An antibacterial material for medical respirator accessories and a forming process thereof

Abstract

The application relates to an antibacterial material for medical respirator accessories and a forming process thereof, and the antibacterial material for medical respirator accessories comprises the following raw materials in parts by weight: 15-25 parts of polyurethane elastomer, 60-80 parts of silica gel, 5-20 parts of a filling agent, 3-5 parts of a dispersing agent, 1-3 parts of a lubricant, 0.5-1 part of an antioxidant, 0.1-1 part of an anti-hydrolysis agent and 1-3 parts of an antibacterial agent, wherein the filling agent comprises graphene oxide and silane modified aramid fiber, the application further limits the silane modified aramid fiber to be epoxy-silane modified aramid fiber, limits the mass ratio of the graphene oxide and the epoxy-silane modified aramid fiber to be 1:(2.5-3.5), and limits the graphene oxide to be polyethyleneimine modified graphene oxide; the prepared antibacterial silica gel material is good in durability and antibacterial property, has excellent biocompatibility and flexibility, and is suitable for the use requirement of medical respirator accessories.

Description

Technical Field

[0001] This application relates to a medical antibacterial silicone material, and more specifically, to an antibacterial material for medical ventilator accessories and its molding process. Background Technology

[0002] Medical-grade silicone has excellent biocompatibility, high and low temperature resistance, flexibility and breathability. It is non-toxic, non-irritating, and resistant to corrosion by a variety of medical disinfectants. Therefore, it has been widely used in the manufacture of various medical and health care products, such as ventilator tubing, masks, seals and other medical ventilator accessories.

[0003] Medical ventilator components are constantly exposed to humid and warm environments and come into direct contact with the human respiratory tract, making them highly susceptible to the growth of bacteria, mold, and other microorganisms. This not only leads to material aging and performance degradation but can also cause cross-infection, endangering patient health. Furthermore, silicone, over long-term use, is susceptible to erosion from moisture and medical disinfectants, resulting in hydrolysis and aging. This causes the material to harden, become brittle, and crack, reducing its lifespan and safety.

[0004] Currently, most medical-grade silicone materials on the market achieve their antibacterial effect by simply adding antibacterial agents. However, the antibacterial durability is poor, and the addition of antibacterial agents can easily affect the flexibility and biocompatibility of the silicone. Furthermore, ordinary silicone has limited hydrolysis resistance and anti-aging properties, making it difficult to meet the requirements for long-term stable use in medical ventilator accessories. In addition, the production technology for high-performance medical antibacterial silicone is concentrated in the hands of a few foreign companies, and domestic products still lag behind in terms of antibacterial durability and longevity. Therefore, how to develop a medical antibacterial silicone material that combines excellent antibacterial properties, durability, and biocompatibility to meet the needs of medical ventilator accessories is an urgent problem to be solved. Summary of the Invention

[0005] To address the issues of poor antibacterial durability and insufficient longevity of medical silicone materials, this application provides an antibacterial material for medical ventilator accessories and its molding process.

[0006] In a first aspect, this application provides an antibacterial material for medical ventilator accessories, comprising the following components in parts by weight: 15-25 parts of polyurethane elastomer, 60-80 parts of silicone, 5-20 parts of filler, 3-5 parts of dispersant, 1-3 parts of lubricant, 0.5-1 part of antioxidant, 0.1-1 part of anti-hydrolysis agent, and 0.5-3 parts of antibacterial agent, wherein the filler comprises graphene oxide and silane-modified aramid fiber.

[0007] By adopting the above solutions, silicone, as the matrix material, possesses excellent biocompatibility, flexibility, and breathability. It is non-toxic and non-irritating, making it perfectly suited for use in medical ventilator components that come into contact with the human respiratory tract. The addition of polyether-type polyurethane elastomers effectively improves the adhesion and elasticity of silicone, preventing brittleness and easy detachment after molding, while also enhancing the material's tear resistance. Adding a certain amount of dispersant ensures more uniform and stable dispersion of fillers, antibacterial agents, and other components within the silicone system, preventing localized agglomeration and ensuring uniform material performance. Adding a certain amount of lubricant reduces shear resistance during mixing, minimizing surface defects and improving molding results. Adding a certain amount of antioxidant slows down the oxidative aging process of silicone and polyurethane elastomers, further enhancing the durability of material performance. Adding a certain amount of anti-hydrolysis agent effectively slows down the hydrolysis rate of silicone in humid environments, preventing material aging and cracking. Adding a certain amount of antibacterial agent directly exerts antibacterial and antifungal effects, reducing safety hazards caused by microbial growth.

[0008] By adding a certain amount of graphene oxide and silane-modified aramid fiber as fillers, graphene oxide itself has a certain antibacterial effect, which can synergistically work with antibacterial agents to improve antibacterial durability, while reducing the amount of antibacterial agent added, avoiding excessive antibacterial agents from affecting the biocompatibility of the material. The surface of graphene oxide has a planar layered structure with a large surface area and high strength, which can be uniformly dispersed in the silicone system to form a dense protective layer, encapsulating and protecting the silicone matrix, reducing the intrusion of moisture and medical disinfectants, and extending the durability of the material. The surface of graphene oxide also has certain groups that can form chemical bonds with silicone molecules and polyurethane elastomer molecules, improving the binding tightness of each component, while eliminating carboxyl groups generated by silicone hydrolysis, avoiding the catalytic effect of carboxyl groups on the hydrolysis reaction, and further improving the hydrolysis resistance of the material.

[0009] Aramid fibers have high strength and good resistance to acids, alkalis, and disinfectants. After silane modification, their compatibility with the silica gel system is significantly improved. They can be uniformly dispersed in silica gel and interpenetrate with the layered graphene oxide to form a three-dimensional network structure, further improving the material's density and mechanical properties. At the same time, silane-modified aramid fibers can disperse stress concentration under stress, improve the material's tear resistance and tensile strength, and reduce the formation of hydrogen bonds between water vapor and the polar groups of silica gel, preventing the material from softening, expanding, and deforming, thus extending its service life.

[0010] In one specific feasible implementation, the silane-modified aramid fiber is an epoxy-silane-modified aramid fiber.

[0011] By adopting the above scheme, the epoxy groups in epoxy-silane modified aramid fibers can chemically react with silicone molecules, polyurethane elastomer molecules, and functional groups on the surface of graphene oxide, further enhancing the bonding strength of each component, making the material structure more compact, reducing moisture intrusion, and extending the material's service life. At the same time, the epoxy groups can effectively eliminate the carboxylic acid produced by silicone hydrolysis, inhibit the catalytic effect of carboxylic acid on the hydrolysis reaction, and can also react with carboxyl groups to generate hydroxyl groups, causing the broken molecular chains produced by hydrolysis to reconnect, playing a role in hydrolysis stabilization, reducing the amount of anti-hydrolysis agent used, while ensuring the material's flexibility and processing performance.

[0012] In one specific feasible implementation, the mass ratio of graphene oxide to epoxy silane modified aramid fiber is 1:(2.5-3.5).

[0013] By adopting the above scheme, graphene oxide and epoxy silane-modified aramid fibers can be uniformly distributed and fully interwoven in the silicone system to form an optimal three-dimensional protective structure. This ensures both the material's density and mechanical properties, while also fully leveraging their synergistic antibacterial and hydrolysis-resistant effects. At this mass ratio, the tensile strength and flexibility of the material remain stable after a period of use. This is because after the initial hydrolysis of silicone to generate carboxylic acids, the epoxy silane-modified aramid fibers can eliminate some of the carboxylic acids. Furthermore, in an acidic environment, the epoxy silane-modified aramid fibers can form ester alcohol chemical bonds with the carboxyl groups on graphene oxide, more tightly binding the initially hydrolyzed silicone molecules and polyurethane elastomer molecules, further slowing down moisture intrusion and extending the material's service life.

[0014] In one specific feasible implementation, the graphene oxide is polyethyleneimine-modified graphene oxide.

[0015] Modifying graphene oxide with polyethyleneimine can further enhance its compatibility and affinity. Meanwhile, polyethyleneimine possesses high adhesion and adsorption properties, exhibiting excellent compatibility with silicone and polyurethane elastomers. This allows the modified graphene oxide to be uniformly dispersed within the silicone system, tightly bonded to all components, further increasing the material's density. Furthermore, polyethyleneimine's diverse cross-bonding and high reactivity enable it to react with the hydroxyl groups of epoxy-silane-modified aramid fibers, further strengthening the bond strength between components, reducing moisture intrusion, and improving the material's durability and antibacterial longevity.

[0016] The preparation steps of polyethyleneimine-modified graphene oxide include: adding graphene oxide into dimethylacetamide (DMAC), dispersing it ultrasonically, then adding polyethyleneimine, reacting at 80-100℃ for 7-9 hours, cooling to room temperature, filtering under reduced pressure, washing, and drying to obtain polyethyleneimine-modified graphene oxide.

[0017] The polyethyleneimine-modified graphene oxide prepared by the above method has a simple and controllable preparation process. The polyethyleneimine and graphene oxide are firmly bonded, which can give full play to its modifying effect and improve the overall performance of the material.

[0018] In one specific feasible implementation, the antibacterial agent includes one or more of the following: silver, zinc, copper ions, or their oxides / nanoparticles; quaternary ammonium salts, isothiazolinones, organosilicon quaternary ammonium salts; chitosan, aloe vera extract, and chitosan.

[0019] Preferably, the antibacterial agent includes chitosan. As a natural antibacterial agent, chitosan's molecular chain is rich in amino and hydroxyl groups. Both of these groups can bond with epoxy groups within the system, allowing chitosan to be directly "anchored" to surfaces containing epoxy groups, further enhancing its antibacterial stability.

[0020] It possesses excellent antibacterial and antifungal properties, with a broad antibacterial spectrum and long-lasting effect. It also has good compatibility with silicone systems and will not affect the flexibility and biocompatibility of the material. It can inhibit the reproduction of microorganisms by destroying the cell membrane structure of bacteria and fungi, thus protecting silicone materials for a long time and avoiding the decline in material performance caused by microbial degradation. This allows the material to maintain high mechanical properties and antibacterial effects for a long time.

[0021] In one specific implementation scheme, the polyurethane elastomer is a polyether-type polyurethane elastomer.

[0022] By adopting the above-mentioned approach, polyether-type polyurethane elastomers exhibit excellent elasticity and good compatibility with silicone. This effectively improves the adhesion and tear resistance of silicone, preventing problems such as brittleness and detachment after silicone molding. At the same time, it enhances the material's resistance to damp heat and works synergistically with silicone to further improve the material's durability.

[0023] In one specific feasible implementation, the silicone is medical-grade methyl vinyl silicone with a Shore hardness of 50-70A.

[0024] By adopting the above solutions, medical-grade methyl vinyl silicone is non-toxic, non-irritating, and has excellent biocompatibility, meeting medical material standards. The silicone with a Shore hardness of 50-70A has both good flexibility and support, which can meet the usage requirements of medical ventilator accessories (such as tubing, masks, and seals). It will not cause discomfort due to being too hard, nor will it affect the structural stability due to being too soft.

[0025] Secondly, this application provides a molding process for an antibacterial material used in medical ventilator accessories, comprising the following steps: S1: Add silicone, polyurethane elastomer, filler, and dispersant into an internal mixer and mix at 80-100℃ for 0.2-0.5 hours; S2: Mix the product obtained from S1 with the other remaining components evenly, continue kneading for 0.2-0.5 hours, then send it into a vulcanizing machine and vulcanize for 10-20 minutes at 160-180℃ and 0.3-0.5MPa pressure. After cooling, trim to obtain the finished product.

[0026] The molding process described above aligns with the thermosetting characteristics of silicone materials, is simple and controllable, and is suitable for the composition of the antibacterial silicone material of this application. By first mixing silicone, polyurethane elastomer, filler, and dispersant, the filler can be uniformly dispersed in the silicone system, avoiding agglomeration and improving the uniformity of material performance. Subsequent addition of other components and continued mixing ensures that all components are fully integrated. The vulcanization step allows silicone molecules to undergo a cross-linking reaction, forming a stable three-dimensional network structure, improving the material's mechanical properties, hydrolysis resistance, and antibacterial durability. The aseptic treatment after vulcanization further enhances the material's medical safety and meets the usage requirements of ventilator accessories.

[0027] In one specific implementation scheme, the internal mixer rotates at a speed of 30-50 r / min, and the vulcanized finished product needs to undergo aseptic treatment.

[0028] By adopting the above-mentioned approach, a mixer speed of 30-50 r / min can ensure that all components are fully mixed, while avoiding material degradation caused by excessive speed. Aseptic treatment after vulcanization (such as high-pressure steam sterilization or ultraviolet sterilization) can thoroughly remove microorganisms from the material surface, ensuring that the material meets medical standards and avoiding the risk of cross-infection.

[0029] In summary, this application has the following beneficial effects: 1. This application uses medical-grade silicone as the matrix, combined with polyether-type polyurethane elastomer modification, and adds graphene oxide and epoxy silane-modified aramid fibers as fillers. The layered graphene oxide and aramid fibers are uniformly dispersed and interwoven in the silicone system. Polyethylene imine-modified graphene oxide further enhances the bonding strength of each component. The resulting antibacterial silicone material has a dense structure, making it difficult for water vapor and medical disinfectants to penetrate, effectively delaying the hydrolysis and aging of the material and improving its durability.

[0030] 2. This application utilizes the synergistic effect of graphene oxide with antibacterial agents such as titanium dioxide and zinc oxide to enhance antibacterial durability, effectively inhibit the growth of bacteria and mold, reduce the decline in material performance caused by microbial degradation, reduce the amount of antibacterial agents used, ensure the biocompatibility of the material, and meet medical requirements.

[0031] 3. This application uses epoxy silane to modify aramid fibers, which not only improves the compatibility and bonding strength between aramid fibers and silicone systems, but also eliminates carboxyl groups generated by silicone hydrolysis, inhibits the catalytic effect of hydrolysis reaction, and further improves the hydrolysis resistance and durability of the material; the molding process is in line with the characteristics of silicone, is simple and controllable, and is suitable for industrial production. Detailed Implementation

[0032] The following describes the technical solution of the present invention in more detail with reference to several specific implementation examples. The embodiments are only some embodiments of the present invention, not all of them. The following specific embodiments can be combined with each other, and the same or similar concepts or processes may not be repeated in some embodiments.

[0033] Unless otherwise specified, the experimental reagents used in the preparation examples, embodiments, and comparative examples are all from commercially available brands or obtained through conventional preparation processes.

[0034] In the preparation examples, embodiments, and comparative examples: the polyether-type polyurethane elastomer was purchased from BASF; medical-grade methyl vinyl silicone (Shore hardness 60A) was purchased from Shenzhen Dongjue Organosilicon Materials Co., Ltd.; polyethyleneimine was purchased from Shanghai Demao Co., Ltd.; graphene oxide was purchased from Beijing Carbon Century Technology; the dispersant was SP-762 (compatible with silicone systems) from Dongguan Xinbocheng Environmental Protection Materials Co., Ltd.; the lubricant was 469 from OKS, Germany; the antioxidant was 1076 from Jihong; the anti-hydrolysis agent was UN-03025 from Youen Chemical Co., Ltd.; and the antibacterial agent was jdj-111 (titanium dioxide-zinc oxide composite antibacterial agent) from Jiedejia Co., Ltd.

[0035] Preparation Example Preparation Example 1 Epoxysilane modified aramid fibers: 100g of aramid fiber was added to 2000ml of toluene and ultrasonically dispersed for 30 minutes at a power of 300W to obtain a suspension. 5g of epoxy silane coupling agent KH-560 was added to the mixture and ultrasonicated for 5 minutes at a power of 300W. The mixture was then filtered and reacted for 6 hours at a reaction temperature of 90℃. After drying at 80℃ for 6 hours, the mixture was filtered to obtain epoxy silane modified aramid fiber.

[0036] Preparation Example 2 Polyethyleneimine-modified graphene oxide 100g of graphene oxide was added to 3000mL of dimethylacetamide (DMAC) and ultrasonically dispersed for 30 minutes at a power of 300W. Then, 120g of polyethyleneimine was added, and the mixture was reacted at 90℃ for 8 hours. After cooling to room temperature, the mixture was filtered under reduced pressure, washed twice with ethanol, and dried to obtain polyethyleneimine-modified graphene oxide.

[0037] Preparation Example 3 Aminosilane modified aramid fibers 120g of aramid fiber and 20g of aminosilane coupling agent KH-602 were added to 1500ml of 20% ethanol aqueous solution and mixed. The mixture was stirred at 90℃ for 2 hours, filtered, washed with deionized water, and dried at 50℃ to obtain aminosilane modified aramid fiber.

[0038] Preparation Example 4 Epoxysilane modified carbon fiber 100g of carbon fiber was added to 2000ml of toluene and ultrasonically dispersed for 30 minutes to obtain a suspension. The power was 300W. 8g of epoxy silane coupling agent KH-560 was added to the mixture, ultrasonicated for 5 minutes, filtered, and then reacted for 6 hours at a reaction temperature of 100℃. The mixture was then dried at 80℃ for 6 hours, filtered, and then dried at 80℃ for 6 hours to obtain epoxy silane modified carbon fiber. Example Example

[0039] An antibacterial material for medical ventilator accessories comprises the following raw materials by weight: 200g polyurethane elastomer, 600g silicone, 40g graphene oxide, 120g epoxy silane modified aramid fiber prepared in Preparation Example 1, 40g dispersant, 20g lubricant, 7g antioxidant, 7g anti-hydrolysis agent, and 15g antibacterial agent.

[0040] The molding process for antibacterial materials used in medical ventilator accessories is as follows: S1: Add silicone, polyurethane elastomer, epoxy silane modified aramid fiber, graphene oxide and dispersant into a mixer and mix at 80℃ and 30r / min for 0.5 hours. S2: Mix the product obtained from S1 with lubricant, antioxidant, anti-hydrolysis agent and antibacterial agent evenly, continue to knead for 0.5 hours, then send it into a vulcanizing machine, vulcanize at 160℃ and 0.3MPa pressure for 20 minutes, cool and trim, and sterilize by high pressure steam to obtain the finished product. Example

[0041] An antibacterial material for medical ventilator accessories comprises the following raw materials by weight: 200g polyurethane elastomer, 800g silicone, 40g graphene oxide, 120g epoxy silane modified aramid fiber prepared in Preparation Example 1, 40g dispersant, 30g lubricant, 10g antioxidant, 7g anti-hydrolysis agent, and 15g antibacterial agent.

[0042] The molding process for antibacterial materials used in medical ventilator accessories is as follows: S1: Add silicone, polyurethane elastomer, epoxy silane modified aramid fiber, graphene oxide and dispersant into a mixer and mix at 80℃ and 30r / min for 0.5 hours. S2: Mix the product obtained from S1 with lubricant, antioxidant, anti-hydrolysis agent and antibacterial agent evenly, continue to knead for 0.5 hours, then send it into a vulcanizing machine, vulcanize at 160℃ and 0.3MPa pressure for 20 minutes, cool and trim, and sterilize by high pressure steam to obtain the finished product. Example

[0043] An antibacterial material for medical ventilator accessories comprises the following raw materials by weight: 250g polyurethane elastomer, 600g silicone, 40g graphene oxide, 120g epoxy silane-modified aramid fiber prepared in Preparation Example 1, 50g dispersant, 20g lubricant, 7g antioxidant, 8g anti-hydrolysis agent, and 15g antibacterial agent.

[0044] The molding process for antibacterial materials used in medical ventilator accessories is as follows: S1: Add silicone, polyurethane elastomer, epoxy silane modified aramid fiber, graphene oxide and dispersant into a mixer and mix at 90℃ and 40r / min for 0.5 hours. S2: Mix the product obtained from S1 with lubricant, antioxidant, anti-hydrolysis agent and antibacterial agent evenly, continue to knead for 0.5 hours, then send it into a vulcanizing machine, vulcanize at 170℃ and 0.4MPa pressure for 15 minutes, cool and trim, and sterilize by high pressure steam to obtain the finished product. Example

[0045] An antibacterial material for medical ventilator accessories comprises the following raw materials by weight: 250g polyurethane elastomer, 600g silicone, 32g graphene oxide, 128g epoxy silane modified aramid fiber prepared in Preparation Example 1, 50g dispersant, 20g lubricant, 7g antioxidant, 8g anti-hydrolysis agent, and 15g antibacterial agent.

[0046] The molding process for antibacterial materials used in medical ventilator accessories is as follows: S1: Add silicone, polyurethane elastomer, epoxy silane modified aramid fiber, graphene oxide and dispersant into a mixer and mix at 90℃ and 40r / min for 0.5 hours. S2: Mix the product obtained from S1 with lubricant, antioxidant, anti-hydrolysis agent and antibacterial agent evenly, continue to knead for 0.5 hours, then send it into a vulcanizing machine, vulcanize at 170℃ and 0.4MPa pressure for 15 minutes, cool and trim, and sterilize by high pressure steam to obtain the finished product. Example

[0047] An antibacterial material for medical ventilator accessories comprises the following raw materials by weight: 250g polyurethane elastomer, 600g silicone, 50g graphene oxide, 110g epoxy silane modified aramid fiber prepared in Preparation Example 1, 50g dispersant, 20g lubricant, 7g antioxidant, 8g anti-hydrolysis agent, and 15g antibacterial agent.

[0048] The molding process for antibacterial materials used in medical ventilator accessories is as follows: S1: Add silicone, polyurethane elastomer, epoxy silane modified aramid fiber, graphene oxide and dispersant into a mixer and mix at 90℃ and 40r / min for 0.5 hours. S2: Mix the product obtained from S1 with lubricant, antioxidant, anti-hydrolysis agent and antibacterial agent evenly, continue to knead for 0.5 hours, then send it into a vulcanizing machine, vulcanize at 170℃ and 0.4MPa pressure for 15 minutes, cool and trim, and sterilize by high pressure steam to obtain the finished product. Example

[0049] An antibacterial material for medical ventilator accessories, comprising the following raw materials by weight: 250g polyurethane elastomer, 600g silicone, 40g graphene oxide, 120g aramid fiber, 50g dispersant, 20g lubricant, 7g antioxidant, 8g anti-hydrolysis agent, and 15g antibacterial agent.

[0050] The molding process for antibacterial materials used in medical ventilator accessories is as follows: S1: Add silicone, polyurethane elastomer, aramid fiber, graphene oxide and dispersant into a mixer and mix at 90℃ and 40r / min for 0.5 hours; S2: Mix the product obtained from S1 with lubricant, antioxidant, anti-hydrolysis agent and antibacterial agent evenly, continue to knead for 0.5 hours, then send it into a vulcanizing machine, vulcanize at 170℃ and 0.4MPa pressure for 15 minutes, cool and trim, and sterilize by high pressure steam to obtain the finished product. Example

[0051] An antibacterial material for medical ventilator accessories comprises the following raw materials by weight: 250g polyurethane elastomer, 600g silicone, 40g graphene oxide, 120g aminosilane-modified aramid fiber prepared in Preparation Example 3, 50g dispersant, 20g lubricant, 7g antioxidant, 8g anti-hydrolysis agent, and 15g antibacterial agent.

[0052] The molding process for antibacterial materials used in medical ventilator accessories is as follows: S1: Add silicone, polyurethane elastomer, aminosilane modified aramid fiber, graphene oxide and dispersant into a mixer and mix at 90℃ and 40r / min for 0.5 hours. S2: Mix the product obtained from S1 with lubricant, antioxidant, anti-hydrolysis agent and antibacterial agent evenly, continue to knead for 0.5 hours, then send it into a vulcanizing machine, vulcanize at 170℃ and 0.4MPa pressure for 15 minutes, cool and trim, and sterilize by high pressure steam to obtain the finished product. Example

[0053] An antibacterial material for medical ventilator accessories comprises the following raw materials by weight: 250g polyurethane elastomer, 600g silicone, 40g polyethyleneimine-modified graphene oxide prepared in Preparation Example 2, 120g epoxy silane-modified aramid fiber prepared in Preparation Example 1, 50g dispersant, 20g lubricant, 7g antioxidant, 8g anti-hydrolysis agent, and 15g antibacterial agent.

[0054] The molding process for antibacterial materials used in medical ventilator accessories is as follows: S1: Add silicone, polyurethane elastomer, epoxy silane modified aramid fiber, polyethyleneimine modified graphene oxide, and dispersant into a mixer and mix at 100℃ and 50r / min for 0.5 hours. S2: Mix the product obtained from S1 with lubricant, antioxidant, anti-hydrolysis agent and antibacterial agent evenly, continue to knead for 0.5 hours, then send it into a vulcanizing machine, vulcanize at 180℃ and 0.5MPa pressure for 10 minutes, cool and trim, and sterilize by high pressure steam to obtain the finished product. Example

[0055] An antibacterial material for medical ventilator accessories comprises the following raw materials by weight: 250g polyurethane elastomer, 600g silicone, 40g polyethyleneimine-modified graphene oxide prepared in Preparation Example 2, 120g epoxy silane-modified aramid fiber prepared in Preparation Example 1, 50g dispersant, 20g lubricant, 7g antioxidant, 8g anti-hydrolysis agent, 12g antibacterial agent, and 3g chitosan.

[0056] The molding process for antibacterial materials used in medical ventilator accessories is as follows: S1: Add silicone, polyurethane elastomer, epoxy silane modified aramid fiber, polyethyleneimine modified graphene oxide, and dispersant into a mixer and mix at 100℃ and 50r / min for 0.5 hours. S2: Mix the product obtained from S1 with lubricant, antioxidant, anti-hydrolysis agent, antibacterial agent and chitosan evenly, continue to knead for 0.5 hours, then send it into a vulcanizing machine and vulcanize at 180℃ and 0.5MPa pressure for 10 minutes. After cooling and trimming, sterilize by high pressure steam to obtain the finished product.

[0057] Comparative Example Comparative Example 1 An antibacterial material for medical ventilator accessories comprises the following raw materials by weight: 250g polyurethane elastomer, 600g silicone, 40g graphene oxide, 120g epoxy silane modified carbon fiber prepared in Preparation Example 4, 50g dispersant, 20g lubricant, 7g antioxidant, 8g anti-hydrolysis agent, and 15g antibacterial agent.

[0058] The molding process for antibacterial materials used in medical ventilator accessories is as follows: S1: Add silicone, polyurethane elastomer, epoxy silane modified carbon fiber, graphene oxide and dispersant into a mixer and mix at 90℃ and 40r / min for 0.5 hours. S2: Mix the product obtained from S1 with lubricant, antioxidant, anti-hydrolysis agent and antibacterial agent evenly, continue to knead for 0.5 hours, then send it into a vulcanizing machine, vulcanize at 170℃ and 0.4MPa pressure for 15 minutes, cool and trim, and sterilize by high pressure steam to obtain the finished product.

[0059] Comparative Example 2 An antibacterial material for medical ventilator accessories comprises the following raw materials by weight: 100g polyurethane elastomer, 900g silicone, 40g graphene oxide, 120g epoxy silane modified aramid fiber prepared in Preparation Example 1, 50g dispersant, 20g lubricant, 7g antioxidant, 8g anti-hydrolysis agent, and 15g antibacterial agent.

[0060] The molding process for antibacterial materials used in medical ventilator accessories is as follows: S1: Add silicone, polyurethane elastomer, epoxy silane modified aramid fiber, graphene oxide and dispersant into a mixer and mix at 90℃ and 40r / min for 0.5 hours. S2: Mix the product obtained from S1 with lubricant, antioxidant, anti-hydrolysis agent and antibacterial agent evenly, continue to knead for 0.5 hours, then send it into a vulcanizing machine, vulcanize at 170℃ and 0.4MPa pressure for 15 minutes, cool and trim, and sterilize by high pressure steam to obtain the finished product.

[0061] Comparative Example 3 An antibacterial material for medical ventilator accessories comprises the following raw materials by weight: 250g polyurethane elastomer, 600g silicone, 40g silica, 120g epoxy silane-modified aramid fiber prepared in Preparation Example 1, 50g dispersant, 20g lubricant, 7g antioxidant, 8g anti-hydrolysis agent, and 15g antibacterial agent.

[0062] The molding process for antibacterial materials used in medical ventilator accessories is as follows: S1: Add silicone, polyurethane elastomer, epoxy silane modified aramid fiber, silica, and dispersant into a mixer and mix at 90℃ and 40r / min for 0.5 hours. S2: Mix the product obtained from S1 with lubricant, antioxidant, anti-hydrolysis agent and antibacterial agent evenly, continue to knead for 0.5 hours, then send it into a vulcanizing machine, vulcanize at 170℃ and 0.4MPa pressure for 15 minutes, cool and trim, and sterilize by high pressure steam to obtain the finished product.

[0063] Comparative Example 4 An antibacterial material for medical ventilator accessories comprises the following raw materials by weight: 250g polyurethane elastomer, 600g silicone, 160g epoxy silane modified aramid fiber prepared in Preparation Example 1, 50g dispersant, 20g lubricant, 7g antioxidant, 8g anti-hydrolysis agent, and 15g antibacterial agent.

[0064] The molding process for antibacterial materials used in medical ventilator accessories is as follows: S1: Add silicone, polyurethane elastomer, epoxy silane modified aramid fiber and dispersant into a mixer and mix at 90℃ and 40r / min for 0.5 hours; S2: Mix the product obtained from S1 with lubricant, antioxidant, anti-hydrolysis agent and antibacterial agent evenly, continue to knead for 0.5 hours, then send it into a vulcanizing machine, vulcanize at 170℃ and 0.4MPa pressure for 15 minutes, cool and trim, and sterilize by high pressure steam to obtain the finished product.

[0065] Comparative Example 5 An antibacterial material for medical ventilator accessories comprises the following raw materials by weight: 250g polyurethane elastomer, 600g silicone, 160g polyethyleneimine-modified graphene oxide prepared in Preparation Example 2, 50g dispersant, 20g lubricant, 7g antioxidant, 8g anti-hydrolysis agent, and 15g antibacterial agent.

[0066] The molding process for antibacterial materials used in medical ventilator accessories is as follows: S1: Add silicone, polyurethane elastomer, polyethyleneimine-modified graphene oxide, and dispersant into a mixer and mix at 90℃ and 40r / min for 0.5 hours. S2: Mix the product obtained from S1 with lubricant, antioxidant, anti-hydrolysis agent and antibacterial agent evenly, continue to knead for 0.5 hours, then send it into a vulcanizing machine, vulcanize at 170℃ and 0.4MPa pressure for 15 minutes, cool and trim, and sterilize by high pressure steam to obtain the finished product.

[0067] Performance testing Test 1: The tensile strength of the antibacterial materials prepared according to the examples and comparative examples in GB / T528-2009 was tested. The samples were then soaked in 20% hydrochloric acid at a constant temperature of 90°C for two weeks, and the tensile strength was tested again. The change rate of tensile strength was calculated.

[0068] Test 2: Referring to standard GB / T31402-2015, using Staphylococcus aureus ATCC8739 as the test object, the antibacterial rate of the antibacterial materials prepared in each example and comparative example was tested.

[0069] Test 3: Referring to standard GB / T24128-2009, using Aspergillus niger AS3.315 as the test object, the mold growth of the antibacterial materials prepared in each example and comparative example was tested and rated. Grade 0 indicates no mold growth, Grade 1 indicates mold growth area <10%, Grade 2 indicates mold growth area ≥10% and <30%, Grade 3 indicates mold growth area ≥30% and <60%, and Grade 4 indicates mold growth area ≥60% and ≤100%.

[0070] Test 4: Referring to standard GB / T31402-2015, the sterilization process of medical tubing materials was simulated. Then, using Staphylococcus aureus ATCC8739 as the test object, the antibacterial rate of the antibacterial materials prepared in each example and comparative example was repeatedly tested.

[0071] The results are summarized in Table 1.

[0072] Table 1

[0073] Based on Examples 1-3, Examples 6-7, Comparative Examples 1-5, and Table 1, the antibacterial silicone materials with each component within the mass range of this application are not easily hydrolyzed in acidic and humid environments, exhibit good durability, low tensile deformation rate, high antibacterial rate, and good antifungal effect. However, when the amount of polyurethane elastomer exceeds the limits specified in this application (Comparative Example 2), the elasticity and hydrolysis resistance of the material decrease, and the antibacterial and antifungal effects also diminish. When silica is used instead of graphene oxide (Comparative Example 3) or no graphene oxide is added (Comparative Example 4), the antibacterial and antifungal effects significantly decrease, indicating that the synergistic effect of graphene oxide and the antibacterial agent can effectively improve antibacterial durability.

[0074] In conjunction with Examples 3-5 and Table 1, this application demonstrates that by limiting the mass ratio of graphene oxide to epoxy silane-modified aramid fiber to 1:(2.5-3.5), the resulting antibacterial silicone material exhibits better durability and antibacterial performance. When the ratio exceeds this range, the tensile change rate increases slightly, and the antibacterial effect decreases slightly.

[0075] In conjunction with Examples 3 and 8 and Table 1, this application demonstrates that by modifying graphene oxide with polyethyleneimine, the durability and antibacterial performance of the antibacterial silicone material can be further improved, with a lower tensile deformation rate and a higher antibacterial rate. This indicates that polyethyleneimine modification can enhance the compatibility and bonding strength between graphene oxide and the silicone system.

[0076] This specific embodiment is merely an explanation of this application and is not intended to limit it. After reading this specification, those skilled in the art can make modifications to this embodiment without contributing any inventive step, but such modifications are protected by patent law as long as they fall within the scope of the claims of this application.

Claims

1. An antibacterial material for medical ventilator accessories, characterized in that: The raw materials comprise the following parts by weight: 15-25 parts polyurethane elastomer, 60-80 parts silicone, 5-20 parts filler, 3-5 parts dispersant, 1-3 parts lubricant, 0.5-1 part antioxidant, 0.1-1 part anti-hydrolysis agent, and 1-3 parts antibacterial agent, wherein the filler includes graphene oxide and silane-modified aramid fiber.

2. The antibacterial material for medical ventilator accessories according to claim 1, characterized in that: The silane-modified aramid fiber is an epoxy-silane-modified aramid fiber.

3. The antibacterial material for medical ventilator accessories according to claim 2, characterized in that: The mass ratio of the graphene oxide and the epoxy silane modified aramid fiber is 1:(2.5-3.5).

4. The antibacterial material for medical ventilator accessories according to claim 1, characterized in that: The graphene oxide is polyethyleneimine-modified graphene oxide.

5. The antibacterial material for medical ventilator accessories according to claim 4, characterized in that: The preparation steps of the polyethyleneimine-modified graphene oxide include: Graphene oxide was added to dimethylacetamide and ultrasonically dispersed. Then polyethyleneimine was added and reacted at 80-100℃ for 7-9 hours. After cooling to room temperature, the mixture was filtered under reduced pressure, washed, and dried to obtain polyethyleneimine-modified graphene oxide.

6. The antibacterial material for medical ventilator accessories according to claim 1, characterized in that: The antibacterial agent includes one or more of the following: silver, zinc, copper ions, or their oxides / nanoparticles; quaternary ammonium salts, isothiazolinones, organosilicon quaternary ammonium salts; chitosan, aloe vera extract, and chitosan.

7. The antibacterial material for medical ventilator accessories according to claim 1, characterized in that: The polyurethane elastomer is a polyether-type polyurethane elastomer.

8. The antibacterial material for medical ventilator accessories according to claim 1, characterized in that: The silicone is methyl vinyl silicone with a Shore hardness of 50-70A.

9. A molding process for an antibacterial material for medical ventilator accessories according to any one of claims 1-8, characterized in that: The molding process includes the following steps: S1: Add silicone, polyurethane elastomer, filler, and dispersant into an internal mixer and mix at 80-100℃ for 0.2-0.5 hours; S2: Mix the product obtained from S1 with the other remaining components evenly, continue kneading for 0.2-0.5 hours, then send it into a vulcanizing machine and vulcanize for 10-20 minutes at 160-180℃ and 0.3-0.5MPa pressure. After cooling, trim to obtain the finished product.

10. The molding process for the antibacterial material for medical ventilator accessories according to claim 9, characterized in that: The internal mixer operates at a speed of 30-50 r / min, and the finished product after vulcanization needs to undergo aseptic treatment.

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