A composite antibacterial and highly efficient air filtration membrane, its preparation method and application

Abstract

The present invention relates to the field of electrospun fiber membranes, and discloses a composite antibacterial and highly efficient air filtration membrane, a preparation method thereof and an application. The preparation method includes the following steps: (1) Prepare a modified zein, a polyvinyl alcohol solution, a polyvinyl butyral acetate ethanol solution and a polyvinyl acetate solution; (2) Mix and dissolve the modified zein with the polyvinyl alcohol solution to obtain a mixed solution A; Use the mixed solution A as an electrospinning solution to perform electrospinning to obtain a first-layer fiber membrane; (3) Use the polyvinyl butyral acetate ethanol solution to perform electrospinning on the first-layer fiber membrane to obtain a two-layer fiber membrane; (4) Mix ciprofloxacin hydrochloride, the polyvinyl alcohol solution and the polyvinyl acetate solution to obtain a mixed solution C; Use the mixed solution C to perform electrospinning on the two-layer fiber membrane to obtain a composite antibacterial and highly efficient air filtration membrane. The filtration membrane of the present invention has good air filtration performance and antibacterial performance.

Description

Technical Field

[0001] The present invention relates to the field of electrospun fiber membranes, in particular to a composite antibacterial and highly efficient air filtration membrane, a preparation method thereof, and an application thereof. Background Art

[0002] With the development of industrial technology, people's living standards have been increasing day by day. However, this has also brought serious air pollution problems. Bacteria and fine particles in the air are easily attached with toxic and harmful substances (such as heavy metals, microorganisms, etc.), and have a long residence time and a long transportation distance in the atmosphere, which has a great impact on human health. With the improvement of people's health awareness, more and more people choose to buy home air purifiers. Currently, most families choose to use air purifiers with high-efficiency air filters. When the air purifier is in use, in the humid environment in the south, particulate matter will continuously deposit in the filter membrane, and accompanied by the growth of mold. Seriously, it can release harmful microbial aerosols into the air, greatly reducing the purification performance of the air purifier. Summary of the Invention

[0003] Therefore, it is necessary to provide a composite antibacterial and highly efficient air filtration membrane, a preparation method thereof, and an application thereof to solve the problem that the air filtration membrane of the existing purifier cannot achieve a good antibacterial effect and affects the purification performance.

[0004] To achieve the above object, the present invention provides a preparation method of a composite antibacterial and highly efficient air filtration membrane. The composite antibacterial and highly efficient air filtration membrane includes a filtration layer and an antibacterial layer. The preparation method of the composite antibacterial and highly efficient air filtration membrane includes the following steps:

[0005] (1) Raw material preparation:

[0006] Dissolve zein in solvent A, fully stir to form a stable solution, and then stand for 24 - 72 h to form a paste-like solid of modified zein.

[0007] Dissolve polyvinyl alcohol in solvent A, place it in a water bath and heat until completely dissolved to obtain a polyvinyl alcohol solution.

[0008] Dissolve polyvinyl butyral in an ethanol solution to obtain a polyvinyl butyral ethanol solution.

[0009] Dissolve polyvinyl acetate in solvent A to prepare a polyvinyl acetate solution.

[0010] (2) Mix and dissolve the paste-like solid of modified zein with the polyvinyl alcohol solution, stir evenly to obtain a mixed solution A; use the mixed solution A as an electrospinning solution for electrospinning to obtain a first layer of fiber membrane.

[0011] (3) Use a polyvinyl butyral ethanol solution as the electrospinning solution to perform electrospinning on the first-layer fiber membrane to obtain a two-layer fiber membrane.

[0012] (4) Mix a polyvinyl alcohol solution and a polyvinyl acetate solution to obtain a mixed solution B; dissolve ciprofloxacin hydrochloride in the mixed solution B to obtain a mixed solution C. Use the mixed solution C as the electrospinning solution to perform electrospinning on the two-layer fiber membrane to obtain a three-layer fiber membrane, and the three-layer fiber membrane is the composite antibacterial and highly efficient air filtration membrane.

[0013] Furthermore, in the mixed solution A, the mass ratio of the modified zein to polyvinyl alcohol is 1-3:1-3.

[0014] Furthermore, in the mixed solution A, the mass percentage of the modified zein is 5%-10%, and the mass percentage of polyvinyl alcohol is 5%-10%.

[0015] Furthermore, the mass percentage of polyvinyl butyral is 2%-12%.

[0016] Furthermore, in the mixed solution C, the mass percentage of ciprofloxacin hydrochloride is 5%-12%, the mass percentage of polyvinyl alcohol is 5%-12%, and the mass percentage of polyvinyl acetate is 5%-12%.

[0017] Furthermore, the solvent A is an acetic acid-aqueous solution, and the mass ratio of acetic acid to water is 1-3:1-3. The type of the polyvinyl alcohol is type 1799, type 1788 or type 124.

[0018] Furthermore, in the acetic acid-aqueous solution, the mass ratio of acetic acid to water is 1:1.

[0019] Furthermore, the type of the polyvinyl alcohol is different types of polyvinyl alcohol such as type 1799, type 1788, type 124, etc.

[0020] Furthermore, when electrospinning the mixed solution A: use a 22G needle, the spinning voltage is 15-20 kV, and the feeding rate is 0.3-0.7 mL / h;

[0021] When electrospinning the polyvinyl butyral ethanol solution: use a 26G needle, the spinning voltage is 5-10 kV, and the feeding rate is 1.5-4.5 mL / h;

[0022] When electrospinning the mixed solution C: use a 22G needle, the spinning voltage is 18-24 kV, and the feeding rate is 0.3-1.0 mL / h.

[0023] The composite antibacterial and highly efficient air filtration membrane prepared by the above-mentioned preparation method of the composite antibacterial and highly efficient air filtration membrane comprises, from outside to inside, a zein-polyvinyl alcohol electrospun fiber membrane, a polyvinyl butyral electrospun fiber membrane, and a supported ciprofloxacin hydrochloride-polyvinyl alcohol-polyvinyl acetate electrospun fiber membrane.

[0024] The application of the composite antibacterial and highly efficient air filtration membrane prepared by the above-mentioned preparation method of the composite antibacterial and highly efficient air filtration membrane is applied to masks, window screens or air purification filters.

[0025] The above technical solution has the following beneficial effects:

[0026] (1) All components in the composite antibacterial and highly efficient air filtration membrane prepared by the present invention can be completely degraded by green solvents. The surface characteristics of air pollutants basically depend on the OH, CO and other functional groups present therein. Zein and polyvinyl alcohol fiber membranes can bind to different types of pollutants, effectively improving the filtration efficiency. By electrospinning a layer of polyvinyl butyral fiber membrane on the surface of the zein and polyvinyl alcohol fiber membrane, the water resistance and mechanical strength of the air filtration membrane are improved, further improving the air filtration efficiency and service life.

[0027] (2) Ciprofloxacin hydrochloride is mixed with polyvinyl alcohol and polyvinyl acetate and then electrospun. The prepared fiber membrane has a higher specific surface area, smaller pore size and enhanced electrostatic effect brought by an extremely fine diameter, which can effectively intercept and adsorb ultrafine particles, greatly increasing the air filtration performance. Its filtration efficiency for PM0.3 reaches more than 99%, and the resistance pressure drop does not exceed 85 Pa, successfully achieving efficient air filtration.

[0028] (4) In the present invention, the preparation process of the filtration membrane uses a full polymer solution for electrospinning, effectively avoiding the nano-toxicity brought by the introduction of inorganic nanoparticles, realizing the preparation of a highly efficient air filtration membrane with safe and efficient antibacterial properties, and further broadening the application field of the prepared nano air filtration membrane. Description of the Drawings

[0029] Figure 1 Schematic diagram of the preparation process of the composite antibacterial and highly efficient air filtration membrane prepared in the specific embodiment;

[0030] Figure 2 Flow chart of the preparation of the composite antibacterial and highly efficient air filtration membrane described in the specific embodiment.

[0031] Figure 3 Scanning electron microscope image of the composite antibacterial and highly efficient air filtration membrane prepared for Experimental Group 13.

[0032] Figure 4 Scanning electron microscope image of the composite antibacterial and highly efficient air filtration membrane prepared for Experimental Group 35.

[0033] Figure 5 The composite antibacterial and highly efficient air filtration membrane prepared for Test Group 13 inhibits Escherichia coli.

[0034] Figure 6 The composite antibacterial and highly efficient air filtration membrane prepared for Test Group 13 against Candida albicans.

[0035] Figure 7 Scanning electron micrograph of the composite antibacterial and highly efficient air filtration membrane prepared for Test Group 9.

[0036] Figure 8 Scanning electron micrograph of the composite antibacterial and highly efficient air filtration membrane prepared for Test Group 10.

[0037] Figure 9 Scanning electron micrograph of the composite antibacterial and highly efficient air filtration membrane prepared for Test Group 14.

[0038] Figure 10 Scanning electron micrograph of the composite antibacterial and highly efficient air filtration membrane prepared for Test Group 16. Detailed implementation manners

[0039] To illustrate in detail the technical content, structural features, achieved objectives and effects of the technical solution, the following is a detailed description in conjunction with specific embodiments and accompanied by drawings.

[0040] In the embodiments of the present invention, the type of the polyvinyl alcohol can be type 1799, type 1788 or type 124. In the following test groups, the type of polyvinyl alcohol is all type 1799.

[0041] I. Test Groups 1 - 8: The effects of different mass fractions of polyvinyl alcohol and zein in the mixed solution A, and different acetic acid - water ratios of the solvent A on the composite antibacterial and highly efficient air filtration membrane.

[0042] The preparation process of the composite antibacterial and highly efficient air filtration membrane includes the following steps:

[0043] (1) Dissolve zein in the solvent A, stir well to form a stable solution, and then let it stand for 48 h to form a pale yellow paste - like solid of modified zein. The mass fraction of zein in the solvent A is 10%.

[0044] Dissolve polyvinyl alcohol in the solvent A, place it in a water bath and heat until completely dissolved to obtain a polyvinyl alcohol solution. The mass ratio of the polyvinyl alcohol solution can be 3%, 5%, 9%, 10%.

[0045] Dissolve polyvinyl butyral in an ethanol solution to obtain a polyvinyl butyral ethanol solution, and prepare mass fractions of 4% respectively;

[0046] Dissolve polyvinyl acetate in solvent A to prepare a polyvinyl acetate solution; solvent A is an acetic acid - aqueous solution, and the mass ratio of acetic acid to water in the acetic acid - aqueous solution is 1 - 3:1 - 3;

[0047] (2) Take the paste - like solid in step (1) and dissolve it in a polyvinyl alcohol solution to obtain a mixed solution A. The mass percentage of polyvinyl alcohol and zein in the mixed solution A can be 3%, 9%, 4%, 8%, 9%, 3%, 5%, 5%, 10%, 10%, 5%, 10%. After mixing the mixed solution A evenly, add it to a syringe. Under the conditions that the output voltage of the high - voltage power supply is 18 kV, the distance between the needle and the receiving device is 10 cm, and the liquid supply speed is 0.5 mL / h, use an electrospinning machine to spin - form the first - layer fiber membrane.

[0048] (3) Conduct electrospinning experiments on a 4% polyvinyl butyral ethanol solution. Under the conditions that the output voltage of the high - voltage power supply is 7 kV, the distance between the needle and the receiving device is 10 cm, and the liquid supply speed is 2.5 mL / h, use the first - layer fiber membrane obtained in step (2) as the collection substrate to conduct electrospinning to obtain a two - layer fiber membrane.

[0049] (4) Mix the polyvinyl alcohol solution and the polyvinyl acetate solution to obtain a mixed solution B; dissolve ciprofloxacin hydrochloride in the mixed solution B to obtain a mixed solution C. The mass percentage of ciprofloxacin hydrochloride in the mixed solution C is 10%, the mass percentage of polyvinyl alcohol is 10%, and the mass percentage of polyvinyl acetate is 10%. Under the conditions that the output voltage of the high - voltage power supply is 22 kV, the distance between the needle and the receiving device is 10 cm, and the liquid supply speed is 0.5 mL / h, use the two - layer fiber membrane obtained in step (3) as the collection substrate to spin - form a three - layer fiber membrane. The three - layer fiber membrane is the composite antibacterial and highly efficient air - filtering membrane.

[0050] Through different mass fractions of polyvinyl alcohol and zein and different acetic acid - water ratios of solvent A, the performance of the prepared composite antibacterial and highly efficient air - filtering membrane is detected as shown in Table 1 below. Table 1, the filtering performance of the composite antibacterial and highly efficient air - filtering membrane

[0051]

[0052]

[0053] As can be seen from the above table, when the best mass fraction of polyvinyl alcohol in the mixed solution A is 10%, the mass fraction of zein is 10%, and the mass ratio of acetic acid to water in solvent A is 1:1, the prepared air - filtering membrane has strong filtering performance.

[0054] II. Test groups 9 - 18: The influence of different percentages of polyvinyl butyral concentration on the prepared air - filtering membrane

[0055] The preparation process of the composite antibacterial and highly efficient air filtration membrane includes the following steps:

[0056] (1) Dissolve zein in solvent A, stir well to form a stable solution, and then let it stand for 24 - 72 h to form a light yellow paste-like solid of modified zein. The mass fraction of zein in solvent A is 10%.

[0057] Dissolve polyvinyl alcohol in solvent A, place it in a water bath and heat until completely dissolved to obtain a polyvinyl alcohol solution. The mass ratio of the polyvinyl alcohol solution is 10%.

[0058] Dissolve polyvinyl butyral in an ethanol solution to obtain a polyvinyl butyral ethanol solution, and prepare mass fractions of 2%, 4%, 4.5%, 5%, 6.5%, 7%, 7.5%, 8%, 10%, and 12% respectively.

[0059] Dissolve polyvinyl acetate in solvent A to prepare a polyvinyl acetate solution.

[0060] Solvent A is an acetic acid - aqueous solution, and the mass ratio of acetic acid to water in the acetic acid - aqueous solution is 1 - 1.

[0061] (2) Take the paste-like solid in step (1) and dissolve it in the polyvinyl alcohol solution to obtain mixed solution A. The mass ratio of polyvinyl alcohol to zein in mixed solution A is 1:2 or 1:1. After mixing mixed solution A evenly, add it to a syringe, and use an electrospinning machine to spin at an output voltage of 18 kV of the high-voltage power supply, a distance of 10 cm between the needle and the receiving device, and a feeding speed of 0.5 mL / h to obtain the first-layer fiber membrane.

[0062] (3) Conduct electrospinning experiments on 2%, 4%, 4.5%, 5%, 6.5%, 7%, 7.5%, 8%, 10%, or 12% polyvinyl butyral ethanol solutions respectively. Using the first-layer fiber membrane obtained in step (2) as the collection substrate, conduct electrospinning at an output voltage of 7 kV of the high-voltage power supply, a distance of 10 cm between the needle and the receiving device, and a feeding speed of 2.5 mL / h to obtain a two-layer fiber membrane.

[0063] (4) Mix the polyvinyl alcohol solution and the polyvinyl acetate solution to obtain mixed solution B; dissolve ciprofloxacin hydrochloride in mixed solution B to obtain mixed solution C. The mass percentage of ciprofloxacin hydrochloride in mixed solution C is 10%, the mass percentage of polyvinyl alcohol is 10%, and the mass percentage of polyvinyl acetate is 10%. Using the two-layer fiber membrane obtained in step (3) as the collection substrate, conduct electrospinning at an output voltage of 22 kV of the high-voltage power supply, a distance of 10 cm between the needle and the receiving device, and a feeding speed of 0.5 mL / h to obtain a three-layer fiber membrane, and the three-layer fiber membrane is the composite antibacterial and highly efficient air filtration membrane.

[0064] The detection performance of the composite antibacterial and highly efficient air filtration membrane prepared by electrospinning with polyvinyl butyral ethanol solutions of different mass ratios is shown in Table 2 below.

[0065] Table 2, Filtration performance of the composite antibacterial and highly efficient air filtration membrane

[0066]

[0067]

[0068] As can be seen from the above table, the optimal concentration of the polyvinyl butyral ethanol solution is 6.5%, and the prepared air filtration membrane has strong filtration performance. The composite antibacterial and highly efficient air filtration membrane prepared in Test Group 13 was used for the inhibition test of Escherichia coli and Candida albicans, and the test results are as Figure 5 and Figure 6 .

[0069] The scanning electron microscope images of the composite antibacterial and highly efficient air filtration membranes prepared in Test Groups 9, 10, 14, and 16 are as Figures 7 - 10 .

[0070] III. Tests 19 - 25: Effects of different mass percentages of ciprofloxacin hydrochloride, polyvinyl alcohol, and polyvinyl acetate in mixed solution C on the air filtration membrane

[0071] The preparation process of the composite antibacterial and highly efficient air filtration membrane includes the following steps:

[0072] (1) Dissolve zein in solvent A, fully stir to form a stable solution, and then let it stand for 24 - 72 h to form a light yellow paste - like solid of modified zein. The mass fraction of zein in solvent A is 10%;

[0073] Dissolve polyvinyl alcohol in solvent A, place it in a water bath and heat until completely dissolved to obtain a polyvinyl alcohol solution. Dissolve polyvinyl butyral in an ethanol solution to obtain a polyvinyl butyral ethanol solution, and respectively prepare a mass fraction of 8%;

[0074] Dissolve polyvinyl acetate in solvent A to obtain a polyvinyl acetate solution; Solvent A is an acetic acid aqueous solution with a ratio of 1:1.

[0075] (2) Take the paste - like solid in step (1) and dissolve it in the polyvinyl alcohol solution to form mixed solution A. The mass ratio of polyvinyl alcohol to zein in mixed solution A is 1:2. After mixing mixed solution A evenly, add it to a syringe, and use an electrospinning machine to spin - cast to obtain the first - layer fiber membrane under the conditions that the output voltage of the high - voltage power supply is 18 kV, the distance between the needle and the receiving device is 10 cm, and the liquid supply speed is 0.5 mL / h.

[0076] (3) Electrospin the 8% polyvinyl butyral ethanol solution respectively. Under the conditions that the output voltage of the high-voltage power supply is 7 kV, the distance between the needle and the receiving device is 10 cm, and the liquid supply speed is 2.5 mL / h, use the first-layer fiber membrane obtained in step (2) as the collection substrate to perform electrospinning to obtain a two-layer fiber membrane.

[0077] (4) Mix the polyvinyl alcohol solution and the polyvinyl acetate solution to obtain mixed solution B; dissolve ciprofloxacin hydrochloride in mixed solution B to obtain mixed solution C. The mass percentage of ciprofloxacin hydrochloride in mixed solution C is 5%, 8%, 10%, 12%, the mass percentage of polyvinyl alcohol is 5%, 8%, 10%, 12%, and the mass percentage of polyvinyl acetate is 5%, 8%, 10%, 12%.

[0078] Under the conditions that the output voltage of the high-voltage power supply is 22 kV, the distance between the needle and the receiving device is 10 cm, and the liquid supply speed is 0.5 mL / h, use the two-layer fiber membrane obtained in step (3) as the collection substrate, and electrospin to obtain a three-layer fiber membrane. The three-layer fiber membrane is the composite antibacterial high-efficiency air filtration membrane.

[0079] The performance of the composite antibacterial high-efficiency air filtration membrane prepared by electrospinning with different mass concentration ratios of ciprofloxacin hydrochloride, polyvinyl alcohol solution and polyvinyl acetate in mixed solution C is as shown in Table 3 below.

[0080] Table 3, Filtration performance and antibacterial performance of the composite antibacterial high-efficiency air filtration membrane

[0081]

[0082]

[0083] As can be seen from the above table, the optimal mass fractions of ciprofloxacin hydrochloride, polyvinyl alcohol and polyvinyl acetate in mixed solution C are 10%:10%:10%. At this time, the prepared air filtration membrane has strong filtration performance and bactericidal performance.

[0084] IV. Experiments 26 - 34: Effects of different electrospinning conditions on the air filtration membrane.

[0085] The preparation process of the composite antibacterial high-efficiency air filtration membrane includes the following steps:

[0086] (1) Dissolve zein in solvent A, fully stir to form a stable solution, and then let it stand for 24 - 72 h to form a light yellow paste solid of modified zein. The mass fraction of zein in solvent A is 10%.

[0087] Dissolve polyvinyl alcohol in solvent A, place it in a water bath and heat it until completely dissolved to obtain a polyvinyl alcohol solution, and the mass ratio of the polyvinyl alcohol solution is 10%;

[0088] Dissolve polyvinyl butyral in an ethanol solution to obtain a polyvinyl butyral ethanol solution, and prepare mass fractions of 8% respectively;

[0089] Dissolve polyvinyl acetate in solvent A to prepare a polyvinyl acetate solution; Solvent A is an acetic acid aqueous solution with a ratio of 1:1.

[0090] (2) Take the paste-like solid in step (1) and dissolve it in the polyvinyl alcohol solution to obtain mixed solution A. The mass ratio of polyvinyl alcohol to zein in mixed solution A is 1:2. After mixing mixed solution A evenly, add it to a syringe. Use a 22G needle, and under the conditions of an output voltage of 18 kV of the high-voltage power supply, a distance of 10 cm between the needle and the receiving device, and a liquid supply speed of 0.5 mL / h, use an electrospinning machine to spin to obtain the first layer of fiber membrane.

[0091] (3) Conduct electrospinning experiments on the 8% polyvinyl butyral ethanol solution respectively. Use a 26G needle, and under the conditions of an output voltage of 7 kV of the high-voltage power supply, a distance of 10 cm between the needle and the receiving device, and a liquid supply speed of 2.5 mL / h, use the first layer of fiber membrane obtained in step (2) as the collection substrate to conduct electrospinning to obtain a two-layer fiber membrane.

[0092] (4) Mix the polyvinyl alcohol solution and the polyvinyl acetate solution to obtain mixed solution B; Dissolve ciprofloxacin hydrochloride in mixed solution B to obtain mixed solution C. The mass percentage of ciprofloxacin hydrochloride in mixed solution C is 10%, the mass percentage of polyvinyl alcohol is 10%, and the mass percentage of polyvinyl acetate is 10%. Use a 22G needle, and under the conditions of an output voltage of 22 kV of the high-voltage power supply, a distance of 10 cm between the needle and the receiving device, and a liquid supply speed of 0.5 mL / h, use the two-layer fiber membrane obtained in step (3) as the collection substrate to spin to obtain a three-layer fiber membrane, and the three-layer fiber membrane is the composite antibacterial high-efficiency air filtration membrane.

[0093] The performance of the composite antibacterial high-efficiency air filtration membrane prepared by the three-layer fiber membrane through different electrospinning processes is shown in Table 4 below.

[0094] Table 4, Filtration performance of the composite antibacterial high-efficiency air filtration membrane

[0095]

[0096]

[0097] As can be seen from the above table, the electrospinning conditions in step (2) are 15 kV and the liquid supply rate is 0.5 mL / h. The electrospinning conditions in step (3) are 7 kV and the liquid supply rate is 3.0 mL / h. The electrospinning conditions in step (4) are 18 kV and the liquid supply rate is 0.5 mL / h. At this time, the prepared air filtration membrane has strong filtration performance and bactericidal performance.

[0098] Experimental group 35

[0099] Compared with experimental group 13, the difference is that during preparation: the mass fraction of the acetic acid solution is 90%, and electrospinning is carried out using an electrospinning machine under the conditions of an output voltage of 18 kV of the high-voltage power supply, a distance of 10 cm between the needle head and the receiving device, and a liquid supply rate of 0.5 mL / h to obtain the first layer of nanofiber membrane.

[0100] The air filtration efficiency is 52.1%, the resistance pressure drop is 90 Pa, and the electron micrograph of the fiber membrane is as Figure 4 shown. The fiber distribution is uneven, and at the same time, spindle shapes appear, affecting the filtration performance.

[0101] Experimental group 36

[0102] Compared with experimental group 13, the difference is that during preparation: a 10% ciprofloxacin hydrochloride - polyvinyl alcohol - polyvinyl acetate solution, where the mass ratio of ciprofloxacin hydrochloride: polyvinyl alcohol: polyvinyl acetate is 0.5:0.5:1, is electrospun under the conditions of an output voltage of 22 kV of the high-voltage power supply, a distance of 10 cm between the needle head and the receiving device, and a liquid supply rate of 0.5 mL / h.

[0103] Regarding the effect of inhibiting Candida albicans, when the proportion of polyvinyl acetate is relatively large, due to its water-insoluble property, the release amount of ciprofloxacin hydrochloride in the mixed solution decreases, resulting in a poor antibacterial effect.

[0104] Experimental group 37

[0105] Compared with experimental group 13, the difference is that during preparation: zein is dissolved in solvent A, and after fully stirring to form a stable solution, it is directly mixed with the PVA solution and then electrospun.

[0106] Its air filtration efficiency is 99.6%, and the resistance is 102 Pa.

[0107] It should be noted that in this text, relational terms such as first and second are only used to distinguish one entity or operation from another entity or operation, and do not necessarily require or imply any actual relationship or order between these entities or operations. Moreover, the term "comprising", "including" or any other variant thereof is intended to cover non-exclusive inclusion, so that a process, method, article or terminal device comprising a series of elements not only includes those elements, but also includes other elements not expressly listed, or further includes elements inherent to such process, method, article or terminal device. Without further limitation, elements defined by the statement "comprising..." or "including..." do not preclude the existence of additional elements in the process, method, article or terminal device comprising the said elements. In addition, in this text, "greater than", "less than", "more than" etc. are understood not to include the base number; "above", "below", "within" etc. are understood to include the base number.

[0108] Although the above embodiments have been described, those skilled in the art can make additional changes and modifications once they know the basic creative concept. Therefore, the above description is only the embodiments of the present invention, and does not limit the patent protection scope of the present invention. Any equivalent structure or equivalent process transformation made by using the content of the specification and drawings of the present invention, or directly or indirectly applied to other related technical fields, is similarly included in the patent protection scope of the present invention.

Claims

1. A preparation method of a composite antibacterial and highly efficient air filtration membrane, characterized in that, The composite antibacterial and highly efficient air filtration membrane comprises a filtration layer and an antibacterial layer. The preparation method of the composite antibacterial and highly efficient air filtration membrane comprises the following steps: (1) Raw material preparation: Dissolve zein in solvent A, fully stir to form a stable solution, and then stand for 24 - 72 h to form a paste-like solid of modified zein; Dissolve polyvinyl alcohol in solvent A, place it in a water bath and heat until completely dissolved to obtain a polyvinyl alcohol solution; Dissolve polyvinyl butyral in an ethanol solution to obtain a polyvinyl butyral ethanol solution; Dissolve polyvinyl acetate in solvent A to prepare a polyvinyl acetate solution; (2) Mix and dissolve the paste-like solid of modified zein and the polyvinyl alcohol solution, stir evenly to obtain a mixed solution A; use the mixed solution A as an electrospinning solution to perform electrospinning to obtain a first-layer fiber membrane; (3) Use the polyvinyl butyral ethanol solution as an electrospinning solution to perform electrospinning on the first-layer fiber membrane to obtain a two-layer fiber membrane, (4) Mix the polyvinyl alcohol solution and the polyvinyl acetate solution to obtain a mixed solution B; Dissolve ciprofloxacin hydrochloride in the mixed solution B to obtain a mixed solution C, use the mixed solution C as an electrospinning solution to perform electrospinning on the two-layer fiber membrane to obtain a three-layer fiber membrane, and the three-layer fiber membrane is the composite antibacterial and highly efficient air filtration membrane.

2. The preparation method of the composite antibacterial and highly efficient air filtration membrane according to claim 1, characterized in that, In the mixed solution A, the mass ratio of modified zein to polyvinyl alcohol is 1 - 3:1 - 3.

3. The preparation method of the composite antibacterial and highly efficient air filtration membrane according to claim 2, characterized in that, In the mixed solution A, the mass percentage of modified zein is 5% - 10%, and the mass percentage of polyvinyl alcohol is 5% - 10%.

4. The preparation method of the composite antibacterial and highly efficient air filtration membrane according to claim 1, characterized in that, The mass percentage of polyvinyl butyral is 2% - 12%.

5. The preparation method of the composite antibacterial and highly efficient air filtration membrane according to claim 1, characterized in that In the mixed solution C, the mass percentage of ciprofloxacin hydrochloride is 5% - 12%, the mass percentage of polyvinyl alcohol is 5% - 12%, and the mass percentage of polyvinyl acetate is 5% - 12%.

6. The preparation method of the composite antibacterial and highly efficient air filtration membrane according to claim 1, characterized in that, The solvent A is an acetic acid - aqueous solution, and the mass ratio of acetic acid to water is 1 - 3:1 - 3. The model of the polyvinyl alcohol is type 1799, type 1788 or type 124.

7. The preparation method of the composite antibacterial and highly efficient air filtration membrane according to claim 6, characterized in that, In the acetic acid - aqueous solution, the mass ratio of acetic acid to water is 1:

1.

8. The preparation method of the composite antibacterial and highly efficient air filtration membrane according to claim 1, characterized in that, When electrospinning the mixed solution A: use a 22G needle, the spinning voltage is 15 - 20 kV, and the liquid supply rate is 0.3 - 0.7 mL / h; When electrospinning the polyvinyl butyral ethanol solution: use a 26G needle, the spinning voltage is 5 - 10 kV, and the liquid supply rate is 1.5 - 4.5 mL / h; When electrospinning the mixed solution C: use a 22G needle, the spinning voltage is 18 - 24 kV, and the liquid supply rate is 0.3 - 1.0 mL / h.

9. The composite antibacterial and highly efficient air filtration membrane prepared by the preparation method of the composite antibacterial and highly efficient air filtration membrane according to any one of claims 1-8, characterized in that, From the outside to the inside, it includes a zein - polyvinyl alcohol electrospun fiber membrane, a polyvinyl butyral electrospun fiber membrane, and a loaded ciprofloxacin hydrochloride - polyvinyl alcohol - polyvinyl acetate electrospun fiber membrane.

10. Application of the composite antibacterial and highly efficient air filtration membrane prepared by the preparation method of the composite antibacterial and highly efficient air filtration membrane according to any one of claims 1-8, characterized in that, It is applied to masks, window screens or air purification filters.

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