CN113996187B - Graphene oxide air sterilization film and preparation method thereof - Google Patents
Graphene oxide air sterilization film and preparation method thereof Download PDFInfo
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- CN113996187B CN113996187B CN202111189286.9A CN202111189286A CN113996187B CN 113996187 B CN113996187 B CN 113996187B CN 202111189286 A CN202111189286 A CN 202111189286A CN 113996187 B CN113996187 B CN 113996187B
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D46/0027—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions
- B01D46/0028—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours with additional separating or treating functions provided with antibacterial or antifungal means
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D46/54—Particle separators, e.g. dust precipitators, using ultra-fine filter sheets or diaphragms
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- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
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- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The application relates to the technical field of air purification, and particularly discloses a graphene oxide air sterilization film and a preparation method thereof, wherein the graphene oxide air sterilization film comprises a substrate, graphene oxide coated on the substrate, an antibacterial agent and a high polymer; the graphene oxide, the antibacterial agent and the high molecular polymer are respectively dissolved by a solvent and then are coated on a substrate, wherein the concentration of the graphene oxide, the antibacterial agent and the high molecular polymer in the solvent is respectively 1 multiplied by 10 ‑4 ～10×10 ‑4 g/g、2.5×10 ‑4 ～100×10 ‑4 g/g and 5X 10 ‑4 ～10×10 ‑4 g g/g. The application has the advantages of convenience and effectiveness in sterilizing and purifying air.
Description
Technical Field
The application relates to the technical field of air purification, in particular to a graphene oxide air sterilization film and a preparation method thereof.
Background
With the increase of human economy, the current environmental pollution is more serious. With the deterioration of the environment, diseases transmitted through air as a medium, such as cholera, hepatitis, influenza, mumps, varicella-zoster infection, hand-foot-and-mouth disease, tuberculosis, and new crown pneumonia, are also increasing. Therefore, the air disinfection in public places where people are active becomes an important guarantee of public health and safety.
The current common air disinfection and sterilization methods are mainly three methods of physical, chemical and biological methods. The physical method mainly comprises a thermal sterilization method and an ultraviolet sterilization method, but is limited by the use condition and the use method, and the thermal sterilization method is commonly used for sterilizing high-temperature resistant instruments; ultraviolet disinfection is harmful to human body, has high cost, and is difficult to be applied to air disinfection in various spaces. The chemical disinfection has the defects of poor disinfection effect, residual pollution, strong corrosiveness, high disinfection cost or expensive disinfection equipment manufacturing cost, complex use process and the like; the biological disinfectant uses animals, plants, microorganisms or metabolites thereof as active ingredients for killing pathogenic microorganisms, has high cost, is generally used in the industries of food and the like, and is difficult to be used in large scale in the air.
Currently, there are various disadvantages in the air sterilization method, so that it is highly demanded to study an air sterilization film capable of performing air sterilization.
Disclosure of Invention
In order to facilitate and effectively sterilizing and purifying air, the application provides a graphene oxide air sterilizing film and a preparation method thereof.
In a first aspect, the present application provides a graphene oxide air sterilization film and a preparation method thereof, which adopts the following technical scheme:
a graphene oxide air sterilization film comprises a substrate, and graphene oxide, an antibacterial agent and a high-molecular polymer which are coated on the substrate; the graphene oxide, the antibacterial agent and the high molecular polymer are respectively dissolved by a solvent and then are coated on a substrate, wherein the concentration of the graphene oxide, the antibacterial agent and the high molecular polymer in the solvent is respectively 1 multiplied by 10 -4 ～10×10 -4 g/g、2.5×10 -4 ～ 100×10 -4 g/g and 5X 10 -4 ～10×10 -4 g/g。
By adopting the technical scheme, a large amount of bacteria, mold and viruses are easy to remain in the air in public places because of large mobility of people, great harm is generated to the health of people in public places, people with low immunity such as respiratory diseases and allergic symptoms can be caused by long-term contact with mold, headache, fever, asthma, skin or mucous membrane inflammation and tonsillitis can be caused, and cancerogenic substances can be seriously generated. Especially in a hospital environment, pathogenic bacteria mainly come from patients, a great deal of patients flow, the pathogenic bacteria are combined with dust particles in the air of the hospital, are attached to a wall body and fly to the ground, and are bred and reproduced in a proper environment, so that the pathogenic bacteria are easily transmitted to medical staff and patients in the doctor. The graphene oxide and the antibacterial agent are introduced on the matrix to play an antibacterial and bactericidal role.
Graphene oxide is a novel green environment-friendly material, when the graphene oxide is in direct contact with bacteria, the sharp edges of the lamellar layers of the graphene oxide directly damage the cell membrane structure through mechanical damage or damage the cell membrane through large-scale direct extraction of phospholipid molecules on the cell membrane, so that the damage of the bacterial structure and the disorder of functions are caused; meanwhile, the charged groups rich in the surface of the graphene oxide can enter the microorganism after interacting with the microorganism, so that the metabolism balance of the microorganism free radicals is disturbed, and the biological film and the macromolecular substances are damaged by peroxidation, thereby achieving the antibacterial effect.
The antibacterial agent can be divided into four types of organic antibacterial agents, inorganic antibacterial agents, natural antibacterial agents and organic-inorganic composite antibacterial agents according to different materials, wherein the organic antibacterial agents have good sterilization effects on bacillus dysenteriae, escherichia coli and staphylococcus aureus, and the inherent stability of the organic antibacterial agents and the high efficiency and broad spectrum of antibacterial components are combined, so that the antibacterial agent has an effect on various bacteria, and the broad spectrum and the high efficiency of the antibacterial film are further improved by adopting the organic antibacterial agents.
The addition of the high molecular polymer has the following advantages: firstly, improving the synergistic antibacterial effect between graphene oxide and an antibacterial agent; secondly, the combination of graphene oxide and an antibacterial agent with a substrate is more stable due to the addition of the high molecular polymer, so that the mechanical property of the prepared sterilizing film is effectively improved; finally, the use of the high molecular polymer can improve the compactness and sterilization effect of the sterilizing film, and the prepared sterilizing film is a compact film, so that dust particles in the air can be trapped on the basis of effectively killing bacteria, mold and viruses in the air, and the circulation of the air is not influenced.
Preferably, the lateral dimension of the graphene oxide material is at least one of 0.1-0.2 μm, 1-2 μm and 5-10 μm.
Preferably, the content of the oxygen-containing groups of the graphene oxide is 10% -40%.
Through adopting above-mentioned technical scheme, adopt above-mentioned transverse dimension and oxygen group's graphene oxide not only can guarantee the degree of compactness of sterilizing film, but also have better antibiotic effect.
Preferably, the antibacterial agent is at least one of a biguanide disinfectant and a quaternary ammonium salt disinfectant.
More preferably, the mass ratio of the biguanide disinfectant to the quaternary ammonium salt disinfectant in the antibacterial agent is 1:1-4.
Preferably, the biguanide disinfectant is at least one selected from polyhexamethylene biguanide hydrochloride, polyaminopropyl biguanide salt, chlorhexidine acetate and chlorhexidine gluconate.
By adopting the technical scheme, the biguanide antibacterial agent has quite strong broad-spectrum antibacterial and bactericidal effects and has effects on various bacteria. Besides bacteriostasis, it can kill bacteria. Mainly destroy the permeable barrier on the bacterial plasma membrane, the low concentration can lead to partial cytoplasmic leakage, and the high concentration can lead to cytoplasmic coagulation and denaturation, thereby sterilizing. Its advantages are low irritation and less anaphylactic reaction.
Preferably, the quaternary ammonium salt is at least one selected from didecyl dimethyl ammonium chloride, didodecyl dimethyl ammonium chloride, benzalkonium bromide and benzalkonium chloride.
By adopting the technical scheme, the quaternary ammonium salt disinfectant is a cationic surfactant, has the characteristics of low toxicity, small irritation, wide antibacterial spectrum and the like, can change the permeability of bacterial cytoplasmic membranes, and can cause the exosmosis of bacterial cytoplasmic substances to prevent the bacterial cytoplasmic substances from metabolizing so as to play a role in killing. They have strong bactericidal power, can inactivate fat-soluble viruses, has no irritation to skin and tissues, has no toxicity to human bodies, and has no corrosion to metal and rubber products.
Preferably, the molecular weight of the high molecular polymer is between 1.5 and 20 kDa.
Preferably, the high molecular polymer is at least one of polymethacrylic acid, polyamide, polyethyleneimine, polyethylene glycol and chitosan.
Through adopting above-mentioned technical scheme, adopt above-mentioned polymer and graphene oxide, antiseptic to combine, the compound film of being applied to air sterilization that develops not only has good air disinfection performance, avoids the propagation of other dust and macroparticles in the space to a certain extent moreover, still has better mechanical properties simultaneously, and the life of sterilizing film is longer, but reuse has reduced manufacturing and use cost.
Preferably, the substrate is any one of non-woven fabric, polyacrylonitrile, polyvinylidene fluoride, nylon and polycarbonate.
By adopting the technical scheme, the substrate material is easy to obtain and has better mechanical properties. Meanwhile, the graphene oxide, the antibacterial agent and the high-molecular polymer used in the application have a wide applicable fiber range, and can be used for preparing the sterilizing film by adopting the substrate fiber. The fiber has smaller gaps, so that the effect of the sterilizing film on trapping dust in the air can be improved to a certain extent.
In a second aspect, the application provides a graphene oxide air sterilization film and a preparation method thereof, and the technical scheme is as follows:
the preparation method of the graphene oxide air sterilization film comprises the following steps: uniformly dispersing graphene oxide, an antibacterial agent and a high polymer in a solvent to prepare a graphene oxide solution, an antibacterial agent solution and a high polymer solution respectively; coating a high polymer solution, a graphene oxide solution, an antibacterial agent solution and a graphene oxide solution on a substrate in sequence to form a film; and then repeating the sequential film forming operation until the required cycle times are reached, and preparing the graphene oxide air sterilization film through heat treatment.
Preferably, the coating method includes any one of spin coating, spray coating, dip-coating and pulling.
Preferably, the number of repeating the film forming operation is 30 to 60.
Through adopting above-mentioned technical scheme, carry out the preparation of graphene oxide solution, antibacterial agent solution and polymer solution respectively, can make graphene oxide, antibacterial agent and polymer respectively more even dispersion in the solvent, reduce the probability that produces the agglomeration because of the valence bond effect between each material when mixing jointly for the film formation is even, and the coating in turn is more favorable to the compact degree of rete, is difficult for forming big defect. The number of times of forming the film is less than 30, and the prepared sterilizing film has poor density and poor sterilizing and dust-trapping effects; when the film forming times are more than 60 times, the effects of sterilizing and trapping dust of the sterilizing film are not greatly improved, and the film forming operation effect is better by adopting 30-60 times.
The substrate is coated with the high polymer solvent firstly, so that the high polymer solvent is adhered to the substrate firstly, and the subsequent solution can be uniformly coated; and then coating the graphene oxide solvent and the antibacterial agent solvent, wherein the graphene oxide solvent and the antibacterial agent solvent exist stably through valence bond action, are used for synergistic sterilization, and are repeatedly subjected to the coating operation for a plurality of times until the set circulation times are reached, so that the prepared sterilizing film has a good sterilizing effect, and can intercept dust under the condition of not influencing air circulation. The preparation method is simple and is easy for industrial production.
Preferably, the solvent is at least one of water, methanol, ethanol and dimethyl sulfoxide.
By adopting the technical scheme, the graphene oxide, the antibacterial agent and the high-molecular polymer can be uniformly and effectively dispersed in the solvent by adopting the solvent.
Preferably, the graphene oxide is dispersed in a solvent, and ultrasonic treatment is adopted for 0.5-1 h, so that the graphene oxide is uniformly dispersed.
Preferably, the heat treatment is carried out at 45-80 ℃ for 3-6 hours.
By adopting the technical scheme, the heat treatment temperature is lower than 45 ℃, the drying time is longer, and when the temperature is higher than 80 ℃, the damage of the sterilizing film is easily caused, and the performance of the sterilizing film is influenced. Through the research of the inventor, the heat treatment temperature can be adopted to reduce the damage of heat treatment to the sterilizing film while the sterilizing film is rapidly dried and molded.
In summary, the present application has the following beneficial effects:
1. graphene oxide, an antibacterial agent and a high molecular polymer are used as raw materials, and the surface of a substrate is alternately coated and overlapped to form a film by a coating method, so that the prepared sterilizing film has a good sterilizing effect, and dust can be trapped under the condition of not influencing air circulation; the membrane with various scales can be prepared according to the requirements, and can be used for disinfecting and purifying air in various places, such as air conditioning, air purifier and other various devices for compositely purifying air.
2. The air sterilizing film prepared by the application has high mechanical property and long service life, can be repeatedly used, and reduces the production and use costs.
3. The preparation method is simple and easy for industrial production.
Detailed Description
The present application is described in further detail below with reference to examples.
The raw materials used in the present application are all commercially available.
Examples
Example 1
The graphene oxide air sterilization film is prepared by the following method:
adding 0.25g graphene oxide (with transverse dimension of 1-2 μm and oxygen-containing group content of 40%) into mixed solvent of 250g water and 250g ethanol, and treating with ultrasound (600W) for 1 hr to dissolve completely to obtain a solution with concentration of 5×10 -4 g/g graphene oxide solvent; 1g of polyhexamethylene biguanide hydrochloride and 1g of didecyl dimethyl ammonium chloride are taken and dissolved in 200g of waterStirring thoroughly to obtain a concentration of 100×10 -4 Standing g/g of antibacterial agent solvent for standby; dissolving 0.1g polyethylenimine (molecular weight 10 kDa) in 200g water, stirring thoroughly to obtain a solution with a concentration of 5×10 -4 And g/g of high polymer solvent is kept stand for standby.
Placing the polyacrylonitrile fiber on a spin Tu Yi, and then coating the prepared high polymer solution, graphene oxide solution and antibacterial agent solution on the whole surface of the polyacrylonitrile fiber alternately and uniformly according to the steps (1500 rpm/s,15 s); the spin coating sequence is that after a layer of high polymer solution is spin coated, a layer of graphene oxide solution is spin coated, and after a layer of antibacterial agent solution is spin coated, a layer of graphene oxide solution is spin coated.
Repeating the steps for 50 times, and treating for 3 hours at 60 ℃ to obtain the graphene oxide air sterilization film.
Examples 2 to 16 differ from example 1 in the amount of the raw materials added, as shown in tables 1 and 2.
TABLE 1 amounts of raw materials to be added in examples 1 to 8
TABLE 2 amounts of raw materials to be added in examples 9 to 16
/represent no addition of
Example 17
Example 17 differs from example 1 in that the number of cycles was 30.
Example 18
Example 18 differs from example 1 in that the number of cycles was 60.
Comparative example
Comparative example 1
Comparative example 1 differs from example 1 in that the concentration of graphene oxide in the solvent is 0.1X10 -4 g/g, concentration of the antibacterial agent in the solvent is 1×10 -4 g/g, the concentration of the high molecular polymer in the solvent is 4X 10 -4 g/g。
Comparative example 2
Comparative example 2 differs from example 1 in that the concentration of graphene oxide in the solvent is 40×10 -4 g/g, the concentration of the antibacterial agent in the solvent is 200X 10 -4 g/g, the concentration of the high molecular polymer in the solvent is 15 multiplied by 10 -4 g/g。
Performance test
The following performance tests were performed on the bactericidal films prepared in examples 1 to 18 and comparative examples 1 to 2 described above:
(1) Filtration test
And (3) testing the air filtration performance, namely testing the filtration performance of the membrane by adopting a filter material comprehensive performance test bench. Wherein the particle size of the test dust is 0.3 μm, and the filtration efficiency (η,%) is calculated as η= (1-p) ×100%. Wherein p is the transmittance (%) of the film member to the particles; the detection results are shown in Table 3.
(2) Sterilization test
The prepared sterilizing film is cut into a proper size, and is placed into an air purifier, and the cutting size of the sterilizing film is in order to cover the air outlet of the air purifier. The air purifier was placed in a closed room, and the room was sampled to determine the colony count. Then two persons enter the room for normal operation every hour, stay for 10min, close the door to ensure the airtight space when entering and exiting the room, and continuously operate the air purifier with the sterilizing film during the period, and sample every 1 hour. Under the same experimental conditions in the same room, the control group without the sterilizing film is used for finally calculating the average elimination rate of bacteria.
TABLE 3 filtration and sterilization Properties in examples 1-18 and comparative examples 1-2
As can be seen by combining examples 1-18 and comparative examples 1-2 and combining table 3, the sterilizing film prepared by the method has good air sterilizing performance, and meanwhile, on the basis of enhancing the sterilizing performance of the film, the propagation of other dust and large particles in space is avoided to a certain extent; the air sterilizing film prepared by the application has high mechanical property, long service life and repeated use, and has good sterilizing performance after being used for a period of time, thereby reducing the production and use cost. The preparation method is characterized in that after a layer of high polymer solution is formed on the surface of the polyacrylonitrile fiber, the high polymer slightly infiltrates to enhance the bonding property between the high polymer and a substrate, so that the mechanical property of the film is improved, a foundation is laid for the subsequent coating and assembling process of the film, a layer of graphene oxide solution is then spin-coated, rich oxygen-containing groups on the graphene oxide sheet can be connected with the polyethyleneimine through hydrogen bonds, covalent bonds and electrostatic effects, and chemical action sites are provided for the introduction of a subsequent antibacterial agent, so that the uniform distribution of the film material is ensured, and the compactness and the antibacterial property are improved.
As can be seen from Table 1, the properties of example 5 in the present application are superior to those of the other examples and comparative examples, i.e., the concentrations of graphene oxide, the antibacterial agent and the high molecular polymer in the solvent are 5X 10 in the present application -4 g/g、100×10 -4 g/g and 5X 10 -4 At g/g, the molecular weight of the high molecular polymer is 10k Da, the antibacterial agent is mixed by polyhexamethylene biguanide hydrochloride and didecyl dimethyl ammonium chloride according to the mass ratio of 1:2.5, and the prepared sterilizing film has the best effect when the number of cycles is 50.
As can be seen in combination with examples 9-15 and with table 2, graphene oxide is not the better the larger the lateral dimension, the higher the added quality; the reason may be that the graphene oxide is too large in size or too high in addition quality, so that a film layer formed by coating is uneven easily, macropores are formed, and the filtration sterilization performance is reduced. And the higher the oxidation degree of the graphene oxide is, the more binding sites are formed, so that the antibacterial agent and the polymer are uniformly distributed, and the compactness degree and the sterilization performance of the film are improved.
Compared with example 1, the concentrations of graphene oxide, antibacterial agent and high molecular polymer in the solvent are lower than the concentration ranges defined in the application, while the concentrations of graphene oxide, antibacterial agent and high molecular polymer in the solvent are higher than the concentration ranges defined in the application in comparative example 2, and it can be seen by combining example 1 with comparative examples 1 and 2 and combining table 2 that the sterilization rate of comparative examples 1 and 2 is lower than that of example 1, namely, after the concentrations of graphene oxide, antibacterial agent and high molecular polymer in the solvent are beyond the concentration ranges defined in the application, the sterilization performance of the sterilization film is not greatly improved, and other performances of the sterilization film are also reduced. The reason may be that when the concentration of the film material is too high, the film material is unevenly distributed in the film layer, so that defect holes are easily formed in the subsequent film layer coating and assembling process, and finally the compactness degree and sterilization performance of the film are affected. When the three contents are too low, the sterilization performance of the sterilization film is too low.
The present embodiment is merely illustrative of the present application and is not intended to be limiting, and those skilled in the art, after having read the present specification, may make modifications to the present embodiment without creative contribution as required, but is protected by patent laws within the scope of the claims of the present application.
Claims (6)
1. The graphene oxide air sterilization film is characterized by comprising a substrate, and graphene oxide, an antibacterial agent and a high-molecular polymer which are coated on the substrate; the graphene oxide, the antibacterial agent and the high molecular polymer are respectively dissolved by a solvent and then are coated on a substrate, wherein the concentration of the graphene oxide, the antibacterial agent and the high molecular polymer in the solvent is respectively 1 multiplied by 10 -4 ～10×10 -4 g/g、2.5×10 -4 ～100×10 -4 g/g and 5X 10 -4 ～10×10 -4 g/g；
The antibacterial agent is at least one of biguanide disinfectant and quaternary ammonium salt disinfectant;
the molecular weight of the high molecular polymer is between 1.5 and 20 kDa;
the high molecular polymer is at least one of polymethacrylic acid, polyamide, polyethyleneimine, polyethylene glycol and chitosan;
the preparation method of the graphene oxide air sterilization film comprises the following steps: uniformly dispersing graphene oxide, an antibacterial agent and a high polymer in a solvent to prepare a graphene oxide solution, an antibacterial agent solution and a high polymer solution respectively; coating a high polymer solution, a graphene oxide solution, an antibacterial agent solution and a graphene oxide solution on a substrate in sequence to form a film; and then repeating the film forming operation in turn until the required cycle times are reached, and preparing the graphene oxide air sterilization film through heat treatment.
2. The graphene oxide air sterilization film according to claim 1, wherein: the transverse dimension of the graphene oxide material is at least one of 0.1-0.2 mu m, 1-2 mu m and 5-10 mu m.
3. The graphene oxide air sterilization film according to claim 2, wherein: the content of the oxygen-containing groups of the graphene oxide is 10% -40%.
4. The graphene oxide air sterilization film according to claim 1, wherein: the substrate is any one of non-woven fabrics, polyacrylonitrile, polyvinylidene fluoride, nylon and polycarbonate.
5. The graphene oxide air sterilization film according to claim 1, wherein: the solvent is at least one of water, methanol, ethanol and dimethyl sulfoxide.
6. The graphene oxide air sterilization film according to claim 1, wherein: the heat treatment is carried out at 45-80 ℃ for 3-6 hours.
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Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101641474A (en) * | 2006-11-24 | 2010-02-03 | 诺瓦潘萨克股份公司 | Film material with antimicrobial and/or odor-absorbing coating and sanitary article |
| CN205695864U (en) * | 2016-05-03 | 2016-11-23 | 韩淑敏 | There is the mask of oxygen-supplying function |
| CN106310978A (en) * | 2016-10-17 | 2017-01-11 | 江苏新风环保科技有限公司 | Compound air filter membrane based on chitosan and graphene oxide and preparation method of compound air filter membrane |
| WO2017190352A1 (en) * | 2016-05-06 | 2017-11-09 | 宝峰时尚国际控股有限公司 | Air disinfection purifier and method for preparing photocatalytic film used thereby |
| KR20180000781A (en) * | 2016-06-23 | 2018-01-04 | 중앙대학교 산학협력단 | Multilayer nanofilms and manufacturing method thereof |
| CN107674283A (en) * | 2017-10-20 | 2018-02-09 | 福建恒安卫生材料有限公司 | The preparation method of biaxial tension ventilated membrane |
| CN108854601A (en) * | 2018-07-31 | 2018-11-23 | 合肥峰腾节能科技有限公司 | A kind of preparation method of farm's air cleaning film |
| CN109224878A (en) * | 2018-10-29 | 2019-01-18 | 成都新柯力化工科技有限公司 | A kind of air cleaning composite antibacterial film and preparation method |
| CN211185966U (en) * | 2019-10-31 | 2020-08-07 | 弓立（厦门）医疗用品有限公司 | Gauze mask |
| CN212233223U (en) * | 2020-04-21 | 2020-12-29 | 杭州一菲信息技术有限公司 | Protective mask |
| CN212464991U (en) * | 2020-03-05 | 2021-02-05 | 东莞市容鑫防静电技术有限公司 | Anti-static anti-droplet mask |
| CN112870845A (en) * | 2020-12-30 | 2021-06-01 | 湖南翰坤实业有限公司 | Active carbon-based air purification material and preparation method thereof |
| KR20210095397A (en) * | 2020-01-23 | 2021-08-02 | 손지훈 | Filter using graphene and polymer, and manufacturing thereof |
| CN113402747A (en) * | 2021-06-03 | 2021-09-17 | 华东理工大学 | High-strength edible antibacterial packaging film and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20180326359A1 (en) * | 2017-05-15 | 2018-11-15 | Aspen Products Group, Inc. | Layered Membrane and Methods of Preparation Thereof |
| AU2019288482A1 (en) * | 2018-06-21 | 2021-01-14 | Nitto Denko Corporation | Selectively permeable graphene oxide membrane for dehydration of a gas |
| CN111331976B (en) * | 2020-03-24 | 2020-12-22 | 大连双迪桃花卫生用品有限公司 | Composite protective material for epidemic prevention of neocoronary pneumonia and preparation method thereof |
-
2021
- 2021-10-12 CN CN202111189286.9A patent/CN113996187B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101641474A (en) * | 2006-11-24 | 2010-02-03 | 诺瓦潘萨克股份公司 | Film material with antimicrobial and/or odor-absorbing coating and sanitary article |
| CN205695864U (en) * | 2016-05-03 | 2016-11-23 | 韩淑敏 | There is the mask of oxygen-supplying function |
| WO2017190352A1 (en) * | 2016-05-06 | 2017-11-09 | 宝峰时尚国际控股有限公司 | Air disinfection purifier and method for preparing photocatalytic film used thereby |
| KR20180000781A (en) * | 2016-06-23 | 2018-01-04 | 중앙대학교 산학협력단 | Multilayer nanofilms and manufacturing method thereof |
| CN106310978A (en) * | 2016-10-17 | 2017-01-11 | 江苏新风环保科技有限公司 | Compound air filter membrane based on chitosan and graphene oxide and preparation method of compound air filter membrane |
| CN107674283A (en) * | 2017-10-20 | 2018-02-09 | 福建恒安卫生材料有限公司 | The preparation method of biaxial tension ventilated membrane |
| CN108854601A (en) * | 2018-07-31 | 2018-11-23 | 合肥峰腾节能科技有限公司 | A kind of preparation method of farm's air cleaning film |
| CN109224878A (en) * | 2018-10-29 | 2019-01-18 | 成都新柯力化工科技有限公司 | A kind of air cleaning composite antibacterial film and preparation method |
| CN211185966U (en) * | 2019-10-31 | 2020-08-07 | 弓立（厦门）医疗用品有限公司 | Gauze mask |
| KR20210095397A (en) * | 2020-01-23 | 2021-08-02 | 손지훈 | Filter using graphene and polymer, and manufacturing thereof |
| CN212464991U (en) * | 2020-03-05 | 2021-02-05 | 东莞市容鑫防静电技术有限公司 | Anti-static anti-droplet mask |
| CN212233223U (en) * | 2020-04-21 | 2020-12-29 | 杭州一菲信息技术有限公司 | Protective mask |
| CN112870845A (en) * | 2020-12-30 | 2021-06-01 | 湖南翰坤实业有限公司 | Active carbon-based air purification material and preparation method thereof |
| CN113402747A (en) * | 2021-06-03 | 2021-09-17 | 华东理工大学 | High-strength edible antibacterial packaging film and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 石墨烯功能化纳米纤维空气净化材料研究进展;陈梦艳等;南京工业大学学报（自然科学版）;第43卷(第4期);第411-418页 * |
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