CN119455700A

CN119455700A - A method for preparing a plasma surface modified porous polytetrafluoroethylene chemically deposited double-chain quaternary ammonium salt polymer alloy film

Info

Publication number: CN119455700A
Application number: CN202510067339.1A
Authority: CN
Inventors: 余媛; 张丽莉; 曾繁昆; 朱海霖; 郭雨杰; 李梦华; 胡佳琪; 徐瑞鑫
Original assignee: Zhejiang Sci Tech University ZSTU
Current assignee: Zhejiang Sci Tech University ZSTU
Priority date: 2025-01-15
Filing date: 2025-01-15
Publication date: 2025-02-18
Anticipated expiration: 2045-01-15
Also published as: CN119455700B

Abstract

The application provides a preparation method of a plasma surface modified porous polytetrafluoroethylene chemical deposition double-chain quaternary ammonium salt polymer alloy film, belonging to the technical field of functional films. Adding water into PVA to dissolve to obtain PVA water solution, adding zinc chloride to obtain zinc chloride PVA solution, adding PTFE into the zinc chloride PVA solution, stirring uniformly, dissolving the obtained solution into an organic solvent to obtain spinning solution, carrying out electrostatic spinning on the spinning solution to obtain a porous polytetrafluoroethylene film, carrying out plasma surface activation treatment on the porous polytetrafluoroethylene film, carrying out chemical surface modification by using double-chain quaternary ammonium salt, drying, and carrying out thermal crosslinking to obtain the finished product.

Description

Preparation method of plasma surface modified porous polytetrafluoroethylene chemical deposition double-chain quaternary ammonium salt polymer alloy film

Technical Field

The application relates to a preparation method of a plasma surface modified porous polytetrafluoroethylene chemical deposition double-chain quaternary ammonium salt polymer alloy film, belonging to the technical field of functional films.

Background

With climate change, population growth and acceleration of globalization process, water resource crisis is continuously aggravated, and water availability is continuously declining. With the importance of water resources, water treatment technology is becoming mature. Currently, membrane technology, iron-carbon micro-electrolysis treatment technology, fenton and Fenton-like oxidation method, ozonization method, magnetic separation technology, plasma water treatment technology and the like have been applied to the purification treatment of organic matters, microorganisms, dyes, heavy metal ions and the like in water bodies. Among them, the membrane technology has been widely used in sewage treatment and sea water desalination as one of the most successful and cost-effective technologies. Polytetrafluoroethylene (PTFE) is a high-performance polymeric material with high thermal stability and good flexibility, mechanical properties and film forming properties. However, the conventional PTFE membrane has a strong hydrophobicity, and the commercial PTFE membrane has a problem of water permeability degradation due to membrane contamination during filtration, which has prevented the wide application of the conventional PTFE membrane and the commercial PTFE membrane. Meanwhile, in addition to membrane contamination caused by inorganic deposition and organic attachment, poor adhesion and growth of microorganisms on the membrane is also a common form of membrane contamination, so-called biological contamination. Biological contamination can lead to reduced water permeability, today resulting in increased energy consumption and operating costs of the membrane process. Solving biological fouling of membranes has become one of the most challenging problems of membrane technology. In the current research, much work has been focused on improving the anti-biofouling properties of films by adding antimicrobial agents to prepare composite films, i.e., adding very small amounts of antimicrobial agents such as metal ions (Ag, zn, cu, etc.) and oxide photocatalysts (such as TiO ₂, zn0, etc.) to the films, thereby imparting a certain antimicrobial property to the prepared films. However, the antibacterial property and the effect of inhibiting the biological contamination of the film are not ideal.

Disclosure of Invention

In view of the above, the application provides a preparation method of a plasma surface modified porous polytetrafluoroethylene chemical deposition double-chain quaternary ammonium salt polymer alloy membrane, which not only endows the membrane with a larger specific surface area and improves the plasma activation efficiency, but also obviously improves the antibacterial and filtering properties.

Specifically, the application is realized by the following scheme:

the preparation method of the plasma surface modified porous polytetrafluoroethylene chemical deposition double-chain quaternary ammonium salt polymer alloy film comprises the following steps:

step one, adding water into polyvinyl alcohol (PVA) to dissolve to obtain PVA water solution, adding zinc chloride (white solid powder, purity is more than 98%) to obtain zinc chloride PVA solution,

The PVA is preferably of medium and low molecular weight and moderate alcoholysis degree, the molecular weight of the PVA is 5000-50000, the alcoholysis degree is 80-100%,

The mass concentration of the PVA aqueous solution is 1-30%,

The addition amount of zinc chloride is 0.5-5% of the mass of PVA.

In the process, PVA is added with water and stirred for 10-30 min, zinc chloride is added after the PVA is uniformly dissolved, and stirring is continued for 15-30 min to obtain a zinc chloride PVA solution, wherein the stirring speeds are 100-300 r/min.

And secondly, adding PTFE into the zinc chloride PVA solution, and uniformly stirring, wherein the addition amount of the PTFE is 100-900% of the PVA.

In the process, PTFE powder is added into a zinc chloride PVA aqueous solution, and the mixture is stirred at a high speed for 20-60 min, wherein the stirring speed is 600-1000 r/min, and finally a uniform emulsion state is obtained.

And thirdly, dissolving the solution obtained in the second step into an organic solvent to prepare a spinning solution, and carrying out electrostatic spinning on the spinning solution to obtain the porous polytetrafluoroethylene film, wherein the concentration of the spinning solution is 5-30%, the spinning voltage of electrostatic spinning is 10-100 KV, the spinning range is 10-40 cm, and the propelling speed is 0.06-6 mm/min ‌.

And step four, performing low-temperature plasma surface activation treatment on the porous polytetrafluoroethylene membrane, and then performing chemical surface modification by using double-chain quaternary ammonium salt, drying and thermal crosslinking to obtain a finished product.

Further, as preferable:

In the first step, the first step is to perform,

The molecular weight of the PVA is 20000-40000, and the alcoholysis degree is 80-90%. And the molecular weight of PVA is 30000-40000, the alcoholysis degree is preferably 85-90%, and the molecular weight of PVA is 30000, and the alcoholysis degree is preferably 88%.

The mass concentration of the PVA aqueous solution is 1-2.4%, the zinc chloride addition amount is 0.5-2% of the mass of the PVA, and the mass concentration of the PVA aqueous solution is 1.8%, and the zinc chloride addition amount is 1.5% of the mass of the PVA.

In the second step, the second step is to carry out the process,

The PTFE content is 400 to 900% by mass of PVA, and the PTFE content is preferably 733% by mass of PVA.

In the third step, the first step is performed,

The concentration of the spinning solution is 5-20%, the spinning distance is 10-25 cm, and the propelling speed is 0.06-0.84 mm/min ‌. And the concentration of the spinning solution is 15%, the spinning range is 25cm, and the propelling speed is 0.72mm/min ‌.

The organic solvent is any one of ethanol, acetone and dimethyl amide (DMF), and the concentration of the spinning solution is changed by controlling the addition amount of the organic solvent.

In the fourth step, the first step is performed,

The treatment power of the low-temperature plasma surface activation treatment is 5-20 MHz, the treatment time is 10-60 min, and the treatment temperature is 20-30 ℃. And preferably 5 to 15MHz for 10 to 20 minutes.

And carrying out chemical surface modification on the film by using double-stranded quaternary ammonium salt in a surface coating deposition mode, wherein the coating amount of the double-stranded quaternary ammonium salt is 0.1-2% of the mass of the porous polytetrafluoroethylene film. More preferably, the coating amount is 0.1 to 1% by mass of the porous polytetrafluoroethylene film. And the coating amount is preferably 0.8% of the mass of the porous polytetrafluoroethylene film.

The double-chain quaternary ammonium salt is specifically didecyl dimethyl ammonium chloride or didecyl dimethyl ammonium bromide.

The drying temperature is 60-120 ℃ and the drying time is 30-120 min.

The temperature of the thermal crosslinking is 120-240 ℃, and the thermal crosslinking time is 60-180 min.

And (3) washing the heat-crosslinked product with water at 20-50 ℃ for 1-5 times to remove unreacted double-chain quaternary ammonium salt on the surface.

The invention adopts the double-chain quaternary ammonium salt as the organic antibacterial agent, combines the double-chain quaternary ammonium salt with the PTFE film, increases the deposition and chemical reaction performance of the double-chain quaternary ammonium salt on the surface of the film through a plasma activation technology, and increases the hydrophilicity and the plasma activation efficiency of the film by the added PVA component, thereby improving the filtration efficiency and the antibacterial performance of the film, and improving the antibacterial efficiency by 50 percent compared with the inorganic antibacterial powder, thereby being particularly suitable for the development of masks, air conditioners and water treatment filter materials.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments or the description of the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings can be obtained according to these drawings without inventive effort for a person skilled in the art.

The left image in fig. 1 is an SEM image of the film after drying in step (4) in example 34, and the right image in fig. 1 is an SEM image of the film after thermal crosslinking in step (5) in example 34.

Detailed Description

In order to make the technical problems, technical solutions and advantageous effects to be solved by the present application more clear, the technical solutions in the embodiments of the present application will be further described in detail below with reference to the accompanying drawings in the embodiments of the present application, and it should be understood that the specific embodiments described herein are only for explaining the present application and are not intended to limit the technical solutions of the present application. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.

Example 1

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1% PVA aqueous solution, wherein the PVA has a molecular weight of 5000 and an alcoholysis degree of 80%, adding deionized water into PVA, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 0.5% of the mass of the PVA, and the stirring speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 400% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 5%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing 60 ℃ drying treatment and drying for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt didecyl dimethyl ammonium chloride.

The obtained film is tested according to the test standard of GB/T20944.3-2008, the antibacterial effect is 72/73/71 on escherichia coli, staphylococcus aureus and candida albicans, the filtering and blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS mask, wherein M is the electrostatic spinning film, the filtering efficiency is 87%, and the contact angle is 58 degrees.

Since PVA molecular weight is too low, resulting in severe fluid loss during the later elution, affecting the pore size of the membrane, medium molecular weight PVA was selected for testing.

Example 2

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1% PVA aqueous solution, wherein the PVA molecular weight is 20000, the alcoholysis degree is 80%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 0.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 400% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 5%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing 60 ℃ drying treatment and drying for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt didecyl dimethyl ammonium chloride.

The obtained film is tested according to the test standard of GB/T20944.3-2008, the antibacterial effect is 72/73/71 on escherichia coli, staphylococcus aureus and candida albicans, the filtering and blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS mask, wherein M is the electrostatic spinning film, the filtering efficiency is 89%, and the contact angle is 51 degrees.

Example 3

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 80%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 0.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 400% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 5%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested by SEM observation with the diameter of 2 microns according to the test standard of GB/T20944.3-2008, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 72/73/71, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 92%, and the contact angle is 49 degrees.

Example 4

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1% PVA aqueous solution with a PVA molecular weight of 40000 and an alcoholysis degree of 80%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 0.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 400% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 5%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested by SEM observation with the diameter of 2.2 microns according to the test standard of GB/T20944.3-2008, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 71/72/70, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 91%, and the contact angle is 55 degrees.

The molecular weight filtering efficiency is further increased and is reduced, the molecular weight is too high, so that the viscosity of the classical spinning solution is too high, the fiber diameter is increased, the filtering efficiency is reduced, the smaller the contact angle is, namely the hydrophilicity is considered to be better, the smaller the contact angle is, the better the hydrophilicity is when the molecular weight of PVA is smaller, but the lower molecular weight is easy to be dissolved in water to be separated out, and the content of the film is lower, so that the embodiment shows that the molecular weight of PVA is 20000-40000, the molecular weight of PVA is 30000-40000 is better, and the effect is best when the molecular weight of PVA is 30000.

Example 5

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 85%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 0.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 400% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 5%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested by SEM observation diameter of 2 microns according to the test standard of GB/T20944.3-2008, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 72/73/71, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 93%, and the contact angle is 48 degrees.

Example 6

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 0.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 400% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 5%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested by SEM observation with the diameter of 2 microns according to the test standard of GB/T20944.3-2008, the antibacterial effect on escherichia coli, staphylococcus aureus and candida albicans is 72/73/71, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 94%, and the contact angle is 46 degrees.

Example 7

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 90%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 0.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 400% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 5%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested by SEM observation diameter of 2 microns according to the test standard of GB/T20944.3-2008, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 72/73/71, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 93%, and the contact angle is 47 degrees.

In summary, the alcoholysis degree is preferably 80-90%, and is preferably 85-90%, and when the PVA alcoholysis degree is 88%, the PVA has the best water solubility, so that the spinning solution is the most uniform, and the filtering effect is the best.

Example 8

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 2% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 0.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 250% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 5%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T209444.3-2008 by SEM observation diameter of 2.5 micrometers, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 68/70/69, the filtering and blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film, the filtering efficiency is 90 percent and the contact angle is 45 degrees.

At this time, the ratio of PVA to PTFE was adjusted, and it was found that when the PVA content in the electrospinning solution was increased, the fiber became thicker, and the filtration efficiency and antibacterial performance were lowered. Therefore, the amount of PTFE to be added is preferably controlled to 250% or more of the PVA mass.

Example 9

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 0.7% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 0.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 614% of the PVA mass, stirring at a high speed for 40min and the stirring speed is 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 5%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested by SEM observation with the diameter of 1.5 microns according to the test standard of GB/T20944.3-2008, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 75/77/74, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 95%, and the contact angle is 46 degrees.

Example 10

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 0.6% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 0.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 5%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested by SEM observation with the diameter of 1.3 microns according to the test standard of GB/T20944.3-2008, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 78/79/76, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 96%, and the contact angle is 47 degrees.

Example 11

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 0.5% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 0.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 900% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 5%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested by SEM observation with the diameter of 1.4 microns according to the test standard of GB/T20944.3-2008, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 78/79/76, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 95%, and the contact angle is 50 degrees.

At this time, the ratio of PVA in the electrostatic spinning solution is continuously reduced, the fiber diameter is thickened, and the filtration efficiency and the antibacterial performance are reduced, so that the PTFE addition amount is suitably controlled to 400-900% of the PVA mass, and when the ratio of PVA to PTFE is 100:733 (namely, the PTFE addition amount is 733% of the PVA mass), the PTFE addition amount is optimal.

Example 12

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.2% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 0.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 10%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested by SEM observation with the diameter of 1.2 microns according to the test standard of GB/T20944.3-2008, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 79/81/78, the filtering and blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtering efficiency is 97%, and the contact angle is 43 degrees.

Example 13

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 0.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested by SEM observation with the diameter of 1.2 microns according to the test standard of GB/T20944.3-2008, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 81/84/80, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 98%, and the contact angle is 41 degrees.

Example 14

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 2.4% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 0.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 20%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested by SEM observation with the diameter of 1.3 microns according to the test standard of GB/T20944.3-2008, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 80/82/79, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 97%, and the contact angle is 42 degrees.

At this time, the concentration of the electrostatic spinning solution is continuously increased, and the antibacterial and filtering efficiency is reduced, so that the concentration of the spinning solution is properly controlled to be 5-20%, and the optimal spinning concentration is 15%.

Example 15

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T209444.3-2008 by SEM observation diameter of 1.2 micrometers, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 82/85/81, the filtering and blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtering efficiency is 98%, and the contact angle is 40 degrees.

Example 16

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested by SEM observation with the diameter of 1.2 microns according to the test standard of GB/T20944.3-2008, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 84/86/82, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 98%, and the contact angle is 40 degrees.

Example 17

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 2% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 10cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested by SEM observation with the diameter of 1.2 microns according to the test standard of GB/T20944.3-2008, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 83/84/81, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 96%, and the contact angle is 41 degrees.

At this time, zinc chloride is continuously added, so that the antibacterial filtration efficiency is not increased, but the antibacterial efficiency is reduced due to uneven pores caused by the increase of the content of the zinc chloride, and meanwhile, the filtration efficiency is also reduced, so that the zinc chloride addition amount is 0.5-2% of the PVA mass, and is optimal when the zinc chloride addition amount is 1.5% of the PVA mass.

Example 18

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 15cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T20944.3-2008 by SEM observation diameter of 0.9 micrometer, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 86/89/85, the filtering and blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtering efficiency is 99%, and the contact angle is 35 degrees.

Example 19

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 20cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T209444.3-2008 by SEM observation with the diameter of 0.5 micrometer, the antibacterial effect on Escherichia coli, staphylococcus aureus and white twisting coccus is 89/90/87, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 99%, and the contact angle is 35 degrees.

Example 20

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 25cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested by SEM observation with the diameter of 0.3 micron, the antibacterial effect is 91/92/89 to the escherichia coli, staphylococcus aureus and white twisting coccus according to the test standard of GB/T20944.3-2008, the filtering and blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtering efficiency is 99 percent, and the contact angle is 34 degrees.

Example 21

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 30cm, and the propelling speed is 0.06mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

At this time, the spinning range is too long, the film is uneven, and the film cannot be sampled for testing, so that the spinning range is properly controlled to be 10-25 cm, and the optimal spinning range is 25cm.

Example 22

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 25cm, and the propelling speed is 0.12mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T209444.3-2008 by SEM observation with the diameter of 0.3 micrometer, the antibacterial effect on Escherichia coli, staphylococcus aureus and white twisting coccus is 92/93/90, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 99%, and the contact angle is 34 degrees.

Example 23

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 25cm, and the propelling speed is 0.24mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T20944.3-2008 by SEM observation diameter, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 93/94/91, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is more than 99%, and the contact angle is 34 degrees.

Example 24

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 25cm, and the propelling speed is 0.48mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T20944.3-2008 by SEM observation diameter, the antibacterial effect is 94/94/92 on escherichia coli, staphylococcus aureus and white twisting coccus, the filtering and blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtering efficiency is more than 99%, and the contact angle is 33 degrees.

Example 25

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 25cm, and the propelling speed is 0.60mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T20944.3-2008 by SEM observation diameter of 0.2 micrometer, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 94/94/94, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is more than 99%, and the contact angle is 31 degrees.

Example 26

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 25cm, and the propelling speed is 0.72mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T209444.3-2008 by SEM observation diameter of 0.1 micrometer, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 95/96/95, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is more than 99%, and the contact angle is 30 degrees.

Example 27

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 25cm, and the propelling speed is 0.84mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 5MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T20944.3-2008 by SEM observation diameter of 0.2 micrometer, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 94/95/93, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 99%, and the contact angle is 32 degrees.

At this time, the advancing speed of the electrostatic spinning solution is continuously increased, the fiber diameter is thickened, and the antibacterial and filtering efficiency is reduced, so that the advancing speed of the electrostatic spinning solution is properly controlled to be 0.06-0.84 mm/min ‌, and the optimal speed is 0.72 mm/min.

Example 28

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 25cm, and the propelling speed is 0.72mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 10MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T209444.3-2008 by SEM observation diameter of 0.1 micrometer, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 96/97/95, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is more than 99%, and the contact angle is 30 degrees.

Example 29

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 25cm, and the propelling speed is 0.72mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 15MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T209444.3-2008 by SEM observation diameter of 0.1 micrometer, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 97/97/96, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is more than 99%, and the contact angle is 30 degrees.

Example 30

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 25cm, and the propelling speed is 0.72mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 20MHz, the treatment time is 10min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

At this time, the plasma treatment power is continuously increased, the antibacterial effect is not increased any more, and the plasma surface activation treatment power of 5-15 MHz is better, and the best effect can be achieved when the treatment power is 15 MHz.

Example 31

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 25cm, and the propelling speed is 0.72mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 15MHz, the treatment time is 20min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T209444.3-2008 by SEM observation diameter of 0.1 micrometer, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 97/98/97, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is more than 99%, and the contact angle is 30 degrees.

Example 32

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 25cm, and the propelling speed is 0.72mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 15MHz, the treatment time is 30min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.5% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The antibacterial effect is not increased any more when the plasma treatment time is continuously increased, which indicates that the plasma surface activation treatment time of 10-20 min is more suitable, and the treatment time is enough when the treatment time is 20 min.

Example 33

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 25cm, and the propelling speed is 0.72mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 15MHz, the treatment time is 20min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.1% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T209444.3-2008 by SEM observation diameter of 0.1 micrometer, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 77/78/75, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is more than 99%, and the contact angle is 35 degrees.

Example 34

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 25cm, and the propelling speed is 0.72mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 15MHz, the treatment time is 20min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 0.8% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T209444.3-2008 by SEM observation diameter of 0.1 micrometer, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 100/100/99, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is more than 99%, and the contact angle is 28 degrees.

Example 35

(1) Preparing a zinc chloride PVA aqueous solution, namely preparing a 1.8% PVA aqueous solution, wherein the PVA molecular weight is 30000, the alcoholysis degree is 88%, stirring for 20min to dissolve uniformly, adding zinc chloride, continuously stirring for 20min, wherein the adding amount of the zinc chloride is 1.5% of the PVA mass, and the stirring rotating speed is 200r/min. (2) The compounding technology of the zinc chloride PVA aqueous solution and polytetrafluoroethylene comprises the steps of adding PTFE powder into the uniformly stirred zinc chloride PVA aqueous solution, wherein the addition amount is 733% of the PVA mass, and stirring at a high speed for 40min at a stirring speed of 800r/min. (3) Preparing a porous polytetrafluoroethylene film by electrostatic spinning, namely preparing the porous polytetrafluoroethylene film by an electrostatic spinning process, wherein the concentration of a spinning solution is 15%, the spinning voltage is 60KV, the spinning range is 25cm, and the propelling speed is 0.72mm/min ‌. The medium of the spinning solution is the compound in the step (2), and the solvent is DMF. (4) And (3) performing low-temperature plasma surface activation treatment on the film obtained in the step (3), wherein the power is 15MHz, the treatment time is 20min, the treatment temperature is 25 ℃, then performing chemical surface modification on the film by using didecyl dimethyl ammonium chloride in a surface coating deposition mode, wherein the coating amount of the didecyl dimethyl ammonium chloride is 1.0% of the mass of the film, and performing drying treatment at 60 ℃ for 90min after the modification. (5) And (3) carrying out heat crosslinking treatment on the antibacterial hydrophilic porous polytetrafluoroethylene filter membrane obtained in the step (4), wherein the heat crosslinking temperature is 120 ℃, the heat crosslinking time is 120min, and then washing (3 times of washing at 20 ℃) to remove unreacted double-chain quaternary ammonium salt.

The obtained film is tested according to the test standard of GB/T209444.3-2008 by SEM observation diameter of 0.1 micrometer, the antibacterial effect on escherichia coli, staphylococcus aureus and white twisting coccus is 100/100/100, the filtration blocking efficiency is tested according to the test standard of GB/T19083-2010, and the test sample is prepared into an SMS type mask, wherein M is the electrostatic spinning film of the invention, the filtration efficiency is 98 percent, and the contact angle is 31 degrees.

The coating amount of the double-stranded quaternary ammonium salt is the biggest factor influencing the antibacterial property, but as the coating amount increases, the porosity of the film is reduced, and the filtration efficiency is reduced mainly due to the reduction of the porosity caused by the thermal crosslinking of the film, and the coating amount of the double-stranded quaternary ammonium salt is preferably 0.1-2% of the mass of the porous polytetrafluoroethylene film.

In combination with the antibacterial and filtering properties of the above examples, example 34 is an optimal preparation process, and the film before and after thermal crosslinking is subjected to electron microscopy, so that the surface is that after the thermal crosslinking treatment of the present application, double-chain quaternary ammonium salt is anchored on the surface of the film through chemical action, and meanwhile, PVA in the film cannot be dissolved and migrate into water in the later use process, resulting in reduced hydrophilic and filtering properties.

The above examples only represent a few possible embodiments of the invention, which are described in more detail and are not to be construed as limiting the scope of the invention, nor are they intended to limit the scope of the invention as claimed. It will be apparent to those skilled in the art that various modifications and improvements can be made without departing from the spirit of the invention, and it is intended to include the present invention in all equivalent implementations or modifications.

Claims

1. The preparation method of the plasma surface modified porous polytetrafluoroethylene chemical deposition double-chain quaternary ammonium salt polymer alloy film is characterized by comprising the following steps of:

step one, PVA is added with water to be dissolved to obtain PVA aqueous solution, then zinc chloride is added to obtain zinc chloride PVA solution,

The molecular weight of the PVA is 5000-50000, the alcoholysis degree is 80-100%,

The mass concentration of the PVA aqueous solution is 1-30%,

The addition amount of zinc chloride is 0.5-5% of the PVA mass;

Adding PTFE into the zinc chloride PVA solution, and uniformly stirring, wherein the addition amount of the PTFE is 100-900% of the PVA;

Step three, dissolving the solution obtained in the step two in an organic solvent to obtain a spinning solution, and carrying out electrostatic spinning on the spinning solution to obtain a porous polytetrafluoroethylene film, wherein the concentration of the spinning solution is 5-30%, the spinning voltage of electrostatic spinning is 10-100 KV, the spinning range is 10-40 cm, and the propelling speed is 0.06-6 mm/min ‌;

And step four, performing plasma surface activation treatment on the porous polytetrafluoroethylene membrane, and then performing chemical surface modification by using double-chain quaternary ammonium salt, drying and thermal crosslinking to obtain a finished product.

2. The method for preparing the plasma surface modified porous polytetrafluoroethylene chemical deposition double-chain quaternary ammonium salt polymer alloy film according to claim 1, wherein the molecular weight of PVA is 20000-40000, and the alcoholysis degree is 80-90%.

3. The method for preparing the plasma surface modified porous polytetrafluoroethylene chemical deposition double-chain quaternary ammonium salt polymer alloy film according to claim 1, wherein the molecular weight of PVA is 30000-40000, and the alcoholysis degree is 88-90%.

4. The preparation method of the plasma surface modified porous polytetrafluoroethylene chemical deposition double-chain quaternary ammonium salt polymer alloy film is characterized in that the mass concentration of the PVA aqueous solution is 1-2.4%, the zinc chloride addition amount is 0.5-2% of the PVA mass, and the PTFE addition amount is 400-900% of the PVA mass.

5. The preparation method of the plasma surface modified porous polytetrafluoroethylene chemical deposition double-chain quaternary ammonium salt polymer alloy film is characterized in that the concentration of the spinning solution is 5-20%, the spinning range is 10-25 cm, and the advancing speed is 0.06-0.84 mm/min ‌.

6. The preparation method of the plasma surface modified porous polytetrafluoroethylene chemical deposition double-chain quaternary ammonium salt polymer alloy film is characterized in that the treatment power of the plasma surface activation treatment is 5-20 MHz, and the treatment time is 10-60 min.

7. The preparation method of the plasma surface modified porous polytetrafluoroethylene chemical deposition double-chain quaternary ammonium salt polymer alloy film is characterized in that the double-quaternary ammonium salt is deposited on the porous polytetrafluoroethylene film in a coating mode, and the coating amount is 0.1-2% of the mass of the porous polytetrafluoroethylene film.

8. The preparation method of the plasma surface modified porous polytetrafluoroethylene chemical deposition double-chain quaternary ammonium salt polymer alloy film is characterized in that the drying temperature is 60-120 ℃ and the drying time is 30-120 min.

9. The preparation method of the plasma surface modified porous polytetrafluoroethylene chemical deposition double-chain quaternary ammonium salt polymer alloy film is characterized in that the thermal crosslinking temperature is 120-240 ℃ and the thermal crosslinking time is 60-180 min.

10. The method for preparing the plasma surface modified porous polytetrafluoroethylene chemically deposited double-chain quaternary ammonium salt polymer alloy film according to any one of claims 1-9, wherein the thermal crosslinking is further followed by water washing at 20-50 ℃ for 1-5 times.