Preparation method of polypropylene-based Ag-(MI (Al) (AB)) MOFs antibacterial melt-blown cloth

Abstract

The invention discloses a preparation method of polypropylene-based Ag-(MI) (AB) MOFs antibacterial melt-blown cloth, and belongs to the technical field of antibacterial melt-blown fibers. The preparation method comprises the following steps: firstly, preparing amino-functionalized silver metal organic framework material Ag-(MI) (AB) MOFs through a hydrothermal synthesis method, then blending the amino-functionalized silver metal organic framework material Ag-(MI) (AB) MOFs with PP, preparing PP / Ag-(MI) (AB) MOFs antibacterial master batches by adopting a melt extrusion method, and finally, spinning into the polypropylene-based Ag-(MI) (AB) MOFs antibacterial melt-blown cloth by adopting melt-blown spinning. According to the method, the reaction process is simple, the technical problems of agglomeration, falling, dissolution and the like of a nano-silver antibacterial agent are effectively solved, the polypropylene-based Ag-(MI) (AB) MOFs antibacterial melt-blown cloth which is efficient in filtration, broad-spectrum antibacterial and comfortable to use is finally prepared, the polypropylene-based Ag-(MI) (AB) MOFs antibacterial melt-blown cloth can be applied to the fields of antibacterial medical masks and the like, and a new strategy is provided for developing efficient and lasting medical protective materials.

Description

TECHNICAL FIELD

[0001] The application belongs to the technical field of antibacterial melt-blown fibers, and particularly relates to a preparation method of a polypropylene-based Ag-(MI)(AB) MOFs antibacterial melt-blown cloth. BACKGROUND

[0002] Polypropylene (PP) material is a widely used textile material, and has become an important base material for antibacterial textiles due to its low cost, good processing performance and strong chemical stability. In particular, melt-blown polypropylene (PP) non-woven cloth has a unique three-dimensional network structure, small fiber diameter and high specific surface area, and thus exhibits excellent filtration performance and is widely used in water treatment and air filtration.

[0003] However, the traditional PP non-woven cloth has certain limitations in terms of antibacterial performance. In order to improve the antibacterial performance of the traditional PP melt-blown cloth, many researchers have explored strategies for compounding antibacterial agents with polypropylene melt-blown cloth or substrates. Among them, the performance of silver-based antibacterial agents is the most outstanding. However, the antibacterial melt-blown cloth prepared by compounding silver-based antibacterial agents with polypropylene still faces some problems, such as the easy agglomeration of nano-silver antibacterial agents, which affects the antibacterial effect; in addition, there is a risk of shedding and dissolving of silver particles, which further affects the durability and safety of the material. SUMMARY

[0004] The purpose of the present application is to improve the antibacterial performance of polypropylene melt-blown cloth and solve the technical problems of agglomeration and shedding of nano-silver antibacterial agents, and a preparation method of a polypropylene-based Ag-(MI)(AB) MOFs antibacterial melt-blown cloth is provided.

[0005] The present application is realized by the following technical solutions: A preparation method of a polypropylene-based Ag-(MI)(AB) MOFs antibacterial melt-blown cloth, comprising the following steps: 1) Preparation of Ag-(MI)(AB) MOFs antibacterial agent AgNO3 is weighed and dissolved in distilled water to obtain an AgNO3 solution.

[0006] 2-Methylimidazole (denoted as 2-MI) and 2-amino benzimidazole (denoted as 2-AB) are weighed and dissolved in anhydrous ethanol to obtain an imidazole solution.

[0007] The AgNO3 solution and the imidazole solution are mixed thoroughly, then the imidazole solution is poured into the AgNO3 solution, mixed and stirred, and then left to stand, and then the solution after standing is centrifuged, washed with anhydrous ethanol and distilled water alternately, and vacuum dried, ground to obtain a white powder, to obtain the amino-modified AgMOF (denoted as Ag-(2-methylimidazole)(2-aminobenzimidazole) MOFs, namely Ag-(2-MI)(2-AB) MOFs), which is the Ag-(MI)(AB) MOFs antibacterial agent.

[0008] 2) Preparation of PP / Ag-(MI)(AB) MOFs antibacterial master batch The Ag-(MI)(AB) MOFs antibacterial agent and the PP master batch are weighed into a ball mill for grinding, the Ag-(MI)(AB) MOFs antibacterial agent and the PP master batch powder which are mixed uniformly are blended by using a double-screw extruder, extruded into a continuous columnar sample by the double-screw extruder, and cut into PP / Ag-(MI)(AB) MOFs antibacterial master batches of uniform length by a granulator.

[0009] 3) Preparation of PP / Ag-(MI)(AB) MOFs antibacterial melt-blown fabric The PP / Ag-(MI)(AB) MOFs antibacterial master batch is poured into a melt-blown spinning machine, the spinning parameters and temperature parameters are set, and finally the PP / Ag-(MI)(AB) MOFs antibacterial melt-blown fabric is prepared, which is the polypropylene-based Ag-(MI)(AB) MOFs antibacterial melt-blown fabric.

[0010] Further, in step 1), the ratio of AgNO3 to distilled water is 600 g:9000 mL, the ratio of 2-methylimidazole to anhydrous ethanol is 97 g:9000 mL, the ratio of 2-aminobenzimidazole to anhydrous ethanol is 8 g:9000 mL, and the mass ratio of AgNO3, 2-methylimidazole and 2-aminobenzimidazole is 600:97:8.

[0011] Further, in step 1), the AgNO3 solution and the imidazole solution are mixed thoroughly, which is specifically stirring for 15 min first and then ultrasonic for 2 min; after the imidazole solution is poured into the AgNO3 solution, stirring for 30 min first and then standing for 3 h; the centrifugal washing is at least 3 times, and the temperature for vacuum drying is 60 ℃ and the time is 12 h.

[0012] Further, in step 3), the spinning parameters are set as follows: hot air pressure 0.4 MPa, extruder pressure 4 MPa, web speed 10.77 Hz, winding speed 6.53 Hz, and metering pump speed 16.53 Hz.

[0013] Further, in step 3), the temperature parameters are set as follows: 125 DEG C for the first zone, 175 DEG C for the second zone, 178 DEG C for the third zone, 180 DEG C for the metering pump and pipeline, 195 DEG C for the nozzle, and 210 DEG C for the hot air.

[0014] The method of the application is the preparation method, which comprises the following steps: preparing the amino-functionalized silver metal organic framework material Ag-(MI)(AB) MOFs by a hydrothermal synthesis method, blending the Ag-(MI)(AB) MOFs with PP to prepare the PP / Ag-(MI)(AB) MOFs antibacterial master batch by a melt extrusion method, and finally spinning the PP / Ag-(MI)(AB) MOFs antibacterial master batch into the antibacterial melt-blown fabric by melt blowing, so as to obtain the polypropylene-based Ag-(MI)(AB) MOFs antibacterial melt-blown fabric.

[0015] The method of the application has the advantages of simple reaction process and effective overcoming of technical problems such as agglomeration, peeling and dissolution of the nano-silver antibacterial agent, and finally, the polypropylene-based Ag-(MI)(AB) MOFs antibacterial melt-blown fabric with high filtration efficiency, broad-spectrum antibacterial property and comfortable use is prepared, the polypropylene-based Ag-(MI)(AB) MOFs antibacterial melt-blown fabric can be applied to the field of antibacterial medical protective masks, and a new strategy is provided for developing efficient and durable medical protective materials. BRIEF DESCRIPTION OF DRAWINGS

[0016] The accompanying drawings, which are included to provide a further understanding of the application and constitute a part of this application, illustrate certain illustrative embodiments of the application and together with the description serve to explain the application.

[0017] Figure 1 The figure is the UV-Vis diffuse reflectance spectrum of Ag-MI and Ag-(MI)(AB) MOFs.

[0018] Figure 2 The figure is the band gap diagram of Ag-MI and Ag-(MI)(AB) MOFs.

[0019] Figure 3 The figure is the electrochemical impedance diagram of Ag-MI and Ag-(MI)(AB) MOFs.

[0020] Figure 4 The figure is the electron paramagnetic resonance spectrum (single-line oxygen) of Ag-(MI)(AB) MOFs.

[0021] Figure 5 The figure is the electron paramagnetic resonance spectrum (superoxide free radical) of Ag-(MI)(AB) MOFs.

[0022] Figure 6 The figure is the electron paramagnetic resonance spectrum (hydroxyl radical) of Ag-(MI)(AB) MOFs.

[0023] Figure 7 The pore volume amount versus pore size graph of the PP and PP / Ag-(MI)(AB) MOFs antibacterial melt-blown cloth.

[0024] Figure 8 The cumulative immersion amount versus pressure graph of the PP and PP / Ag-(MI)(AB) MOFs2 antibacterial melt-blown cloth.

[0025] Figure 9 The colony growth graph when antibacterial against Staphylococcus aureus (I: PP melt-blown cloth; II: PP / Ag-(MI)(AB) MOFs antibacterial melt-blown cloth).

[0026] Figure 10 The antibacterial rate graph of the PP melt-blown cloth and the PP / Ag-(MI)(AB) MOFs antibacterial melt-blown cloth against Staphylococcus aureus.

[0027] Figure 11 The colony growth graph when antibacterial against Escherichia coli (I: PP melt-blown cloth; II: PP / Ag-(MI)(AB) MOFs antibacterial melt-blown cloth).

[0028] Figure 12 The antibacterial rate graph of the PP melt-blown cloth and the PP / Ag-(MI)(AB) MOFs antibacterial melt-blown cloth against Escherichia coli. DETAILED DESCRIPTION

[0029] In order to make the objects, technical solutions and advantages of the present application clearer, the present application will be further described in detail below with reference to the accompanying drawings and examples. It should be understood that the specific examples described herein are only used to explain the present application and do not limit the present application.

[0030] The present embodiment provides a preparation method of a polypropylene-based Ag-(MI)(AB) MOFs antibacterial melt-blown cloth, comprising the following steps: 1) Preparation of Ag-(MI)(AB) MOFs antibacterial agent 0.6 g of AgNO3 was weighed and dissolved in 90 mL of distilled water to obtain an AgNO3 solution; 0.97 g of 2-methylimidazole and 0.08 g of 2-aminobenzimidazole were weighed and dissolved in 90 mL of anhydrous ethanol to obtain an imidazole solution; The AgNO3 solution and the imidazole solution were stirred for 15 min and then ultrasonicated for 2 min, and then the imidazole solution was poured into the AgNO3 solution and stirred for 30 min, and then the solution was left to stand for 3 h, and then the solution after standing was centrifuged and washed with anhydrous ethanol and distilled water alternately for at least 3 times, and then vacuum dried at 60 ℃ for 12 h, and then ground to obtain a white powder, to obtain the amino-modified AgMOF, namely Ag-(2-methylimidazole)(2-aminobenzimidazole) MOFs, namely the Ag-(MI)(AB) MOFs antibacterial agent; 2) Preparation of PP / Ag-(MI)(AB) MOFs antibacterial masterbatch The Ag-(MI)(AB) MOFs antibacterial agent and the PP masterbatch were weighed into a ball mill and ground, and the ground and uniformly mixed Ag-(MI)(AB) MOFs antibacterial agent and PP masterbatch powder were blended by using a double-screw extruder, and the blended product was extruded into a continuous columnar sample by the double-screw extruder, and the continuous columnar sample was cut into PP / Ag-(MI)(AB) MOFs antibacterial masterbatch of uniform length by a pelletizer; 3) Preparation of PP / Ag-(MI)(AB) MOFs antibacterial melt-blown fabric The PP / Ag-(MI)(AB) MOFs antibacterial masterbatch was poured into a melt-blown spinning machine, and the spinning parameters were set as follows: hot air pressure 0.4 MPa, extruder pressure 4 MPa, web speed 10.77 Hz, winding speed 6.53 Hz, and metering pump speed 16.53 Hz; the temperature parameters were set as follows: zone 1 125 ℃, zone 2 175 ℃, zone 3 178 ℃, metering pump and pipeline temperature 180 ℃, nozzle temperature 195 ℃, and hot air temperature 210 ℃; and finally the PP / Ag-(MI)(AB) MOFs antibacterial melt-blown fabric was prepared, namely the polypropylene-based Ag-(MI)(AB) MOFs antibacterial melt-blown fabric.

[0031] Table 1 shows the filtration performance of the conventional PP and the PP / Ag-(MI)(AB) MOFs antibacterial melt-blown fabric prepared in this embodiment.

[0032] Table 1 filtration efficiency pressure drop figure of merit PP 54% 31.8 Pa 0.0256 Pa -1 ]] PP / Ag-(MI)(AB) MOFs 78.11% 31.97 Pa 0.049 Pa -1 ]] From the above table, it can be seen that the addition of Ag-(MI)(AB) MOFs greatly improves the filtration efficiency of the PP / Ag-(MI)(AB) MOFs antibacterial melt-blown fabric.

[0033] Figures 1 to 3UV-Vis diffuse reflectance spectra, band gap, electrochemical impedance spectroscopy of Ag-MI (pointing to the non-amino modified AgMOF) and Ag-(MI)(AB) MOFs. From the figure, the introduction of amino group can broaden the light response range of Ag-(MI)(AB) MOFs material.

[0034] Figures 4 to 6 The paramagnetic resonance spectrogram of Ag-(MI)(AB) MOFs: single line oxygen, superoxide radical, hydroxyl radical. From the figure, the antibacterial mechanism of Ag-(MI)(AB) MOFs is a synergistic antibacterial mechanism of contact sterilization, active oxygen sterilization and chemical sterilization.

[0035] Figure 7 The pore volume and pore size relationship diagram of PP and PP / Ag-(MI)(AB) MOFs antibacterial melt-blown cloth. From the figure, the content of small pore size in the melt-blown cloth increases.

[0036] Figure 8 The cumulative immersion and pressure relationship diagram of PP and PP / Ag-(MI)(AB) MOFs antibacterial melt-blown cloth. From the figure, the fiber diameter distribution is narrowed, which is beneficial to enhance the filtration performance of Ag-(MI)(AB) MOFs melt-blown cloth.

[0037] Figure 9 The growth of S. aureus colony when antibacterial (I: PP melt-blown cloth; II: PP / Ag-(MI)(AB) MOFs antibacterial melt-blown cloth), Figure 10 The antibacterial rate diagram of PP melt-blown cloth and PP / Ag-(MI)(AB) MOFs antibacterial melt-blown cloth on S. aureus. From the figure, at 40 min, the PP / Ag-(MI)(AB) MOFs antibacterial melt-blown cloth completely kills S. aureus.

[0038] Figure 11 The growth of E. coli colony when antibacterial (I: PP melt-blown cloth; II: PP / Ag-(MI)(AB) MOFs antibacterial melt-blown cloth), Figure 12 The antibacterial rate diagram of PP melt-blown cloth and PP / Ag-(MI)(AB) MOFs antibacterial melt-blown cloth on E. coli. From the figure, at 50 min, the PP / Ag-(MI)(AB) MOFs antibacterial melt-blown cloth completely kills E. coli.

[0039] Those skilled in the art will readily understand that the above description is only preferred embodiments of the present application, and is not intended to limit the present application, and any modifications, equivalent replacements and improvements made within the spirit and principle of the present application shall be included in the protection scope of the present application.

Claims

1. A method for preparing a polypropylene-based Ag-(MI)(AB) MOFs antibacterial meltblown fabric, characterized in that, Includes the following steps: 1) Preparation of Ag-(MI)(AB) MOFs antibacterial agents Weigh out AgNO3 and dissolve it in distilled water to obtain an AgNO3 solution; Weigh out 2-methylimidazole and 2-aminobenzimidazole and dissolve them in anhydrous ethanol to obtain an imidazole solution; The AgNO3 solution and the imidazole solution were thoroughly mixed separately. Then the imidazole solution was poured into the AgNO3 solution, mixed and stirred, and allowed to stand. The solution after standing was then centrifuged, washed with anhydrous ethanol and distilled water by alternating centrifugation, and vacuum dried. The solution was then ground to obtain a white powder, which is the amino-modified AgMOF, namely the Ag-(MI)(AB) MOFs antibacterial agent. 2) Preparation of PP / Ag-(MI)(AB) MOFs antibacterial masterbatch Weigh Ag-(MI)(AB) MOFs antibacterial agent and PP masterbatch and grind them in a ball mill. Use a twin-screw extruder to blend the uniformly ground Ag-(MI)(AB) MOFs antibacterial agent and PP masterbatch powder. Extrude the mixture into a continuous columnar sample through a twin-screw extruder. Then, use a granulator to cut it into PP / Ag-(MI)(AB) MOFs antibacterial masterbatch with uniform length. 3) Preparation of PP / Ag-(MI)(AB) MOFs antibacterial meltblown fabric The PP / Ag-(MI)(AB) MOFs antibacterial masterbatch was poured into a meltblown spinning machine, and the spinning parameters and temperature parameters were set to finally prepare the PP / Ag-(MI)(AB) MOFs antibacterial meltblown fabric, which is the polypropylene-based Ag-(MI)(AB) MOFs antibacterial meltblown fabric.

2. The method for preparing polypropylene-based Ag-(MI)(AB) MOFs antibacterial meltblown fabric according to claim 1, characterized in that: In step 1), the ratio of AgNO3 to distilled water is 600 g : 9000 mL, the ratio of 2-methylimidazole to anhydrous ethanol is 97 g : 9000 mL, the ratio of 2-aminobenzimidazole to anhydrous ethanol is 8 g : 9000 mL, and the mass ratio of AgNO3, 2-methylimidazole, and 2-aminobenzimidazole is 600:97:

8.

3. The method for preparing polypropylene-based Ag-(MI)(AB) MOFs antibacterial meltblown fabric according to claim 1, characterized in that: In step 1), the AgNO3 solution and imidazole solution are thoroughly mixed by stirring for 15 min and then sonicating for 2 min; after the imidazole solution is poured into the AgNO3 solution, it is stirred for 30 min and then allowed to stand for 3 h; centrifugation and washing are performed at least 3 times, and vacuum drying is carried out at a temperature of 60 ℃ for 12 h.

4. The method for preparing polypropylene-based Ag-(MI)(AB) MOFs antibacterial meltblown fabric according to claim 1, characterized in that: In step 3), the spinning parameters are set as follows: hot air pressure 0.4 MPa, extruder pressure 4 MPa, mesh belt speed 10.77 Hz, winding speed 6.53 Hz, and metering pump speed 16.53 Hz.

5. The method for preparing polypropylene-based Ag-(MI)(AB) MOFs antibacterial meltblown fabric according to claim 1, characterized in that: In step 3), the temperature parameters are set as follows: Zone 1 125 ℃, Zone 2 175 ℃, Zone 3 178 ℃, metering pump and pipeline temperature 180 ℃, nozzle temperature 195 ℃, and hot air temperature 210 ℃.

Images