Preparation method of silicon-boron-based zinc-silver-loaded antibacterial agent with grape branch chain structure

Abstract

The invention discloses a preparation method of a silicon-boron-based zinc-silver-loaded antibacterial agent with a grape branch chain structure. The silicon-boron-based zinc-silver-loaded antibacterial agent with a grape branch chain structure is successfully prepared by combining antibacterial components with a silicon-based net chain carrier by adopting a sol-gel method through a process of combining zinc and silver ions and a process of combining high-pressure homogenization and hydrothermal treatment. Compared with the problems of limited carrier accommodating sites, difficult release of antibacterial particles wrapped in the carrier and the like in the prior art, the branched carrier disclosed by the invention not only can effectively improve the loading capacity of antibacterial ions, but also can be used for preparing a spherical antibacterial component which is connected to a branched chain instead of being wrapped in the carrier in an application process, so that the spherical antibacterial component is not easily released. The antibacterial effect can be effectively improved, and the situation that the antibacterial agent is wrapped inside and is not easy to release is prevented. Due to the design, the silicon-boron-based zinc-loaded silver antibacterial agent shows an efficient sterilization effect and has relatively high stability and durability, so that the service life of the product is remarkably prolonged.

Description

Technical Field

[0001] The invention belongs to the technical field of silver-carrying antibacterial agent materials, and in particular relates to a preparation method of a silicon-boron-based zinc-carrying silver antibacterial agent with a grape branch chain structure. Background Art

[0002] Harmful bacteria are everywhere in nature. Nosocomial infections, cross infections, infectious diseases, etc. caused by them pose a serious threat to people's lives and safety. Plastic products are widely used in modern people's daily lives. Usually, these products do not have antibacterial properties, and some are even favorable places for the growth of pathogens. After the antibacterial function of plastics, it can quickly kill microorganisms on its surface or inhibit their proliferation, keeping itself clean. The public's awareness of product safety and hygiene has greatly increased, and the antibacterial plastic products industry has entered a stage of rapid development. It is expected that the market size will exceed the trillion yuan mark by 2030.

[0003] Current research shows that some inorganic antimicrobial agents have achieved certain success in the plastics market. However, researchers also realize that there are still some challenges in the field of inorganic antimicrobial agents, such as the complexity of the preparation process, cost considerations, and performance requirements in specific application scenarios. Therefore, further innovation and in-depth research on the preparation and application of inorganic antimicrobial materials has become an important direction of current scientific research.

[0004] The present invention provides a method for preparing a silicon-boron-based zinc-silver antibacterial agent with a grape branch chain structure, which successfully links Zn-Ag antibacterial ions evenly on a mesh silicon-boron-based material by a "sol-gel-hydrothermal" process, thereby forming a silicon-boron-based zinc-silver antibacterial agent with uniform loading and fine particles. The silicon-boron-based zinc-silver antibacterial agent successfully loads a dual antibacterial material of Zn and Ag, significantly improving the antibacterial and sterilization speed and durability of the antibacterial agent. Summary of the invention

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

[0006] To achieve the above object, the present invention adopts the following technical solutions: A method for preparing a silicon-boron-based zinc-silver antibacterial agent having a grape branch chain structure comprises the following steps: S1: Dissolve AgNO3 and ZnCl2 in ionized water to obtain mixed solution A; Dissolve C6H5Na3O7 and HO(CH2CH2O) 136 H is dissolved in deionized water to obtain a mixed solution B; the mixed solution A is added dropwise to the mixed solution B and mixed thoroughly to obtain a mixed solution C; S2: The mixed solution C in step S1 is transferred to a reactor, the temperature in the reactor is raised to 75°C and the reactor is evacuated to 0.05 MPa for reaction for 0.5-1 h. After the reaction is completed, the reaction solution is naturally cooled to room temperature, the reaction solution is taken out and centrifuged on a centrifuge, the obtained precipitate is washed with anhydrous ethanol and distilled water in turn, dried, ground with a grinding mortar to a particle diameter of 1 mm, and then put into a high-speed ball mill at a ball milling speed of 500 r / min for 4-6 h to obtain powder A; S3: mixing K2O and CaO to obtain a K2O / CaO mixture; adding the K2O / CaO mixture, CeO2 and the powder A of step S2 to the hydroalcohol solution, mixing them thoroughly to obtain a suspension A; S4: adding SiO2, B2O3 and Na2CO3 to the suspension A of step S3, mixing thoroughly to obtain suspension B; S5: transferring the suspension B in step S4 to a high-pressure homogenizer for pressure homogenization, and then removing the solvent in a reactor to obtain a silicon-boron-based zinc-silver antibacterial agent having a grape branch chain structure; Further, the amount of AgNO3 is 3 to 8 parts by mass, the amount of ZnCl2 is 6 to 14 parts by mass, the amount of C6H5Na3O7 is 5 to 10 parts by mass, and the amount of HO(CH2CH2O) is 1 to 2 parts by mass. 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; 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 6 parts by mass. 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; Furthermore, the hydroalcohol solution is prepared by mixing deionized water and anhydrous ethanol in a volume ratio of 2:1; Furthermore, the pressure homogenization conditions are: homogenization 3 times at a pressure of 100 MPa and a temperature of 70° C., each time for 20 minutes; Furthermore, the conditions for removing the solvent are: raising the temperature in the reactor to 80° C. and evacuating the reactor to 0.2 MPa to remove the solvent for 30 minutes.

[0007] A boron-silicon-based zinc-silver antibacterial agent with a grape branch chain structure is prepared by the above-mentioned preparation method.

[0008] The application of the above-mentioned silicon boron-based zinc-silver antibacterial agent with a grape branch chain structure in the preparation of antibacterial materials.

[0009] The significant advantages of the present invention are: The Zn-Ag / BSN antibacterial agent with a grape branch chain structure prepared by the present invention has a mesh-shaped boron silicone-based carrier (BSN) that provides a large number of sites for linking and loading antibacterial metal ions, and Zn-Ag ions with antibacterial and bactericidal properties are evenly distributed on it, thereby being able to act synergistically to improve the bactericidal speed and bactericidal effect of the antibacterial agent, and exhibiting excellent antibacterial properties, which is an effect that many single antibacterial metal ions cannot demonstrate.

[0010] The Zn-Ag / BSN antibacterial agent of the present invention has a grape branch chain structure with certain pores, which can link and fix spherical antibacterial particles on a three-dimensional network carrier structure. This structure can not only effectively increase the loading amount of antibacterial ions, but also during the application process, the spherical antibacterial components are connected to the branch chains instead of being wrapped inside the carrier, which can effectively improve the antibacterial effect and prevent them from being wrapped inside and difficult to release; at the same time, during use, the porous structure can effectively absorb moisture, bacteria grow in the pores, and quickly react with the antibacterial ions loaded therein to quickly kill bacteria, thereby extending the service life of the product. BRIEF DESCRIPTION OF THE DRAWINGS

[0011] Figure 1 This is a scanning electron microscope image of the Zn-Ag / BSN antibacterial agent.

[0012] Figure 2 This is the X-ray diffraction pattern of Zn-Ag / BSN antibacterial agent.

[0013] Figure 3 This is the antibacterial effect diagram of Zn-Ag / BSN antibacterial agent.

[0014] Figure 4 The antibacterial effect of Zn-Ag / BSN antibacterial agent in PE. a, Escherichia coli; b, Staphylococcus aureus. DETAILED DESCRIPTION

[0015] In order to make the contents of the present invention easier to understand, the technical solution of the present invention is further described below in conjunction with specific implementation methods, but the present invention is not limited thereto.

[0016] Embodiment 1: S1: Add 3 parts by mass of AgNO3 and 6 parts by mass of ZnCl2 into deionized water, heat and stir in a water bath at 30°C until completely dissolved, to prepare a mixed aqueous solution with a concentration of 1.5 mol / L, recorded as mixed solution A; add 6 parts by mass of C6H5Na3O7 and 6.5 parts by mass of HO(CH2CH2O) 136 H was added into deionized water, heated in a water bath at 40°C and stirred until completely dissolved, to prepare a mixed aqueous solution with a concentration of 0.6 mol / L, recorded as mixed solution B; mixed solution A was added dropwise into mixed solution B, and mixed thoroughly to obtain mixed solution C; S2: The mixed solution C of S1 was transferred to a reactor, the temperature in the reactor was raised to 75°C and the reactor was evacuated to 0.05MPa for 50 minutes. After the reaction was completed, it was naturally cooled to room temperature. The reaction solution was taken out and centrifuged on a centrifuge. The obtained precipitate was washed with anhydrous ethanol and distilled water three times in sequence, dried in an oven at 80°C for 12 hours, ground in a grinding mortar to a particle diameter of 1mm, and then put into a high-speed ball mill at a ball milling speed of 500r / min for 5 hours to obtain powder A; S3: K2O and CaO are mixed in 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 S2 powder A are added to a hydroalcohol solution, the mass of the hydroalcohol solution being 6 times the total mass of the K2O / CaO mixture, CeO2 and powder A, and magnetically stirred at 200 r / min for 0.5 h until fully mixed to obtain a suspension A; wherein the hydroalcohol solution is prepared by mixing deionized water and anhydrous ethanol in a volume ratio of 2:1; S4: 30 parts by mass of SiO2, 25 parts by mass of B2O3 and 15 parts by mass of Na2CO3 were added to the suspension A of S3, and magnetically stirred at 200 r / min for 50 min until fully mixed to obtain a suspension B; S5: The suspension B of S4 was transferred to a high-pressure homogenizer and homogenized three times at a pressure of 100 MPa and a temperature of 70°C for 20 min each time. Then the suspension was transferred to a reactor, the temperature in the reactor was raised to 80°C and the reactor was evacuated to 0.2 MPa to remove the solvent for 30 min to obtain an ultrafine powder of silicon-boron-based zinc-silver antibacterial agent (Zn-Ag / BSN).

[0017] Figure 1 This is a scanning electron microscope image of the Zn-Ag / BSN antibacterial agent. The image clearly shows the morphology of the antibacterial component, showing a distinct grape spherical branch chain structure. This unique structure provides abundant sites for loading Zn and Ag ions, thereby significantly increasing the loading amount of antibacterial ions. At the same time, this structure allows the spherical antibacterial components to be connected to the mesh silicon boron-based branch chains instead of being encapsulated inside the carrier, which can effectively improve the antibacterial effect and prevent the antibacterial ions from being encapsulated and difficult to release.

[0018] Figure 2 This is the X-ray diffraction diagram of the Zn-Ag / BSN antibacterial agent. By analyzing the three strong peaks of the XRD diagram, zinc and silver elements were mainly detected, and there were very few impurities, showing the characteristics of high purity. This further proves the superior performance of the Zn-Ag / BSN antibacterial agent and provides strong support for its reliability in antibacterial applications.

[0019] The antibacterial effect of Zn-Ag / BSN antibacterial agent was tested in accordance with the WS-T 650-2019 standard. The indicator bacteria was Escherichia coli. The test samples with an antibacterial ring diameter of >7mm were judged to have antibacterial effect, and those with an antibacterial ring diameter of ≤7mm were judged to have no antibacterial effect. Figure 3 This is the antibacterial effect diagram of Zn-Ag / BSN antibacterial agent. The results show that the diameter of the inhibition zone of Zn-Ag / BSN antibacterial agent is 40mm, which means that its antibacterial effect is excellent.

[0020] 1 part by mass of Zn-Ag / BSN antimicrobial agent was fully mixed with 99 parts by mass of polyethylene (PE), and melt-cut into pellets using a twin-screw pelletizer at 210°C and 30rpm to obtain antimicrobial PE pellets; the antimicrobial PE pellets were hot-pressed at 180°C for 10 minutes using a hot press to form a 2mm thick sheet. The antimicrobial effect of the obtained antimicrobial PE sheet was tested according to the national standard GB / T 31402-2015, with the indicator bacteria being Escherichia coli and Staphylococcus aureus. The results are as follows Figure 4 As shown, the antibacterial PE sheet can achieve an antibacterial rate of more than 99.9% against both Escherichia coli and Staphylococcus aureus, demonstrating a strong antibacterial effect.

[0021] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention should fall within the scope of the present invention.

Claims

1. A method for preparing a silicon-boron-based zinc-silver antibacterial agent having a grape branch chain structure, characterized in that: The following steps are involved: S1: Dissolve AgNO3 and ZnCl2 in ionized water to obtain mixed solution A; Dissolve C6H5Na3O7 and HO(CH2CH2O) 136 H is dissolved in deionized water to obtain a mixed solution B; the mixed solution A is added dropwise to the mixed solution B and mixed thoroughly to obtain a mixed solution C; S2: The mixed solution C in step S1 is transferred to a reactor, the temperature in the reactor is raised to 75°C and the reactor is evacuated to 0.05 MPa for reaction for 0.5-1 h. After the reaction is completed, the reaction solution is naturally cooled to room temperature, the reaction solution is taken out and centrifuged on a centrifuge, the obtained precipitate is washed with anhydrous ethanol and distilled water in turn, dried, ground with a grinding mortar to a particle diameter of 1 mm, and then put into a high-speed ball mill at a ball milling speed of 500 r / min for 4-6 h to obtain powder A; S3: mixing K2O and CaO to obtain a K2O / CaO mixture; adding the K2O / CaO mixture, CeO2 and the powder A of step S2 to the hydroalcohol solution, mixing them thoroughly to obtain a suspension A; S4: adding SiO2, B2O3 and Na2CO3 to the suspension A of step S3, mixing thoroughly to obtain suspension B; S5: The suspension B of step S4 is transferred to a high-pressure homogenizer for pressure homogenization, and then the solvent is removed in a reactor to obtain a silicon boron-based zinc-silver antibacterial agent with a grape branch chain structure.

2. The preparation method according to claim 1, characterized in that: 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 10-20 parts by mass. 136 The amount of H is 5-10 parts by mass, the mass ratio of K2O and 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.

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

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

1.

5. The preparation method according to claim 1, characterized in that: The pressure homogenization conditions are: homogenization for 3 times at a pressure of 100 MPa and a temperature of 70° C., each time for 20 minutes.

6. The preparation method according to claim 1, characterized in that: The conditions for removing the solvent are: raising the temperature in the reactor to 80° C. and evacuating the reactor to 0.2 MPa to remove the solvent for 30 minutes.

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

8. Use of the silicon-boron-based zinc-silver antibacterial agent according to claim 7 in the preparation of antibacterial materials.

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