CN113430719B - Preparation method of air filtration nanofiber membrane with dendritic multi-level structure - Google Patents

Preparation method of air filtration nanofiber membrane with dendritic multi-level structure Download PDF

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CN113430719B
CN113430719B CN202110793035.5A CN202110793035A CN113430719B CN 113430719 B CN113430719 B CN 113430719B CN 202110793035 A CN202110793035 A CN 202110793035A CN 113430719 B CN113430719 B CN 113430719B
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nanofiber membrane
air filtration
dendritic
spinning solution
filtration nanofiber
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CN113430719A (en
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赵为陶
张珂伟
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Changzhou Vocational Institute of Textile and Garment
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    • D—TEXTILES; PAPER
    • D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
    • D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
    • D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
    • D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
    • D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
    • D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/09—Addition of substances to the spinning solution or to the melt for making electroconductive or anti-static filaments
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties
    • D01F1/103—Agents inhibiting growth of microorganisms
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/02—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/08—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons
    • D01F6/12—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from homopolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds from polymers of halogenated hydrocarbons from polymers of fluorinated hydrocarbons
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2321/00—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D10B2321/04—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons
    • D10B2321/042—Fibres made from polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds polymers of halogenated hydrocarbons polymers of fluorinated hydrocarbons, e.g. polytetrafluoroethene [PTFE]
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/13—Physical properties anti-allergenic or anti-bacterial
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/16—Physical properties antistatic; conductive
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2505/00—Industrial
    • D10B2505/04—Filters
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
    • Y02C20/00—Capture or disposal of greenhouse gases
    • Y02C20/40—Capture or disposal of greenhouse gases of CO2

Abstract

The invention provides a preparation method of an air filtration nanofiber membrane with a dendritic multi-stage structure, wherein the air filtration nanofiber membrane is prepared by adding amino-terminated hyperbranched quaternary ammonium salt into a compound organic solvent system of dimethylacetamide/acetone of polyvinylidene fluoride, preparing a homogeneous spinning solution at a certain temperature through magnetic stirring, and then preparing the homogeneous spinning solution through electrostatic spinning. Based on the principle that electrostatic spinning jet flow can be split, the amino-terminated hyperbranched compound quaternary ammonium salt with a highly branched three-dimensional structure and excellent antibacterial property is added into the spinning solution, the splitting of the spinning jet flow is promoted by the aid of the increase of the conductivity of the spinning solution and the effect of steric hindrance effect, and the air filtration nanofiber membrane with a rich dendritic multi-stage structure is prepared by a one-step method through an electrostatic spinning technology. The preparation method disclosed by the invention is simple in preparation process, high in dendritic structure coverage rate, good in filtering performance, excellent in antibacterial performance and better in application prospect.

Description

Preparation method of air filtration nanofiber membrane with dendritic multi-level structure
Technical Field
The invention relates to a preparation method of an air filtration nanofiber membrane with a dendritic multi-level structure, and belongs to the technical field of textiles.
Background
The pollutants in the atmospheric environment comprise particles, liquid, gas, mixtures thereof and the like, wherein the fine particles have the characteristics of small particle size, easiness in carrying germs, long retention time in the atmosphere, long conveying distance and the like, and bring great harm to the health of human bodies. The traditional air filtering material can play a certain role in filtering micron-sized particles, and is poor in filtering effect on the nano-sized particles. The bionic dendritic nano-fiber prepared by the electrostatic spinning method has a structure like a branch in nature, and comprises a main fiber and a branch fiber. The main fiber can provide mechanical support as a framework, the branch fiber can provide a large specific surface area, a smaller pore size, a mutually communicated pore structure and the like, the filtering effect of the material on micro-nano particles is greatly improved, and the micro-nano particle filtering material has a wide application prospect in the field of air filtration. At present, how to prepare the air filtration nanofiber membrane material with large dendritic structure coverage rate and clear hierarchical structure is the focus of development attention in the technical field.
The hyperbranched polymer is a polymer with an approximately spherical structure, rich terminal groups, high solubility, low viscosity and high chemical reactivity. Amino-terminated hyperbranched compounds are an important branch of hyperbranched compounds. Because of the existence of abundant amino on the surface, the material can be dissolved in water and organic solvent, can be degraded, and is suitable for being used as a cross-linking agent, an antioxidant, a bactericide, a surfactant, a rheological processing additive, a functional material precursor and the like. The amino-terminated hyperbranched compound quaternary ammonium salt is polyquaternary ammonium salt obtained by quaternizing or grafting a quaternary ammonium salt side chain on the amino-terminated hyperbranched compound surface. Such polymers not only have the basic characteristics of hyperbranched polymers, but also have the characteristic features of polycations due to the large number of positive charges in the structure.
Polyvinylidene fluoride (PVDF) is a linear semi-crystalline polymer, has excellent mechanical strength, chemical stability, piezoelectricity, heat resistance, ultraviolet radiation degradation resistance and biocompatibility, and has the advantages of light weight, softness, easy film forming and the like. The PVDF air filtration nanofiber membrane prepared by the electrostatic spinning method is a good base material of an air filtration material. The air filtration nanofiber membrane with the dendritic PVDF multi-level structure is prepared by adding various salt substances, but the coverage rate of the dendritic structure generated by the preparation methods is not high, and the air filtration nanofiber membrane has a single function. How to efficiently prepare the dendritic PVDF multi-stage structure air filtration nanofiber membrane and improve the coverage rate of the dendritic structure of the nanofiber membrane, so that the improvement of the filtration efficiency of the fiber membrane is a key technical difficulty in the field. The filtration efficiency of the air filtration nanofiber membrane is effectively improved, meanwhile, the fiber membrane is endowed with more functionality, for example, harmful microorganisms are effectively inhibited and killed while bacterial and virus-containing particles are filtered, and the trend of the technical development in the field is also included.
Disclosure of Invention
The invention provides a preparation method of an air filtration nanofiber membrane with a dendritic multi-stage structure.
The method is realized by the following technical scheme, and comprises the following steps: (1) compounding dimethylacetamide and acetone to obtain an organic solvent system; (2) adding polyvinylidene fluoride into the organic solvent system compounded in the step (1), and magnetically stirring under a water bath condition until colorless transparent polyvinylidene fluoride spinning solution is obtained; (3) adding an amino-terminated hyperbranched compound quaternary ammonium salt into the polyvinylidene fluoride spinning solution prepared in the step (2), and magnetically stirring under a water bath condition until a homogeneous spinning solution is obtained; (4) and (4) standing and defoaming the spinning solution prepared in the step (3), and then performing electrostatic spinning to obtain the air filtration nanofiber membrane with the dendritic multi-stage structure.
The amino-terminated hyperbranched compound quaternary ammonium salt (HBP-HTC) used in the scheme of the invention is prepared according to the Chinese invention patent 'amino-terminated hyperbranched compound quaternary ammonium salt and a preparation method thereof' [ CN200710191878.8 ]. Preferably, as shown in structural formula i:
Figure GDA0003595281810000021
preferably, in the step (1), the compounding ratio of the dimethylacetamide to the acetone is 7: 3-9: 1.
Preferably, in the step (2), the mass concentration of polyvinylidene fluoride in the prepared polyvinylidene fluoride spinning solution is 10-14 wt%, the water bath temperature is 50-80 ℃, and the magnetic stirring time is 3-5 hours.
Preferably, in the step (3), the mass ratio of the added amount of the amino-terminated hyperbranched compound quaternary ammonium salt to the polyvinylidene fluoride is as follows: 0.15-0.28 ℃, the water bath temperature is 50-80 ℃, and the magnetic stirring time is 5-8 hours.
Preferably, in the step (4), the electrostatic spinning voltage is 20-25 KV, the spinning solution advancing speed is 0.3-0.7 ml/h, the receiving distance is 15-25 cm, the environmental temperature is 25-35 ℃, and the environmental humidity is 25-35%.
Preferably, the coverage rate of the dendritic structure of the air filtration nanofiber membrane obtained in the step (4) is more than 90%.
Preferably, the average diameter of the main fiber and the average diameter of the branch fiber of the air filtration nanofiber membrane obtained in the step (4) are 500-700 nm and 20-30 nm respectively.
Compared with the prior art, the invention has the following advantages:
(1) in the preparation method provided by the invention, the performance of the polyvinylidene fluoride electrostatic spinning solution is greatly improved by adding the HBP-HTC, so that the air filtration nanofiber membrane with a higher coverage rate and a dendritic structure is promoted to be formed; on one hand, HBP-HTC contains a large amount of terminal quaternary ammonium groups, so that the cationic polycation effect is achieved, and the charge density is remarkably increased compared with that of common quaternary ammonium salts, so that the conductivity of the spinning solution is greatly improved, on the other hand, the steric hindrance is increased due to the spherical macromolecular structure of the spinning solution, the splittable branching capability of the spinning jet flow is improved, the nano fiber structure with the dendritic form and high coverage rate is jointly promoted to be generated, the coverage rate of the dendritic structure in the fiber membrane is improved, and the coverage rate of the dendritic structure is enabled to reach more than 90%.
(2) The air filtration nanofiber membrane has excellent antibacterial property due to the addition of the HBP-HTC, compared with a low-molecular bactericide, the HBP-HTC belongs to a high-molecular bactericide, and macromolecules of the HBP-HTC have a large number of hydroxypropyl trimethyl ammonium chloride groups, so that the air filtration nanofiber membrane has the advantages of stable performance, remarkable sterilizing effect, nonvolatility, easiness in processing and storage, no permeation into human or animal epidermis and the like, and the dendritic air filtration nanofiber membrane is endowed with excellent antibacterial property, wherein the antibacterial rate of the air filtration nanofiber membrane on staphylococcus aureus and escherichia coli can reach more than 99%.
(3) Due to the fact that the HBP-HTC is of a spherical structure, molecules are not entangled, high solubility and low viscosity are shown, and due to the fact that a large number of cationic groups in the HBP-HTC molecules repel each other, the intermolecular dispersion is increased, the interaction among polyvinylidene fluoride (PVDF) macromolecules is greatly reduced, the fluidity of the spinning solution is increased, and the spinnability of the spinning solution is effectively improved.
(4) The composite functional air filtration nanofiber membrane with high filtration efficiency and excellent antibacterial property can be prepared by a one-step method, the process flow is short, and the preparation efficiency is high.
(5) The air filtration nanofiber membrane material with the dendritic multi-stage structure, which is constructed by taking polyvinylidene fluoride (PVDF) as a base material, has higher specific surface area, porosity and smaller pore size, so that fine particles are effectively intercepted, the filtration effect of the air filtration nanofiber membrane is greatly increased, and the filtration efficiency of the particles can reach more than 99.0%.
Drawings
FIG. 1 shows the morphology of the dendritic air filtration nanofiber membrane prepared in example 1.
Detailed Description
The present invention is further described below with reference to examples, but the embodiments of the present invention are not limited by the following examples.
The specific test method for the bacteriostatic rate of staphylococcus aureus/escherichia coli by the average diameter of the main fibers, the average diameter of the branch fibers, the coverage rate of the dendritic structure and the particulate matter filtering efficiency of the nanofiber membrane in the following examples is as follows:
(1) average diameter of trunk fiber, average diameter of branch fiber test method: the fiber diameter is measured by adopting Image-pro Plus 5.0 Image analysis software to respectively select 50 main fibers and 50 branch fibers in an electron microscope picture, and the average diameters of the 2 fibers are respectively measured and calculated.
(2) And (3) measuring the coverage rate of the dendritic structure: randomly selecting 10 electron microscope pictures, and using Image-pro Plus 5.0 Image analysis software to circle out a region with dendritic structure fibers in the electron microscope pictures, wherein the dendritic structure coverage rate calculation formula is as follows:
Figure GDA0003595281810000041
in the formula: r: coverage (%);
S0: total area of SEM images;
S1: the sum of the areas covered by all dendritic fibers in the image.
(3) And (3) measuring the filtering efficiency of the particulate matters: according to the standard of GB 2626 plus 2019 respiratory protection self-absorption filter type particulate-prevention respirator, a fiber membrane sample is cut into a round sample with the diameter of 14cm, the filtration efficiency of the sample on saline aerosol (NaCl) particles with the mass median diameter of 0.3 mu m is tested under the condition that the gas flow is 85L/min, 5 samples under the same preparation condition are tested repeatedly, and the minimum value is taken as the final test result.
(4) And (3) determining the bacteriostasis rate, referring to the evaluation part 3 of GB/T20944.3-2008 textile antibacterial performance: according to the standard of the oscillatory method, two most representative strains of gram-negative bacteria and gram-positive bacteria, namely escherichia coli and staphylococcus aureus, are selected as test strains. Calculating the bacteriostasis rate of the sample:
Figure GDA0003595281810000042
in the formula: y: bacteriostatic rate (%);
Wb: oscillating and contacting the standard blank sample for 18h, and then determining the concentration of viable bacteria in the flask;
Wc: and (4) oscillating and contacting the antibacterial fiber membrane sample for 18h, and then keeping the viable bacteria concentration in the flask.
The selected amino-terminated hyperbranched compound quaternary ammonium salt in the following examples 1 to 4 is shown in a structural formula I:
Figure GDA0003595281810000051
the preparation method comprises the following steps: a) HBP-NH2The synthesis of (2): 50ml of diethylenetriamine are placed in a 250ml three-neck flask and cooled in an ice-water bath. Then in N2Under protection, a mixed solution of 43ml of methyl acrylate and 100ml of methanol is slowly dripped into a three-neck flask by using a constant-pressure funnel, after the dripping is finished, the ice water bath is removed, the mixed solution reacts for 6 hours at normal temperature, the solution is in a light yellow transparent state, and then the mixed solution is transferred to a containerRemoving methanol in a rotary evaporator eggplant-shaped flask under reduced pressure, heating to 140 ℃, continuing to react for 4 hours under reduced pressure, stopping the reaction, and obtaining the viscous bright yellow amino-terminated hyperbranched polymer (HBP-NH)2)。
b) Synthesis of HBP-HTC: 10g of an amino-terminated hyperbranched compound (HBP-NH) were weighed2) Adding 50ml of deionized water to dissolve the materials, pouring the materials into a four-neck flask, heating and stirring, adding 10g of glycidol trimethyl ammonium chloride, reacting for 30min at 80 ℃, washing the materials for multiple times by using absolute ethyl alcohol and acetone after the reaction is finished, extracting to obtain light yellow viscous amino-terminated hyperbranched compound quaternary ammonium salt (HBP-HTC), and measuring the weight-average molecular weight of the quaternary ammonium salt (HBP-HTC) by adopting gel chromatography to obtain 12678.
Example 1: 8ml of dimethylacetamide and 2ml of acetone are taken to prepare a mixture with the proportion of 8: 2, a compound organic solvent system; weighing 1.3g of polyvinylidene fluoride (PVDF) according to the mass concentration of 12%, adding the weighed PVDF into a compound organic solvent, and magnetically stirring for 3 hours at the water bath temperature of 80 ℃ to obtain a colorless transparent spinning solution; adding 0.32g of amino-terminated hyperbranched compound quaternary ammonium salt (HBP-HTC) into polyvinylidene fluoride (PVDF) spinning solution, and magnetically stirring for 5 hours at the water bath temperature of 80 ℃ to obtain homogeneous spinning solution; and standing the spinning solution for 1 hour for defoaming, and performing electrostatic spinning under the conditions that the spinning voltage is 25KV, the spinning solution advancing speed is 0.3ml/h, the receiving distance is 25cm, the ambient temperature is 30 ℃ and the ambient humidity is 30% to obtain the air filtration nanofiber membrane (shown in figure 1) with good filtration effect, high efficiency and antibacterial property and rich dendritic multi-stage structure. The coverage of the dendritic structure in the nanofiber membrane was 98.29%, with the average diameter of the main fibers being 548.25nm and the average diameter of the branch fibers being 24.69 nm. The filtering efficiency of the particles of the nanofiber membrane is 99.9943%, the bacteriostasis rate to staphylococcus aureus is 99.92%, and the bacteriostasis rate to escherichia coli is 99.66%.
Example 2: taking 7ml of dimethylacetamide and 3ml of acetone, and preparing the mixture into a mixture with a ratio of 7:3, a compound organic solvent system; weighing 1.0g of polyvinylidene fluoride (PVDF) according to the mass concentration of 10%, adding the weighed PVDF into a compound organic solvent, and magnetically stirring for 3 hours at the water bath temperature of 80 ℃ to obtain a colorless transparent spinning solution; adding 0.28g of amino-terminated hyperbranched compound quaternary ammonium salt (HBP-HTC) into polyvinylidene fluoride (PVDF) spinning solution, and magnetically stirring for 5 hours at the water bath temperature of 80 ℃ to obtain homogeneous spinning solution; and standing the spinning solution for 1 hour for defoaming, and performing electrostatic spinning under the conditions that the spinning voltage is 25KV, the spinning solution advancing speed is 0.3ml/h, the receiving distance is 20cm, the ambient temperature is 30 ℃ and the ambient humidity is 30% to obtain the air filtration nanofiber membrane with good filtration effect, high efficiency and antibacterial property and rich dendritic multi-stage structure. The coverage of the dendritic structure in the nanofiber membrane was 93.80%, with the average diameter of the main fibers being 600.56nm and the average diameter of the branch fibers being 21.86 nm. The filtering efficiency of the particles of the nanofiber membrane is 99.9663%, the bacteriostasis rate to staphylococcus aureus is 99.72%, and the bacteriostasis rate to escherichia coli is 99.34%.
Example 3: 8ml of dimethylacetamide and 2ml of acetone are taken to prepare a mixture with the proportion of 8: 2, a compound organic solvent system; weighing 1.3g of polyvinylidene fluoride (PVDF) according to the mass concentration of 12%, adding the weighed PVDF into a compound organic solvent, and magnetically stirring for 3 hours at the water bath temperature of 80 ℃ to obtain a colorless transparent polyvinylidene fluoride spinning solution; adding 0.28g of amino-terminated hyperbranched compound quaternary ammonium salt (HBP-HTC) into polyvinylidene fluoride (PVDF) spinning solution, and magnetically stirring for 5 hours at the water bath temperature of 80 ℃ to obtain homogeneous spinning solution; and standing the spinning solution for 1 hour for defoaming, and performing electrostatic spinning under the conditions that the spinning voltage is 25KV, the spinning solution advancing speed is 0.5ml/h, the receiving distance is 20cm, the ambient temperature is 30 ℃ and the ambient humidity is 30% to obtain the air filtration nanofiber membrane with good filtration effect, high efficiency and antibacterial property and rich dendritic multi-stage structure. The coverage of the dendritic structure in the nanofiber membrane was 91.30%, with the average diameter of the main fibers being 627.52nm and the average diameter of the branch fibers being 22.86 nm. The filtering efficiency of the particles of the nanofiber membrane is 99.9351%, the bacteriostasis rate to staphylococcus aureus is 99.72%, and the bacteriostasis rate to escherichia coli is 99.34%.
Example 4: taking 9ml of dimethylacetamide and 1ml of acetone solution, and preparing the mixture into a mixture with the ratio of 9:1, a compound organic solvent system; weighing 1.5g of polyvinylidene fluoride (PVDF) according to the mass concentration of 14%, adding the weighed PVDF into a compound organic solvent, and magnetically stirring for 3 hours at the water bath temperature of 80 ℃ to obtain a colorless transparent spinning solution; adding 0.36g of amino-terminated hyperbranched compound quaternary ammonium salt (HBP-HTC) into polyvinylidene fluoride (PVDF) spinning solution, and magnetically stirring for 5 hours at the water bath temperature of 80 ℃ to obtain homogeneous spinning solution; and standing the spinning solution for 1 hour for defoaming, and performing electrostatic spinning under the conditions that the spinning voltage is 25KV, the spinning solution advancing speed is 0.3ml/h, the receiving distance is 20cm, the ambient temperature is 30 ℃ and the ambient humidity is 30% to obtain the air filtration nanofiber membrane with good filtration effect, high efficiency and antibacterial property and rich dendritic multi-stage structure. The coverage of the dendritic structure in the nanofiber membrane was 91.50%, with the average diameter of the main fibers being 650.43nm and the average diameter of the branch fibers being 27.16 nm. The filtering efficiency of the particles of the nanofiber membrane is 99.9147%, the bacteriostasis rate to staphylococcus aureus is 99.98%, and the bacteriostasis rate to escherichia coli is 99.86%.

Claims (8)

1. A preparation method of an air filtration nanofiber membrane with a dendritic multilevel structure is characterized by comprising the following steps:
(1) compounding dimethylacetamide and acetone to obtain an organic solvent system; (2) adding polyvinylidene fluoride into the organic solvent system compounded in the step (1), and magnetically stirring under a water bath condition until colorless transparent polyvinylidene fluoride spinning solution is obtained; (3) adding an amino-terminated hyperbranched compound quaternary ammonium salt into the polyvinylidene fluoride spinning solution prepared in the step (2), and magnetically stirring under a water bath condition until a homogeneous spinning solution is obtained; (4) and (4) standing and defoaming the spinning solution prepared in the step (3), and then performing electrostatic spinning to obtain the air filtration nanofiber membrane with the dendritic multi-stage structure.
2. The method for preparing an air filtration nanofiber membrane with a dendritic multi-stage structure according to claim 1, wherein the amino-terminated hyperbranched compound quaternary ammonium salt is represented by formula I:
Figure 21278DEST_PATH_IMAGE001
the structural formula I.
3. The method for preparing an air filtration nanofiber membrane having a dendritic multi-stage structure as claimed in claim 1, wherein: in the step (1), the compounding ratio of the dimethylacetamide to the acetone is 7: 3-9: 1.
4. The method for preparing an air filtration nanofiber membrane having a dendritic multi-stage structure as claimed in claim 1, wherein: in the step (2), the mass concentration of polyvinylidene fluoride in the prepared polyvinylidene fluoride spinning solution is 10-14 wt%, the water bath temperature is 50-80 ℃, and the magnetic stirring time is 3-5 hours.
5. The method for preparing an air filtration nanofiber membrane having a dendritic multi-stage structure as claimed in claim 1, wherein: in the step (3), the mass ratio of the added amount of the amino-terminated hyperbranched compound quaternary ammonium salt to the polyvinylidene fluoride is as follows: 0.15-0.28 ℃, the water bath temperature is 50-80 ℃, and the magnetic stirring time is 5-8 hours.
6. The method for preparing an air filtration nanofiber membrane having a dendritic multi-stage structure as claimed in claim 1, wherein: in the step (4), the electrostatic spinning voltage is 20-25 KV, the spinning solution advancing speed is 0.3-0.7 ml/h, the receiving distance is 15-25 cm, the environmental temperature is 25-35 ℃, and the environmental humidity is 25% -35%.
7. The method for preparing an air filtration nanofiber membrane having a dendritic multi-stage structure as claimed in claim 1, wherein: the coverage rate of the dendritic structure of the air filtration nanofiber membrane obtained in the step (4) is more than 90%.
8. The method for preparing an air filtration nanofiber membrane having a dendritic multi-stage structure as claimed in claim 1, wherein: the average diameter of the main fiber of the air filtration nanofiber membrane obtained in the step (4) is 500-700 nm, and the average diameter of the branch fiber is 20-30 nm.
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