MPa for 5 minutes to produce a rubber stopper material.

[0083] S5.3: Place the rubber stopper material in a plasma treatment device and perform plasma treatment with nitrogen to obtain a pretreated rubber stopper material. Spray a hydrophobic, antibacterial, and wear-resistant coating on the surface of the pretreated rubber stopper material, and then cure it at room temperature for 12 minutes to obtain a wear-resistant and antibacterial rubber stopper composite material.

[0084] Example 3

[0085] A method for preparing a wear-resistant and antibacterial composite material for a rubber stopper, such as Figure 1 As shown, the following steps are included:

[0086] S1: Preparation of surface-modified carbon-coated silver particles

[0087] S1.1: 5 parts by weight of a 0.5 mol / L silver nitrate solution was added to 90 parts by weight of a 0.5 mol / L glucose aqueous solution. The solution was then transferred to a polytetrafluoroethylene liner and ultrasonically dispersed for 10 minutes. The mixture was then placed in a sealed reactor and reacted at 200°C for 5 hours. After cooling to room temperature, the mixture was centrifuged, washed, and dried at 40°C for 10 hours to obtain carbon-encapsulated silver particles.

[0088] S1.4: Dispersing 5 parts by weight of carbon-coated silver particles in 15 parts by weight of ethanol and ultrasonically dispersing for 30 minutes to obtain a carbon-coated silver particle dispersion, adding 0.5 parts by weight of 3-aminopropyltriethoxysilane to the carbon-coated silver particle dispersion, and stirring and reacting at 60°C under nitrogen for 4 hours. After the reaction, washing the product twice with anhydrous ethanol and centrifuging to obtain surface-modified carbon-coated silver particles, and redispersing the obtained surface-modified carbon-coated silver particles in 15 parts by weight of ethanol and ultrasonically dispersing for 30-60 minutes to obtain a surface-modified carbon-coated silver particle dispersion;

[0089] S2: Preparation of composite antimicrobial agents

[0090] S2.1: 5 parts by weight of benzisothiazolinone and 3 parts by weight of potassium carbonate were mixed, 30 parts by weight of N,N-dimethylformamide were added, and the mixture was stirred at 400 r / min for 20 minutes. Then, 2.3 parts by weight of 1,3-dibromo-2-propanol was added, and the mixture was reacted at 70°C for 14 hours to obtain a reaction solution;

[0091] S2.2: The reaction solution is cooled to room temperature, and then 50 parts by weight of deionized water is added, followed by extraction with ethyl acetate to obtain an organic solution. The organic solution is dried over anhydrous sodium sulfate, and the filtrate is collected by filtration. The filtrate is rotary evaporated and purified using a chromatography column with a dichloromethane:ethyl acetate ratio of 1:1 to obtain an N-substituted benzisothiazolinone compound;

[0092] S2.3: Add 3 parts by weight of an N-substituted benzisothiazolinone compound to 12 parts by weight of tetrahydrofuran, stir and mix for 20 minutes, then add 0.5 parts by weight of triethylamine, and stir and react at room temperature for 30 minutes to obtain a mixed solution;

[0093] S2.4: Add 5 parts by weight of the mixed solution to 12 parts by weight of a dispersion of surface-modified carbon-coated silver particles, and stir the mixture at 50°C for 12 hours under nitrogen. After the reaction, wash the product twice with anhydrous ethanol, centrifuge it, and dry it in a vacuum drying oven at 60°C for 12 hours to obtain a composite antibacterial agent;

[0094] S3: Intercalation modification of zirconium phosphate

[0095] S3.1: 5 parts by weight of zirconium oxychloride were added to 8 parts by weight of deionized water, and the mixture was stirred for 3 minutes to obtain a zirconium oxychloride aqueous solution. 10 parts by weight of phosphoric acid were added to 20 parts by weight of deionized water, and the mixture was stirred for 5 minutes to obtain a phosphoric acid solution. 3 parts by weight of polyethyleneimine were added to 12 parts by weight of deionized water, and the mixture was stirred for 3 minutes to obtain a polyethyleneimine aqueous solution.

[0096] S3.2: Add 0.08 parts by weight of tetrabutyl titanate to 8 parts by weight of deionized water, stir and mix, then add polyethyleneimine aqueous solution, stir for 3 minutes to obtain a mixed solution, then mix zirconium oxychloride aqueous solution and phosphoric acid solution and add them to the mixed solution, stir and mix at 700 rpm for 20 minutes, place the obtained solution in a reactor and place it in an oven at 180°C to react for 24 hours, then wash the product twice with distilled water and twice with anhydrous ethanol, and centrifuge and dry to obtain intercalated modified zirconium phosphate;

[0097] S4: Preparation of hydrophobic, antibacterial and wear-resistant coatings

[0098] S4.1: 8 parts by weight of polydimethylsiloxane was added to 30 parts by weight of ethanol, followed by the addition of 3% dilute sulfuric acid, and the reaction was allowed to proceed for 3 hours. Then, 2 parts by weight of ethyl orthosilicate was added, and the reaction was allowed to proceed for 3 hours. After the reaction, 2 parts by weight of silica nanoparticles were added, and the mixture was stirred for 20 minutes to obtain a composite organosiloxane suspension.

[0099] S4.2: Add 2 parts by weight of vinyl-substituted polysilsesquioxane to the composite organosiloxane suspension, ultrasonically disperse for 20 minutes, then add 0.3 parts by weight of intercalated modified zirconium phosphate and ultrasonically disperse for 12 hours to obtain a hydrophobic, antibacterial, and wear-resistant coating;

[0100] S5: Preparation of wear-resistant and antibacterial rubber stopper composite materials

[0101] S5.1: Prepare the following raw materials: 120 parts by weight of brominated butyl rubber, 30 parts by weight of ethylene-ethyl acrylate copolymer, 3 parts by weight of polyisobutylene, 3 parts by weight of stearic acid, 5 parts by weight of zinc oxide, 0.3 parts by weight of sulfur, 30 parts by weight of calcined kaolin, 2 parts by weight of 2,2'-dibenzothiazole disulfide, and 2 parts by weight of 2,6-di-tert-butyl-p-cresol;

[0102] S5.2: The above raw materials and 8 parts by weight of the composite antimicrobial agent are added to an internal mixer and mixed at 100°C for 10 minutes to obtain a rubber compound. The rubber compound is cooled to below 50°C, rolled, and stored for 24 hours. The rubber compound is sheeted using an open mixer at 75°C, cooled to 20°C, and sliced ​​to obtain a rubber sheet. The rubber sheet is placed in the cavity of a vulcanization mold and vulcanized at 170°C and 15 MPa for 3 minutes to produce a rubber stopper material.

[0103] S5.3: Place the rubber stopper material in a plasma treatment device and perform plasma treatment with nitrogen to obtain a pretreated rubber stopper material. Spray a hydrophobic, antibacterial, and wear-resistant coating on the surface of the pretreated rubber stopper material, and then cure it at room temperature for 10 minutes to obtain a wear-resistant and antibacterial rubber stopper composite material.

[0104] Comparative Example 1

[0105] Compared with Example 1, the difference of Comparative Example 1 is that Comparative Example 1 removes the composite antibacterial agent in steps S1-S2 and step S5.2, and the other steps remain unchanged to prepare the wear-resistant antibacterial rubber stopper composite material, which is recorded as Comparative Example 1.

[0106] Comparative Example 2

[0107] Compared with Example 1, the difference of Comparative Example 2 is that Comparative Example 2 removes the steps of "redispersing the obtained surface-modified carbon-coated silver particles in 10 parts by weight of ethanol, ultrasonically dispersing for 30 minutes, and obtaining a surface-modified carbon-coated silver particle dispersion" in steps S2 and S1.4, and replaces the composite antibacterial agent in step S5.2 with surface-modified carbon-coated silver particles of equal mass. The remaining steps remain unchanged to prepare a wear-resistant and antibacterial rubber stopper composite material, which is recorded as Comparative Example 2.

[0108] Comparative Example 3

[0109] Compared with Example 1, the difference of Comparative Example 3 is that the intercalated modified zirconium phosphate in step S3 and step S4.2 is removed, and the other steps remain unchanged to prepare the wear-resistant and antibacterial rubber stopper composite material, which is recorded as Comparative Example 3.

[0110] Comparative Example 4

[0111] Compared with Example 1, the difference of Comparative Example 4 is that Comparative Example 4 removes steps S3.1 of "adding 2 parts by weight of polyethyleneimine to 10 parts by weight of deionized water, stirring for 3 minutes to obtain a polyethyleneimine aqueous solution" and S3.2 of "stirring and mixing and then adding the polyethyleneimine aqueous solution", and the remaining steps remain unchanged to prepare the wear-resistant and antibacterial rubber stopper composite material, which is recorded as Comparative Example 4.

[0112] Comparative Example 5

[0113] Compared with Example 1, the difference of Comparative Example 5 is that, in step S3.2, "0.06 parts by weight of tetrabutyl titanate is added to 5 parts by weight of deionized water, stirred and mixed, and then an aqueous solution of polyethyleneimine is added and stirred for 3 minutes to obtain a mixed solution" is removed, and the aqueous zirconium oxychloride solution and the phosphoric acid solution in S3.2 are mixed and then added to the aqueous solution of polyethyleneimine. The remaining steps remain unchanged to prepare a wear-resistant and antibacterial rubber stopper composite material, which is recorded as Comparative Example 5.

[0114] Comparative Example 6

[0115] Compared with Example 1, the difference of Comparative Example 6 is that Comparative Example 6 removes step S3, step S4 and step S5.3, and the other steps remain unchanged to prepare the rubber stopper material, that is, the wear-resistant and antibacterial rubber stopper composite material, which is recorded as Comparative Example 6.

[0116] Comparative Example 7

[0117] Compared with Example 1, the difference of Comparative Example 7 is that the vinyl-substituted polysilsesquioxane in step S4.2 is removed in Comparative Example 7, and the other steps remain unchanged to prepare the wear-resistant and antibacterial rubber stopper composite material, which is recorded as Comparative Example 7.

[0118] Comparative Example 8

[0119] Compared with Example 1, the difference of Comparative Example 8 is that Comparative Example 8 removes steps S1 and S2.3-S2.4, replaces the composite antibacterial agent in S5.2 with an N-substituted benzisothiazolinone compound, and the remaining steps remain unchanged to prepare a wear-resistant and antibacterial rubber stopper composite material, which is recorded as Comparative Example 8.

[0120] Antibacterial performance test: Shake bottle method was used: the wear-resistant antibacterial rubber stopper composite material sample was placed in a mixture containing 5 mL of nutrient solution and 1×10 7 CFU E. coli and 1 × 10 7The centrifuge tube containing CFU of Staphylococcus aureus was placed in a 37°C incubator and cultured with shaking for 24 h. 100 μL of the bacterial solution was taken and the OD value was measured at 600 nm using a microplate reader.

[0121] Wear resistance test: Based on EN388:2016 as the reference standard, the wear resistance of the sample was tested using a Martindale abrasion tester. The sample size was Φ38mm and the weight was 9kg. The end point of the experiment was when a through hole >1mm appeared on the sample, and the number of wear circles at this time was recorded.

[0122] The antibacterial properties and wear resistance circles of Examples 1-3 and Comparative Examples 1-8 were measured. The measurement results are shown in Table 1.

[0123] Table 1. Antibacterial performance and wear resistance test results of Examples 1-3 and Comparative Examples 1-8

[0124] Antibacterial rate (%) Wear-resistant circles Example 1 99.99 7484 Example 2 99.99 7529 Example 3 99.99 7503 Comparative Example 1 80.42 6283 Comparative Example 2 84.53 7452 Comparative Example 3 82.34 5382 Comparative Example 4 89.83 6293 Comparative Example 5 87.28 6492 Comparative Example 6 78.43 4293 Comparative Example 7 99.87 6939 Comparative Example 8 82.24 6182

[0125] As can be seen from the data in Table 1, the data of Comparative Examples 1 and 2 are worse than those of the embodiment, indicating that the composite antibacterial agent can improve the antibacterial and wear resistance of the rubber stopper composite material when dispersed in the rubber stopper composite material. The antibacterial rate of Comparative Example 2 is higher than that of Comparative Example 1, indicating that the N-substituted benzisothiazolinone compound has good antibacterial activity, while the antibacterial rates of Comparative Examples 2 and 8 are significantly lower than those of the embodiment. The N-substituted benzisothiazolinone compound illustrates that the combination of the two after being compounded with surface-modified carbon-coated silver particles can produce a synergistic antibacterial effect. As can be seen from the data of Comparative Examples 3-5, the addition of intercalation-modified zirconium phosphate effectively improves the antibacterial and wear resistance of the rubber stopper composite material, and when polyethyleneimine and titanium dioxide are intercalated and modified, the two produce a complementary effect, which can effectively impart antibacterial activity to zirconium phosphate and improve wear resistance. As can be seen from the data of Comparative Example 6, the hydrophobic antibacterial and wear-resistant coating significantly increases the wear resistance and antibacterial properties of the rubber stopper composite material. As can be seen from the data of Comparative Example 7, the introduction of vinyl-substituted polysilsesquioxane can improve wear resistance.

[0126] Long-lasting antibacterial performance test: The samples were stored at room temperature under ventilation conditions for 365 days, and their antibacterial properties were measured.

[0127] The long-lasting antibacterial performance of Examples 1-3 and Comparative Example 7 was tested, and the test results are shown in Table 2.

[0128] Table 2. Test results of long-lasting antibacterial performance of Examples 1-3 and Comparative Examples 1 and 7

[0129] Long-lasting antibacterial property (%) Example 1 99.98 Example 2 99.99 Example 3 99.98 Comparative Example 7 77.34

[0130] From the data in Table 2, it can be seen that the introduction of vinyl-substituted polysilsesquioxane can enable the rubber stopper composite material to achieve a long-lasting antibacterial effect, indicating that vinyl-substituted polysilsesquioxane can also enhance the adhesion between the hydrophobic, antibacterial and wear-resistant coating and the substrate surface and its own physical and chemical stability, thereby achieving a long-lasting hydrophobic, antibacterial and wear-resistant effect.

[0131] Hydrophobicity test: The contact angles of the rubber stopper composite materials of Examples 1-3 and Comparative Example 6 were measured using a JCY-2 contact angle meter (Shanghai Fangrui Instrument Co., Ltd.). The measurement results are shown in Table 3.

[0132] Table 3. Hydrophobicity measurement results of Examples 1-3 and Comparative Example 6

[0133] Water contact angle (°) Example 1 132 Example 2 131 Example 3 132 Comparative Example 6 98

[0134] From the data in Table 3, it can be seen that the hydrophobic, antibacterial and wear-resistant coating has a good hydrophobic effect, so that the rubber stopper composite material has good hydrophobicity, effectively preventing the penetration and adsorption of liquids such as water and blood, and reducing the bacterial growth and corrosion problems caused by liquid residue.

[0135] The wear-resistant and antibacterial rubber stopper composite materials prepared in Examples 1-3 were subjected to puncture tests and sealing tests. The test results are shown in Table 4.

[0136] Table 4. Puncture test and sealing test results of Examples 1-3

[0137] Puncture debris (grains), ≤5 (per 100 needles) Self-sealing Adhesion Example 1 1 No penetration No penetration Example 2 0 No penetration No penetration Example 3 1 No penetration No penetration

[0138] It can be seen from the data in Table 4 that the wear-resistant and antibacterial rubber stopper composite material prepared by the present invention has good sealing performance.

[0139] The above embodiments are merely illustrative of the principles and effects of the present invention and are not intended to limit the present invention. Anyone skilled in the art may modify or alter the above embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by one of ordinary skill in the art without departing from the spirit and technical principles disclosed herein are intended to be covered by the claims of the present invention.

Claims

1. A method for preparing a wear-resistant and antibacterial composite material for rubber stoppers, characterized in that: The steps include: S1: Preparation of surface-modified carbon-coated silver particles, using silver nitrate and glucose as raw materials to prepare carbon-coated silver particles, and then using 3-aminopropyltriethoxysilane to modify the surface of the carbon-coated silver particles to obtain a dispersion of surface-modified carbon-coated silver particles; S2: Preparation of a composite antibacterial agent, comprising reacting benzisothiazolinone, potassium carbonate, N,N-dimethylformamide, and 1,3-dibromo-2-propanol, followed by purification to prepare an N-substituted benzisothiazolinone compound, and grafting the N-substituted benzisothiazolinone compound onto surface-modified carbon-coated silver particles to obtain a composite antibacterial agent; S3: Intercalation modification of zirconium phosphate, using tetrabutyl titanate and polyethyleneimine to intercalate zirconium phosphate to obtain intercalation-modified zirconium phosphate; S4: Preparation of a hydrophobic, antibacterial, and wear-resistant coating: polydimethylsiloxane, dilute sulfuric acid, ethyl orthosilicate, and silica nanoparticles are mixed, vinyl-substituted polysilsesquioxane and intercalated modified zirconium phosphate are added, and ultrasonic dispersion is performed to obtain a hydrophobic, antibacterial, and wear-resistant coating; S5: Preparation of wear-resistant and antibacterial rubber stopper composite materials. Bromobutyl rubber, ethylene-ethyl acrylate copolymer, polyisobutylene, stearic acid, zinc oxide, sulfur, calcined kaolin, 2,2'-dibenzothiazole disulfide, 2,6-di-tert-butyl-p-cresol and composite antibacterial agent are added to an internal mixer for mixing, and then vulcanized to prepare a rubber stopper material. The rubber stopper material is plasma treated to obtain a pretreated rubber stopper material, and a hydrophobic, antibacterial and wear-resistant coating is sprayed on the surface of the pretreated rubber stopper material. After curing, a wear-resistant and antibacterial rubber stopper composite material is obtained.

2. The method for preparing a wear-resistant and antibacterial composite material for rubber stoppers according to claim 1, characterized in that: Step S1: Preparation of surface-modified carbon-coated silver particles, specifically comprising the following steps: S1.1: Add 4-5 parts by weight of a 0.3-0.5 mol / L silver nitrate solution to 80-90 parts by weight of a 0.5 mol / L glucose aqueous solution. Transfer the solution into a polytetrafluoroethylene liner and ultrasonically disperse for 10-20 minutes. Place the solution in a sealed reactor and react at 200-300°C for 5-6 hours. Cool to room temperature, centrifuge, wash, and then dry at 40-50°C for 10-12 hours to obtain carbon-encapsulated silver particles. S1.4: Disperse 3-5 parts by weight of carbon-wrapped silver particles in 10-15 parts by weight of ethanol, and ultrasonically disperse for 30-60 minutes to obtain a carbon-wrapped silver particle dispersion. Add 0.3-0.5 parts by weight of 3-aminopropyltriethoxysilane to the carbon-wrapped silver particle dispersion, and stir and react at 60-80°C under nitrogen protection for 4-6 hours. After the reaction is completed, wash the product with anhydrous ethanol 2-3 times and centrifuge to obtain surface-modified carbon-wrapped silver particles. Re-disperse the obtained surface-modified carbon-wrapped silver particles in 10-15 parts by weight of ethanol, and ultrasonically disperse for 30-60 minutes to obtain a surface-modified carbon-wrapped silver particle dispersion.

3. The method for preparing a wear-resistant and antibacterial composite material for rubber stoppers according to claim 2, characterized in that: Step S2: Preparation of the composite antimicrobial agent, specifically comprising the following steps: S2.1: 3-5 parts by weight of benzisothiazolinone and 2-3 parts by weight of potassium carbonate are mixed, 20-30 parts by weight of N,N-dimethylformamide are added, and the mixture is stirred at 400-500 r / min for 20-30 minutes. Then, 2-2.3 parts by weight of 1,3-dibromo-2-propanol are added, and the mixture is reacted at 70-73° C. for 14-15 hours to obtain a reaction solution; S2.2: The reaction solution is cooled to room temperature, 40-50 parts by weight of deionized water is added, and the mixture is extracted with ethyl acetate to obtain an organic solution. The organic solution is dried over anhydrous sodium sulfate, and the filtrate is collected by filtration. The filtrate is rotary evaporated and purified using a chromatography column with a dichloromethane:ethyl acetate ratio of 1:1 to obtain an N-substituted benzisothiazolinone compound; S2.3: Add 2-3 parts by weight of an N-substituted benzisothiazolinone compound to 10-12 parts by weight of tetrahydrofuran, stir and mix for 20-30 minutes, then add 0.3-0.5 parts by weight of triethylamine, and stir and react at room temperature for 30-60 minutes to obtain a mixed solution; S2.4: Add 3-5 parts by weight of the mixed liquid to 10-12 parts by weight of a dispersion of surface-modified carbon-coated silver particles, and stir the reaction at 50-70°C under nitrogen protection for 12-24 hours. After the reaction is completed, wash the product with anhydrous ethanol 2-3 times, centrifuge it, and place it in a vacuum drying oven at 60-80°C for 12-24 hours to obtain a composite antibacterial agent.

4. The method for preparing a wear-resistant and antibacterial composite material for rubber stoppers according to claim 3, characterized in that: The structure of the N-substituted benzisothiazolinone compound in step S2.2 is:

5. The method for preparing a wear-resistant and antibacterial composite material for rubber stoppers according to claim 4, characterized in that: Step S3: intercalation modification of zirconium phosphate, specifically comprising the following steps: S3.1: Add 4-5 parts by weight of zirconium oxychloride to 6-8 parts by weight of deionized water, and stir for 3-5 minutes to obtain a zirconium oxychloride aqueous solution. Add 8-10 parts by weight of phosphoric acid to 17-20 parts by weight of deionized water, and stir for 5-10 minutes to obtain a phosphoric acid solution. Add 2-3 parts by weight of polyethyleneimine to 10-12 parts by weight of deionized water, and stir for 3-5 minutes to obtain a polyethyleneimine aqueous solution. S3.2: Add 0.06-0.08 parts by weight of tetrabutyl titanate to 5-8 parts by weight of deionized water, stir and mix, then add polyethyleneimine aqueous solution, stir for 3-5 minutes to obtain a mixed solution, then mix the zirconium oxychloride aqueous solution and the phosphoric acid solution and add them to the mixed solution, stir and mix at 700-800 r / min for 20-30 minutes, place the obtained solution in a reactor and place it in an oven at 180-200°C to react for 24-25 hours, then wash the product with distilled water 2-3 times and with anhydrous ethanol 2-3 times, and obtain intercalated modified zirconium phosphate after centrifugal drying.

6. The method for preparing a wear-resistant and antibacterial composite material for rubber stoppers according to claim 5, characterized in that: Step S4 is the preparation of a hydrophobic, antibacterial, and wear-resistant coating, specifically comprising the following steps: S4.1: Add 5-8 parts by weight of polydimethylsiloxane to 20-30 parts by weight of ethanol, then add 2-3% dilute sulfuric acid, and react for 3-5 hours. Then, add 1-2 parts by weight of ethyl orthosilicate, and react for 3-5 hours. After the reaction, add 1-2 parts by weight of silica nanoparticles, and stir and mix for 20-30 minutes to obtain a composite organosiloxane suspension; S4.2: Add 1-2 parts by weight of vinyl-substituted polysilsesquioxane to the composite organosiloxane suspension, ultrasonically disperse for 20-30 minutes, then add 0.2-0.3 parts by weight of intercalated modified zirconium phosphate, and ultrasonically disperse for 10-12 hours to obtain a hydrophobic, antibacterial, and wear-resistant coating.

7. The method for preparing a wear-resistant and antibacterial composite material for rubber stoppers according to claim 6, characterized in that: Step S5 is the preparation of the wear-resistant and antibacterial rubber stopper composite material, which specifically includes the following steps: S5.1: Prepare the following raw materials: 100-120 parts by weight of brominated butyl rubber, 20-30 parts by weight of ethylene-ethyl acrylate copolymer, 2-3 parts by weight of polyisobutylene, 2-3 parts by weight of stearic acid, 3-5 parts by weight of zinc oxide, 0.2-0.3 parts by weight of sulfur, 20-30 parts by weight of calcined kaolin, 1-2 parts by weight of 2,2'-dibenzothiazole disulfide, and 1-2 parts by weight of 2,6-di-tert-butyl-p-cresol; S5.2: Add the above raw materials and 4-8 parts by weight of the composite antibacterial agent to an internal mixer and mix at 100-110°C for 10-12 minutes to obtain a rubber compound. Cool the rubber compound to below 50-60°C, then roll it and store it for 24-48 hours. Sheet it using an open mixer at 75-80°C, then cool it to 20-25°C and slice it to obtain a rubber sheet. Place the rubber sheet in the cavity of a vulcanization mold and vulcanize it at 170-180°C and 15-18 MPa for 3-5 minutes to produce a rubber stopper material. S5.3: Place the rubber stopper material in a plasma treatment device for plasma treatment to obtain a pretreated rubber stopper material, spray a hydrophobic, antibacterial, and wear-resistant coating on the surface of the pretreated rubber stopper material, and then cure it at room temperature for 10-12 minutes to obtain a wear-resistant and antibacterial rubber stopper composite material after curing.

8. The method for preparing a wear-resistant and antibacterial composite material for rubber stoppers according to claim 7, characterized in that: In S5.3, nitrogen gas is used for plasma treatment.

9. A wear-resistant and antibacterial composite material for rubber stoppers, characterized in that: The rubber stopper is prepared by the method for preparing the wear-resistant and antibacterial composite material for the rubber stopper according to any one of claims 1 to 8.

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