Preparation method of silicon-boron-based zinc-silver antibacterial agent with grapevine chain structure

Abstract

The application discloses a preparation method of a silicon-boron-based zinc-silver carrier antibacterial agent with grapevine chain structure. The silicon-boron-based zinc-silver carrier antibacterial agent with grapevine chain structure is successfully prepared by combining antibacterial components and a silicon-based net chain carrier through a sol-gel method, a process of combining zinc and silver ions, and a process of combining high-pressure homogenization and hydrothermal treatment. Compared with the prior art, the grapevine chain carrier can effectively improve the loading capacity of antibacterial ions, and in the application process, the spherical antibacterial components are connected on the grapevine chain instead of being wrapped in the carrier, so that the antibacterial effect can be effectively improved, and the antibacterial components are prevented from being wrapped in the carrier and being difficult to release. The design makes the silicon-boron-based zinc-silver carrier antibacterial agent exhibit high bactericidal effect, has strong stability and durability, and thus the service life of the product is significantly prolonged.

Description

Technical Field

[0001] This invention belongs to the technical field of silver-loaded antibacterial agent materials, specifically relating to a method for preparing a silicon boron-based zinc-silver-loaded antibacterial agent with a grape branch chain structure. Background Technology

[0002] Harmful bacteria are ubiquitous in nature, causing iatrogenic infections, cross-infections, and infectious diseases that pose a serious threat to human life. Plastic products are widely used in modern daily life, and these products typically lack antibacterial properties; some are even favorable environments for bacterial growth. Antibacterial functionalization of plastics can rapidly kill or inhibit the proliferation of microorganisms on their surfaces, maintaining their cleanliness. With significantly increased public awareness of product safety and hygiene, the antibacterial plastic products industry is entering a phase of rapid development, and its market size is projected to exceed one trillion yuan by 2030.

[0003] Current research indicates that some inorganic antibacterial agents have achieved certain success in the plastics market. However, researchers also recognize that challenges remain in the field of inorganic antibacterial agents, such as the complexity of preparation processes, cost considerations, and performance requirements for specific applications. Therefore, further innovation and in-depth research into the preparation and application of inorganic antibacterial materials have become an important direction for current scientific research.

[0004] This invention provides a method for preparing a boron-based zinc-silver loaded antibacterial agent with a grape-branch chain structure. Using a sol-gel-hydrothermal process, Zn-Ag antibacterial ions are successfully and uniformly linked onto a network of boron-based materials, forming a boron-based zinc-silver loaded antibacterial agent with uniform loading and fine particle size. This boron-based zinc-silver loaded antibacterial agent successfully loads a binary antibacterial material of Zn and Ag, significantly improving the antibacterial agent's antibacterial and bactericidal speed and durability. Summary of the Invention

[0005] The purpose of this invention is to provide a method for preparing a silicon boron-based zinc-silver-loaded antibacterial agent with a grape branch chain structure.

[0006] To achieve the above objectives, the present invention adopts the following technical solution:

[0007] A method for preparing a silicon-boron-based zinc-silver-loaded antibacterial agent with a grape branch chain structure includes the following steps:

[0008] S1: Dissolve AgNO3 and ZnCl2 in deionized water to obtain mixed solution A; dissolve C6H5Na3O7 and HO(CH2CH2O) 136 H is dissolved in deionized water to obtain mixed solution B; mixed solution A is added dropwise to mixed solution B and mixed thoroughly to obtain mixed solution C;

[0009] S2: Transfer the mixed solution C from step S1 to a reaction vessel, raise the temperature inside the reaction vessel to 75°C and evacuate to 0.05 MPa for 0.5-1 h. After the reaction is complete, allow it to cool naturally to room temperature. Take out the reaction solution and centrifuge it. Wash the resulting precipitate with anhydrous ethanol and distilled water in sequence, dry it, grind it to a particle diameter of 1 mm using a grinding bowl, and then put it into a high-speed ball mill and ball mill it at a ball milling speed of 500 r / min for 4-6 h to obtain powder A.

[0010] S3: Mix K2O and CaO to obtain a K2O / CaO mixture; add the K2O / CaO mixture, CeO2 and powder A from step S2 to an aqueous alcohol solution and mix thoroughly to obtain suspension A;

[0011] S4: Add SiO2, B2O3 and Na2CO3 to suspension A in step S3 and mix thoroughly to obtain suspension B;

[0012] S5: The suspension B from step S4 is transferred to a high-pressure homogenizer for pressure homogenization, and then the solvent is removed in a reaction vessel to obtain a silicon boron-based zinc-silver antibacterial agent with a grape branch chain structure.

[0013] Furthermore, the amount of AgNO3 is 3-8 parts by mass, the amount of ZnCl2 is 6-14 parts by mass, the amount of C6H5Na3O7 is 5-10 parts by mass, and the amount of HO(CH2CH2O) is... 136 The amount of H is 5-10 parts by mass, the mass ratio of K2O to CaO in the K2O / CaO mixture is 1:9, the amount of the K2O / CaO mixture is 5-10 parts by mass, the amount of CeO2 is 1-2 parts by mass, the amount of SiO2 is 25-35 parts by mass, the amount of B2O3 is 25-40 parts by mass, and the amount of Na2CO3 is 15-20 parts by mass.

[0014] Preferably, the amount of AgNO3 is 3 parts by mass, the amount of ZnCl2 is 6 parts by mass, the amount of C6H5Na3O7 is 6 parts by mass, and the amount of HO(CH2CH2O) is... 136 The amount of H is 6.5 parts by mass, the amount of K2O / CaO mixture is 7 parts by mass, the amount of CeO2 is 1.5 parts by mass, the amount of SiO2 is 30 parts by mass, the amount of B2O3 is 25 parts by mass, and the amount of Na2CO3 is 15 parts by mass.

[0015] Furthermore, the aqueous alcohol solution is prepared by mixing deionized water and anhydrous ethanol in a volume ratio of 2:1.

[0016] Furthermore, the conditions for pressure homogenization are as follows: homogenization is performed three times at a pressure of 100 MPa and a temperature of 70 °C, each time for 20 minutes.

[0017] Furthermore, the solvent removal conditions are as follows: the temperature inside the reactor is raised to 80°C and a vacuum of 0.2 MPa is applied to remove the solvent for 30 minutes.

[0018] A silicon-boron-based zinc-silver-loaded antibacterial agent with a grape branch chain structure is prepared by the above-described preparation method.

[0019] The above-mentioned application of a silicon boron-based zinc-silver loaded antibacterial agent with a grape branch chain structure in the preparation of antibacterial materials.

[0020] The significant advantages of this invention are:

[0021] The Zn-Ag / BSN antibacterial agent with a grape-like branched chain structure prepared by this invention provides a large number of sites for linking loaded antibacterial metal ions through a network-like borosilicate-based carrier (BSN). Zn-Ag ions with antibacterial and bactericidal properties are uniformly distributed on it, thereby achieving a synergistic effect and improving the bactericidal speed and bactericidal effect of the antibacterial agent, exhibiting excellent antibacterial performance, which is an effect that many single antibacterial metal ions cannot achieve.

[0022] The Zn-Ag / BSN antibacterial agent of this invention has a grape-like branched chain structure with certain pores, which can link and fix spherical antibacterial particles onto a three-dimensional network carrier structure. This structure not only effectively increases the loading of antibacterial ions, but also, during application, the spherical antibacterial components are connected to the branches rather than being encapsulated inside the carrier, which can effectively enhance the antibacterial effect and prevent them from being trapped inside and difficult to release. At the same time, during use, the porous structure can effectively absorb moisture, and bacteria grow in the pores, reacting rapidly with the antibacterial ions loaded therein for rapid sterilization, thereby extending the product's service life. Attached Figure Description

[0023] Figure 1 Scanning electron microscope image of Zn-Ag / BSN antibacterial agent.

[0024] Figure 2 X-ray diffraction pattern of Zn-Ag / BSN antibacterial agent.

[0025] Figure 3 The diagram shows the antibacterial effect of the Zn-Ag / BSN antibacterial agent.

[0026] Figure 4 The diagram shows the antibacterial effect of Zn-Ag / BSN antibacterial agent in PE. a, Escherichia coli; b, Staphylococcus aureus. Detailed Implementation

[0027] To make the content of this invention easier to understand, the technical solution of this invention will be further described below with reference to specific embodiments, but this invention is not limited thereto.

[0028] Example 1:

[0029] S1: Add 3 parts by mass of AgNO3 and 6 parts by mass of ZnCl2 to deionized water, heat and stir in a 30°C water bath until completely dissolved, to prepare a mixed aqueous solution with a concentration of 1.5 mol / L, denoted as mixed solution A; add 6 parts by mass of C6H5Na3O7 and 6.5 parts by mass of HO(CH2CH2O) 136 H is added to deionized water and heated in a water bath at 40°C with stirring until completely dissolved, to prepare a mixed aqueous solution with a concentration of 0.6 mol / L, denoted as mixed solution B; mixed solution A is added dropwise to mixed solution B and mixed thoroughly to obtain mixed solution C;

[0030] S2: Transfer the mixed solution C of S1 to the reaction vessel, raise the temperature of the reaction vessel to 75℃ and evacuate to 0.05MPa for 50min. After the reaction is completed, allow it to cool naturally to room temperature. Take out the reaction solution and centrifuge it. Wash the obtained precipitate three times with anhydrous ethanol and distilled water in sequence. Dry it in an oven at 80℃ for 12h. Grind it to a particle diameter of 1mm using a grinding bowl. Then put it into a high-speed ball mill and ball mill it for 5h at a ball milling speed of 500r / min to obtain powder A.

[0031] S3: K2O and CaO are mixed at a mass ratio of 1:9 to obtain a K2O / CaO mixture; 7 parts by mass of the K2O / CaO mixture, 1.5 parts by mass of CeO2 and powder A of S2 are added to an aqueous alcohol solution, the mass of which is 6 times the total mass of the K2O / CaO mixture, CeO2 and powder A. The mixture is magnetically stirred at 200 r / min for 0.5 h until fully mixed to obtain suspension A; wherein, the aqueous alcohol solution is prepared by mixing deionized water and anhydrous ethanol in a volume ratio of 2:1.

[0032] S4: Add 30 parts by mass of SiO2, 25 parts by mass of B2O3 and 15 parts by mass of Na2CO3 to suspension A of S3, and stir magnetically at 200 r / min for 50 min until fully mixed to obtain suspension B;

[0033] S5: Transfer the suspension B of S4 to a high-pressure homogenizer and homogenize it three times for 20 minutes each time at a pressure of 100 MPa and a temperature of 70 °C. Then transfer it to a reaction vessel, raise the temperature inside the reaction vessel to 80 °C and evacuate it to 0.2 MPa to remove the solvent for 30 minutes to obtain an ultrafine powder of silicon boron-based zinc silver-loaded antibacterial agent (Zn-Ag / BSN).

[0034] Figure 1This is a scanning electron microscope (SEM) image of the Zn-Ag / BSN antibacterial agent. The image clearly shows the morphology of the antibacterial component, exhibiting a distinct spherical, branched structure. This unique structure provides abundant sites for loading Zn and Ag ions, thereby significantly increasing the loading capacity of antibacterial ions. Simultaneously, this structure ensures that the spherical antibacterial component is attached to the network of silica-boron-based branches rather than being encapsulated within the carrier, effectively enhancing the antibacterial effect and preventing the antibacterial ions from being trapped and difficult to release.

[0035] Figure 2 The image shows the X-ray diffraction (XRD) pattern of the Zn-Ag / BSN antibacterial agent. Analysis of the three strongest peaks in the XRD pattern revealed the presence of primarily zinc and silver elements, with very few impurities, indicating high purity. This further demonstrates the superior performance of the Zn-Ag / BSN antibacterial agent and provides strong support for its reliability in antibacterial applications.

[0036] The antibacterial effect of Zn-Ag / BSN antibacterial agent was tested according to the WS-T 650-2019 standard. The indicator bacterium was Escherichia coli. The test samples with an inhibition zone diameter > 7 mm were judged to have antibacterial effect, and those with an inhibition zone diameter ≤ 7 mm were judged to have no antibacterial effect. Figure 3 The image shows the antibacterial effect of Zn-Ag / BSN antibacterial agent. The results show that the diameter of the inhibition zone of Zn-Ag / BSN antibacterial agent is 40 mm, indicating that its antibacterial effect is excellent.

[0037] One part by weight of Zn-Ag / BSN antibacterial agent was thoroughly mixed with 99 parts by weight of polyethylene (PE). The mixture was then melt-granulated using a twin-screw extruder at 210℃ and 30 rpm to obtain antibacterial PE granules. These granules were then hot-pressed at 180℃ for 10 minutes to produce sheets with a thickness of 2 mm. The antibacterial effect of the obtained antibacterial PE sheets was tested according to the national standard GB / T 31402-2015, using Escherichia coli and Staphylococcus aureus as indicator bacteria. The results are as follows: Figure 4 As shown, the antibacterial PE sheet can achieve an inhibition rate of over 99.9% against both Escherichia coli and Staphylococcus aureus, demonstrating a powerful antibacterial effect.

[0038] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.

Claims

1. A method for preparing a silicon-boron-based zinc-silver-loaded antibacterial agent with a grape branch chain structure, characterized in that: Includes the following steps: S1: Dissolve AgNO3 and ZnCl2 in deionized water to obtain mixed solution A; dissolve C6H5Na3O7 and HO(CH2CH2O) 136 H is dissolved in deionized water to obtain mixed solution B; mixed solution A is added dropwise to mixed solution B and mixed thoroughly to obtain mixed solution C; S2: Transfer the mixed solution C from step S1 to a reaction vessel, raise the temperature inside the reaction vessel to 75°C and evacuate to 0.05 MPa for 0.5-1 h. After the reaction is complete, allow it to cool naturally to room temperature. Take out the reaction solution and centrifuge it. Wash the resulting precipitate with anhydrous ethanol and distilled water in sequence, dry it, grind it to a particle diameter of 1 mm using a grinding bowl, and then put it into a high-speed ball mill and ball mill it at a ball milling speed of 500 r / min for 4-6 h to obtain powder A. S3: Mix K2O and CaO to obtain a K2O / CaO mixture; add the K2O / CaO mixture, CeO2 and powder A from step S2 to an aqueous alcohol solution and mix thoroughly to obtain suspension A; S4: Add SiO2, B2O3 and Na2CO3 to suspension A in step S3 and mix thoroughly to obtain suspension B; S5: The suspension B from step S4 is transferred to a high-pressure homogenizer for pressure homogenization, and then the solvent is removed in a reaction vessel to obtain a silicon boron-based zinc-silver antibacterial agent with a grape branch chain structure. The amount of AgNO3 used is 3-8 parts by mass, the amount of ZnCl2 used is 6-14 parts by mass, the amount of C6H5Na3O7 used is 5-10 parts by mass, and the amount of HO(CH2CH2O) used is... 136 The amount of H is 5-10 parts by mass, the mass ratio of K2O to CaO in the K2O / CaO mixture is 1:9, the amount of the K2O / CaO mixture is 5-10 parts by mass, the amount of CeO2 is 1-2 parts by mass, the amount of SiO2 is 25-35 parts by mass, the amount of B2O3 is 30-40 parts by mass, and the amount of Na2CO3 is 15-20 parts by mass.

2. The preparation method according to claim 1, characterized in that: The amount of AgNO3 used is 3 parts by mass, the amount of ZnCl2 used is 6 parts by mass, the amount of C6H5Na3O7 used is 6 parts by mass, and the amount of HO(CH2CH2O) used is... 136 The amount of H is 6.5 parts by mass, the amount of the K2O / CaO mixture is 7 parts by mass, the amount of CeO2 is 1.5 parts by mass, the amount of SiO2 is 30 parts by mass, the amount of B2O3 is 25 parts by mass, and the amount of Na2CO3 is 15 parts by mass.

3. The preparation method according to claim 1, characterized in that: The aqueous alcohol solution is prepared by mixing deionized water and anhydrous ethanol in a volume ratio of 2:

1.

4. The preparation method according to claim 1, characterized in that: The conditions for pressure homogenization are as follows: homogenize three times at a pressure of 100 MPa and a temperature of 70 °C, each time for 20 minutes.

5. The preparation method according to claim 1, characterized in that: The conditions for solvent removal are as follows: the temperature inside the reactor is raised to 80°C and the vacuum is drawn to 0.2 MPa to remove the solvent for 30 minutes.

6. A silicon-boron-based zinc-silver-loaded antibacterial agent with a grape branch chain structure, characterized in that: It is prepared by the preparation method according to any one of claims 1 to 5.

7. The application of the silicon boron-based zinc-silver-loaded antibacterial agent according to claim 6 in the preparation of antibacterial materials.

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