CN116905108A - PE/O-Cu 2 Preparation method of O@HNTs composite antibacterial microfiber - Google Patents

Abstract

PE/O-Cu ₂ The preparation method of the O@HNTs composite antibacterial microfiber comprises the following steps: adding deionized water into halloysite nanotubes, adding disodium ethylenediamine tetraacetate after ultrasonic dispersion, stirring for reaction, and then adding CuSO ₄ ·5H ₂ O continuously stirring for reaction, and then dropwise adding NaOH solution and ascorbic acid solution; centrifuging and washing the reaction product, vacuum drying to obtain powder, dispersing the powder into a cyclohexane and n-propylamine composite solution, adding a silane coupling agent, and drying to obtain organically modified O-Cu ₂ O@HNTs composite material; O-Cu is to ₂ The O@HNTs micro-nano hybrid material and polyethylene are kneaded reciprocally in a high temperature kneader to obtain high-concentration PE/O-Cu ₂ O@HNTs micro-nano hybrid material; PE/O-Cu ₂ Carrying out melt-blown spinning on the O@HNTs micro-nano hybrid material and PE through a melt-blown spinning machine to obtain PE/O-Cu ₂ O@HNTs composite antibacterial melt-blown microfiber. PE/O-Cu of the invention ₂ The preparation method of the O@HNTs composite antibacterial melt-blown microfiber better solves the problem of secondary infection of melt-blown microfiber products, and develops and obtains PE melt-blown functional products with high melt index.

Description

PE/O-Cu 2 Preparation method of O@HNTs composite antibacterial microfiber

Technical Field

The invention relates to the field of PE-based melt-blown microfibers, in particular to a PE/O-Cu ₂ A preparation method of O@HNTs composite antibacterial microfiber.

Background

The melt-blown microfiber has the advantages of good filterability, good air permeability, low cost and the like, and is widely applied to the fields of medical sanitary materials such as masks, protective clothing and the like.

Medical and health protection articles made of melt-blown materials such as protective clothing and masks are helpful for preventing the transmission of fine particles such as bacteria and viruses. Studies have shown that SARS-CoV-2 can survive on the surface of meltblown fibers, and even more than 7 days outside of medical surgical masks. Bacteria, viruses, etc. are blocked from the protective nonwoven material surface, but they survive for days and are inhaled even by severe sneezing and coughing, which can cause secondary infections that pose an unexpected hazard to the health of the user. Therefore, the medical and sanitary protection nonwoven fabric is particularly important to sterilize while blocking bacteria.

Most of the melt-blown nonwovens are manufactured by using PP as a raw material at present, but other materials are also used in the melt-blown nonwoven field successively, and the development is continued. Wherein PPS, PS, PET, PA, PLA, PC and the like are used as raw materials to be applied to manufacturing melt-blown products, while PE has the similar advantages of PP, and meanwhile, the PE has better ageing resistance, and the obtained melt-blown fiber has long storage time; the heat conductivity coefficient is high, and the heat is easily led out from the melt-blown product; the flexibility is good, and the comfort of the obtained product is better. However, because the synthesis process of the high melt-index PE suitable for melt-blowing is limited, research on melt-blowing PE microfibers is blank at home and abroad, and development of high melt-index PE melt-blowing products also becomes a hot spot of current research.

Disclosure of Invention

Based on the above, the invention provides a PE/O-Cu ₂ The preparation method of the O@HNTs composite antibacterial microfiber aims at better solving the problem of secondary infection of a microfiber product and developing and obtaining a PE melt-blown microfiber product with high melt index.

To achieve the above object, the present invention provides a PE/O-Cu ₂ The preparation method of the O@HNTs composite antibacterial microfiber comprises the following steps:

s1, adding Halloysite Nanotubes (HNTs) into deionized water, adding disodium ethylenediamine tetraacetate after ultrasonic dispersion, stirring for reaction, and then adding CuSO ₄ ·5H ₂ O, dropwise adding NaOH solution and ascorbic acid solution; centrifuging, washing and vacuum drying the reaction product to obtain Cu ₂ O@HNTs micro-nano hybrid material; then Cu is added ₂ Dispersing the O@HNTs micro-nano hybrid material into a cyclohexane and n-propylamine composite solution, adding a silane coupling agent for treatment, washing with acetone, drying, and collecting to obtain the organized modified O-Cu ₂ O@HNTs micro-nano hybrid material;

s2, according to O-Cu ₂ The mass ratio of the O@HNTs micro-nano hybrid material is 10%, and O-Cu is adopted ₂ The O@HNTs micro-nano hybrid material and the high melt index polyethylene are kneaded reciprocally in a high temperature kneader to obtain PE/O-Cu ₂ O@HNTs micro-nano hybrid material;

s3, according to O-Cu ₂ The mass ratio of the O@HNTs micro-nano hybrid material is 0.1 to 0.6 percent, and PE/O-Cu is adopted ₂ Mixing the O@HNTs micro-nano hybrid material with high-melt-index polyethylene, and carrying out melt-blown spinning by a melt-blown spinning machine to obtain PE/Cu ₂ O@HNTs composite antibacterial microfiber.

As a further preferable technical scheme of the invention, in the step S1, the method uses each 4g halloysite nanotube as a reference and corresponds to CuSO ₄ ·5H ₂ The amount of O is 1 to up4g, the dosage of disodium ethylenediamine tetraacetate is 0.68-2.70 g, the dosage of NaOH solution of 1.5mol/L is 16-64 ml, and the dosage of ascorbic acid solution of 0.1mol/L is 12-48 ml; the amount of cyclohexane solvent was 100ml, the amount of n-propylamine solvent was 0.15ml, and the amount of silane coupling agent-gamma- (2, 3-glycidoxy) propyltrimethoxysilane was 0.5ml.

As a further preferable technical scheme of the invention, in the step S1, after disodium ethylenediamine tetraacetate is added, stirring reaction is carried out for 20-30 min at 35-50 ℃; after adding CuSO ₄ ·5H ₂ After O, stirring and reacting for 0.5-1 h, and then dropwise adding NaOH solution and ascorbic acid solution.

In a further preferable embodiment of the present invention, in step S1, cu is added to the mixture ₂ The O@HNTs micro-nano hybrid material is dispersed into a mixed solution of cyclohexane and n-propylamine, gamma- (2, 3-glycidoxy) propyl trimethoxy silane is added for reaction at room temperature for 35min, and then the reaction is carried out at 70 ℃ for 35min.

As a further preferable embodiment of the present invention, in the step S2, the melt index of the polyethylene is 120 to 1000g/10min and the kneading rotation speed is 200 to 400r/min. In the step S3, the melt index of the polyethylene is 120-1000 g/10min.

As a further preferable embodiment of the present invention, in step S3, the melt-blowing spinning machine includes a screw extruder for extruding PE/O-Cu, a melt-blowing die head, and a web-forming device ₂ Extruding the O@HNTs micro-nano hybrid material into a melt-blowing die head, and enabling the melt-blowing die head to carry out PE/O-Cu under the action of hot air ₂ The O@HNTs micro-nano hybrid material is blown to a net forming device.

As a further preferable technical scheme of the invention, the technological parameters of melt-blowing spinning by the melt-blowing spinning machine are as follows:

the screw of the screw extruder is provided with five temperature areas which are sequentially arranged along the material flow direction, and the temperatures of a first temperature area and a fifth temperature area of the screw extruder are respectively as follows: 120. 160, 210, 230, 240 ℃; the temperature of the hot air is 260 ℃, and the frequency of the hot air is 28-40 Hz; the receiving distance between the melt-blowing die head and the web-forming device is respectively 20-35 cm.

As a further preferable technical scheme of the inventionThe PE/O-Cu obtained in the step S3 ₂ The average diameter of the O@HNTs composite antibacterial microfiber is 2.4-4.6 um.

PE/O-Cu of the invention ₂ The preparation method of the O@HNTs composite antibacterial microfiber can achieve the following beneficial effects by adopting the technical scheme:

1) The invention adopts a chemical in-situ reduction method to prepare O-Cu ₂ O@HNTs micro-nano hybrid material for realizing small-size Cu with average size of 5.5nm ₂ O is loaded on HNTs, and Cu is added with the increase of the dosage of the copper precursor ₂ The loading of O is gradually increased, and the content of the organic modification component is 1.3-2.5%. The antibacterial property test shows that when the contact concentration is 10ug/mL, O-Cu ₂ The antibacterial rate of the O@HNTs on E.coli and S.aureus can reach more than 99.99 percent, which is attributed to HNTs and Cu ₂ Synergistic antimicrobial action of O, cu on hybrid material ₂ The size of O is smaller, the dispersibility is better, and the antibacterial performance of O can be exerted to the greatest extent;

2) The invention takes pure PE melt-blown microfiber as a reference, and the prepared PE/O-Cu ₂ O@HNTs-0.4％、PE/O-Cu ₂ The O@HNTs-0.6% composite melt-blown microfiber has the best antibacterial effect on escherichia coli and staphylococcus aureus, and can reach more than 99.9%, so that the composite melt-blown microfiber has excellent broad-spectrum antibacterial property.

Drawings

The invention will be described in further detail with reference to the drawings and the detailed description.

FIG. 1 shows (a, b) HNTs and (c, d) O-Cu ₂ TEM image of O@HNTs, (e) Cu ₂ Particle size distribution of O, (f) O-Cu ₂ Element profile of o@hnts.

FIG. 2 shows HNTs, cu ₂ O and O-Cu ₂ Colony count (a) and antibacterial rate (b) after O@HNTs were contacted with E.coli and S.aureus for 18 hours.

FIG. 3 is a diagram of PE/O-Cu ₂ (a) digital pictures, (b, c) SEM pictures, and (d) fiber diameter distribution diagrams of the O@HNTs composite antibacterial melt-blown microfibers.

FIG. 4 is a diagram of PE/O-Cu ₂ O@HNTs composite antibacterial melt-blown microfiberNumber of colonies (a) after 18h of exposure to E.coli and S.aureus, antibacterial rate (b).

The achievement of the objects, functional features and advantages of the present invention will be further described with reference to the accompanying drawings, in conjunction with the embodiments.

Detailed Description

The following describes specific embodiments of the present invention in detail with reference to the drawings. It should be understood that the detailed description and specific examples, while indicating and illustrating the invention, are not intended to limit the invention.

Unless defined otherwise, technical terms used in the following examples have the same meaning as commonly understood by one of ordinary skill in the art to which the inventive concepts pertain. The test reagents used in the following examples, unless otherwise specified, are all conventional biochemical reagents; wherein, the high-melting-point polyethylene slice is provided by the synthesis of the department of Chinese academy of chemistry; the experimental methods are conventional methods unless otherwise specified.

Comparative example 1

PE slices with the melt flow rate of 735g/10min are taken as raw materials, and melt-blown spinning is carried out by using a melt-blown spinning machine of camel group to prepare the pure PE melt-blown microfiber. The melt-blowing spinning machine comprises a screw extruder, a melt-blowing die head and a web forming device, wherein the screw extruder is used for extruding PE resin into the melt-blowing die head, and the melt-blowing die head blows PE resin to the web forming device under the action of hot air. The melt-blown fixing parameters were as follows: the temperatures of the first region and the fifth region of the screw are respectively: 120. 160, 210, 230 and 240 ℃, the temperature of hot air is 260 ℃, the frequency of hot air is 28-40 Hz, the winding speed is 9-16 Hz, the induced draft is 45Hz, and the receiving distance between the melt blowing die head and the web forming device is 20-35 cm.

Example 1

(1)、O-Cu ₂ Preparation of O@HNTs micro-nano hybrid material:

4g Halloysite Nanotubes (HNTs) and 200ml deionized water are sequentially added into the three-neck flask, and ultrasonic dispersion is carried out for 30min. Subsequently, 0.68g of disodium ethylenediamine tetraacetate (EDTA-2 Na) was added thereto, and the reaction was stirred at 40℃for 3 hours. Next, 1g of CuSO was added ₄ ·5H ₂ O, stirring and reacting for 1h. Then 16ml of NaOH solution (1.5 mol/L) and anti-deterioration agent are added dropwiseThe blood acid solution (0.1 mol/L) was 12ml. Finally, centrifuging and washing the product, and vacuum drying at 60 ℃; dispersing the powder obtained after drying in a mixed solution of 100ml cyclohexane and 0.15ml n-propylamine solvent, adding 0.5ml gamma- (2, 3-glycidoxy) propyl trimethoxy silane for reacting for 70min, washing with acetone, and drying to obtain O-Cu ₂ O@HNTs micro-nano hybrid material.

(2)、PE/O-Cu ₂ Synthesis of O@HNTs micro-nano hybrid material (also called composite resin):

according to O-Cu ₂ The content of the O@HNTs micro-nano hybrid material is 10 percent, and the mixture is mixed and kneaded with PE slices with the melt flow rate of 735g/10min, and the kneading rotating speed is 200r/min.

(4)、PE/O-Cu ₂ Preparation of O@HNTs composite antibacterial microfiber:

according to O-Cu ₂ The content of the O@HNTs micro-nano hybrid material is 0.1 to 0.6 percent, and PE/O-Cu is adopted ₂ The O@HNTs micro-nano hybrid material and the high melt index polyethylene are mixed and subjected to melt-blown spinning by a melt-blown spinning machine, and the melt-blown spinning process is the same as that of comparative example 1.

For O-Cu of example 1 ₂ Morphology test of O@HNTs micro-nano hybrid material:

observation of HNTs, O-Cu by TEM ₂ Structure and morphology of o@hnts. As can be seen from FIG. 1 (a, b), pure HNTs exhibit regular tubular structures with outer diameters of about 30-100 nm. As shown in FIG. 1 (c, d), O-Cu ₂ HNTs in the O@HNTs hybrid material keep the original tubular structure, and Cu with small size ₂ The O nano particles are attached to the surface of HNTs. For 80 Cu on HNTs ₂ Statistical display of O diameter, cu ₂ The average size of O was 5.5nm (FIG. 1 (e)). To further confirm Cu ₂ O-Cu was analyzed by EDS for O loading ₂ Chemical composition and elemental distribution of O@HNTs. As can be seen from FIG. 1 (f), the Cu element position is consistent with the distribution of Al and Si elements in HNTs, indicating Cu ₂ O is uniformly distributed on the outer surface of HNTs. Cu (Cu) ₂ The small size and uniform distribution of O is due to the coordination of EDTA, which coordinates Cu ₂ The size of O is limited to about 5.5nm, and Cu is contained ₂ O is attached on the surface of HNTs to ensure that the HNTs are uniformly distributed to avoid Cu ₂ Agglomeration of O.

The above shows that Cu has a small size of 5.5nm as an average particle diameter ₂ O is successfully loaded on the outer surface of HNTs. This is due to the addition of CuSO ₄ ·5H ₂ After O, cu due to chelation of EDTA-2Na ²⁺ Is fixed on the surface of HNTs, and cannot be agglomerated; with the addition of ascorbic acid, cu ²⁺ Is reduced in situ to form Cu with small size ₂ O。

For O-Cu of example 1 ₂ Antibacterial property test of O@HNTs micro-nano hybrid material:

to study the antibacterial property of the hybrid material, HNTs and Cu with contact concentration of 10mg/L are respectively contacted ₂ O and O-Cu ₂ The o@hnts were subjected to antibacterial tests, and the results of the number of related colonies and the antibacterial rate are shown in fig. 2.

As can be seen from FIG. 2, the bacterial colony count after the HNTs are contacted is slightly reduced, and the antibacterial rates of the HNTs on escherichia coli and staphylococcus aureus are 64.61% and 69.38%, respectively, which shows that the HNTs have certain antibacterial property because the HNTs have unique tubular structures, and sharp edges of the HNTs can damage cell membranes of bacteria. Cu (Cu) ₂ O、O-Cu ₂ The antibacterial rate of O@HNTs to escherichia coli is 95.13 percent respectively,>99.99% and antibacterial rate against Staphylococcus aureus>99.99%. Although Cu is ₂ O and O-Cu ₂ O@HNTs all exhibit a good antibacterial activity, but as is evident from FIG. 2 (a), they are excellent in comparison with Cu ₂ O compared with O, O-Cu ₂ The number of bacterial colonies after O@HNTs contact is significantly reduced. O-Cu ₂ O@HNTs showed excellent antibacterial properties at low concentrations (10 mg/L) due to HNTs and Cu ₂ Synergistic antibacterial action of O, and organically modified O-Cu on micro-nano hybrid material ₂ The O has smaller size and better dispersibility, and can exert the antibacterial performance to the greatest extent.

Examples 2 to 4

The preparation method and process are the same as in example 1, except that the synthesized O-PE/Cu ₂ O-Cu in O@HNTs composite resin ₂ The content of the O@HNTs micro-nano hybrid material is 0.2%, 0.4% and 0.6% respectively. PE has a melt index of 120 to 1000.

PE/O-Cu prepared in examples 1-4 ₂ O@HNTs composite antibacterial microfiber according to O-Cu ₂ The difference of the contents of the O@HNTs micro-nano hybrid materials is named as PE/O-Cu ₂ O@HNTs-y, y represents O-Cu ₂ Mass fraction of o@hnts.

PE/O-Cu for examples 1-4 ₂ The following experimental tests were carried out on the O@HNTs composite meltblown microfibers, and the PE meltblown microfibers of comparative example 1 were used as a control group:

the dispersibility of the particles in the meltblown microfibers and the fineness of the fibers directly affect the properties of the meltblown microfibers. Observation of O-Cu Using SEM ₂ The dispersibility of O@HNTs in the meltblown microfibers and the diameter distribution of the meltblown microfibers were counted according to SEM image, and the results are shown in FIG. 3.

FIG. 3 (a) is an electron photograph of a composite meltblown microfiber, it being seen that the PE meltblown microfiber is white; the composite melt-blown microfiber is brick red, and along with O-Cu ₂ The addition amount of O@HNTs increases gradually and becomes deeper. FIG. 3 (b-d) is an SEM image and diameter distribution of the composite meltblown microfibers. As can be seen from the figure, O-Cu ₂ O@HNTs have good dispersibility in PE matrix, which shows that the O@HNTs and the PE matrix have good compatibility with each other, and O-Cu ₂ The O@HNTs particle part is embedded in the melt-blown microfiber to make the tubular structure of the melt-blown microfiber not obvious enough, and the surface roughness of the composite antibacterial melt-blown microfiber is increased. Furthermore, with O-Cu ₂ The added amount of O@HNTs is increased, and the diameter of the melt-blown microfiber is increased. This is because the viscosity of the composite material increases with the addition amount of the nanoparticles, and the flow property of the melt deteriorates, so that the drawing efficiency of the hot air to the fibers decreases, resulting in an increase in the fiber diameter. The increase in fiber diameter will have an important effect on the pore size, filtration properties, air permeability, etc., of the meltblown microfibers, preferably O-Cu ₂ The content of O@HNTs is 0.1 to 0.6%, more preferably 0.4 to 0.6%.

The antibacterial performance of the composite antibacterial melt-blown microfiber on escherichia coli and staphylococcus aureus is studied by adopting an oscillation method. PE/O-Cu ₂ O@HNTs composite antibacterial melt-blown microfiber, escherichia coli and staphylococcus aureusThe colony count and antibacterial rate after 18h of contact with Pediococcus are shown in FIG. 4.

As can be seen from FIG. 4, with O-Cu ₂ The colony number of the composite antibacterial melt-blown microfibers is rapidly reduced due to the increase of the addition amount of O@HNTs. The pure PE melt-blown microfiber is used as a reference, and PE/O-Cu ₂ O@HNTs-0.1％、PE/O-Cu ₂ O@HNTs-0.2％、PE/O-Cu ₂ O@HNTs-0.4％、PE/O-Cu ₂ The antibacterial rates of the O@HNTs-0.6% composite antibacterial melt-blown microfiber on the escherichia coli are 49.14%, 91.56%, 99.93% respectively,>99.99%, and the antibacterial rate to staphylococcus aureus is 96.98%, 99.54%, 99.97%, respectively,>99.99%. When O-Cu ₂ When the addition amount of O@HNTs is more than 0.4%, the antibacterial rate of the composite antibacterial melt-blown microfiber is more than 99.9%, which shows that the composite antibacterial melt-blown microfiber has excellent broad-spectrum antibacterial property.

While particular embodiments of the present invention have been described above, it will be appreciated by those skilled in the art that these are merely illustrative, and that many variations or modifications may be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined only by the appended claims.

Claims (8)

1. PE/O-Cu ₂ The preparation method of the O@HNTs composite antibacterial microfiber is characterized by comprising the following steps of:

s1, adding halloysite nanotubes into deionized water, adding disodium ethylenediamine tetraacetate after ultrasonic dispersion, stirring for reaction, and then adding CuSO ₄ ·5H ₂ O, dropwise adding NaOH solution and ascorbic acid solution; centrifuging, washing and vacuum drying the reaction product to obtain Cu ₂ O@HNTs micro-nano hybrid material; then Cu is added ₂ Dispersing the O@HNTs micro-nano hybrid material into a cyclohexane and n-propylamine composite solution, adding a silane coupling agent for treatment, washing with acetone, drying, and collecting to obtain the organized modified O-Cu ₂ O@HNTs micro-nano hybrid material;

s2, according to O-Cu ₂ The mass ratio of the O@HNTs micro-nano hybrid material is 10%, and O-Cu is adopted ₂ O@HNTs micro-nano hybrid material and high melt index polyethylene are processed in a high-temperature kneaderRe-kneading to obtain PE/O-Cu ₂ O@HNTs micro-nano hybrid material;

s3, according to O-Cu ₂ The mass ratio of the O@HNTs micro-nano hybrid material is 0.1 to 0.6 percent, and PE/O-Cu is adopted ₂ Mixing the O@HNTs micro-nano hybrid material with high-melt-index polyethylene, and carrying out melt-blown spinning by a melt-blown spinning machine to obtain PE/Cu ₂ O@HNTs composite antibacterial microfiber.

2. The PE/O-Cu according to claim 1 ₂ The preparation method of the O@HNTs composite antibacterial microfiber is characterized in that in the step S1, the method uses each 4g halloysite nanotube as a reference and corresponds to CuSO ₄ ·5H ₂ The dosage of O is 1-4 g, the dosage of disodium ethylenediamine tetraacetate is 0.68-2.70 g, the dosage of NaOH solution of 1.5mol/L is 16-64 ml, and the dosage of ascorbic acid solution of 0.1mol/L is 12-48 ml; the amount of cyclohexane solvent was 100ml, the amount of n-propylamine solvent was 0.15ml, and the amount of silane coupling agent-gamma- (2, 3-glycidoxy) propyltrimethoxysilane was 0.5ml.

3. The PE/O-Cu according to claim 1 ₂ The preparation method of the O@HNTs composite antibacterial microfiber is characterized in that in the step S1, after disodium ethylenediamine tetraacetate is added, stirring reaction is carried out for 20-30 min at 35-50 ℃; adding CuSO ₄ ·5H ₂ After O, stirring and reacting for 0.5-1 h, and then dropwise adding NaOH solution and ascorbic acid solution.

4. The PE/O-Cu according to claim 1 ₂ The preparation method of the O@HNTs composite antibacterial microfiber is characterized by comprising the following steps of in step S1, adding Cu ₂ Dispersing the O@HNTs micro-nano hybrid material into a mixed solution of cyclohexane and n-propylamine, adding gamma- (2, 3-glycidoxy) propyl trimethoxy silane, reacting for 30-35min at room temperature, and then reacting for 30-35min at 60-70 ℃.

5. The PE/O-Cu according to claim 1 ₂ The preparation method of the O@HNTs composite antibacterial microfiber is characterized in that in the step S2, the melt index of polyethylene is 120-1000g/10min, and kneading rotation speed is 200-400 r/min; in the step S3, the melt index of the polyethylene is 120-1000 g/10min.

6. The PE/O-Cu according to claim 1 ₂ The preparation method of the O@HNTs composite antibacterial microfiber is characterized in that in the step S3, a melt-blowing spinning machine comprises a screw extruder, a melt-blowing die head and a net forming device, wherein the screw extruder is used for extruding PE/O-Cu ₂ Extruding the O@HNTs micro-nano hybrid material into a melt-blowing die head, and enabling the melt-blowing die head to carry out PE/O-Cu under the action of hot air ₂ The O@HNTs micro-nano hybrid material is blown to a net forming device.

7. The PE/O-Cu according to claim 6 ₂ The preparation method of the O@HNTs composite antibacterial microfiber is characterized by comprising the following technological parameters of melt-blowing spinning by a melt-blowing spinning machine:

the screw of the screw extruder is provided with five temperature areas which are sequentially arranged along the material flow direction, and the temperatures of a first temperature area and a fifth temperature area of the screw extruder are respectively as follows: 120. 160, 210, 230, 240 ℃; the temperature of the hot air is 260 ℃, and the frequency of the hot air is 28-40 Hz; the receiving distance between the melt-blowing die head and the web-forming device is respectively 20-35 cm.

8. The PE/O-Cu according to claim 7 ₂ The preparation method of the O@HNTs composite antibacterial microfiber is characterized by comprising the following step S3 of obtaining PE/O-Cu ₂ The average diameter of the O@HNTs composite antibacterial microfiber is 2.4-4.6 um.