CN112126154A - Method for modifying polypropylene by combining ZnO/chitosan/ZIF-8, filter material and anti-virus mask - Google Patents
Method for modifying polypropylene by combining ZnO/chitosan/ZIF-8, filter material and anti-virus mask Download PDFInfo
- Publication number
- CN112126154A CN112126154A CN202011001876.XA CN202011001876A CN112126154A CN 112126154 A CN112126154 A CN 112126154A CN 202011001876 A CN202011001876 A CN 202011001876A CN 112126154 A CN112126154 A CN 112126154A
- Authority
- CN
- China
- Prior art keywords
- polypropylene
- chitosan
- mask
- zif
- zno
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D13/00—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches
- A41D13/05—Professional, industrial or sporting protective garments, e.g. surgeons' gowns or garments protecting against blows or punches protecting only a particular body part
- A41D13/11—Protective face masks, e.g. for surgical use, or for use in foul atmospheres
- A41D13/1192—Protective face masks, e.g. for surgical use, or for use in foul atmospheres with antimicrobial agent
-
- A—HUMAN NECESSITIES
- A41—WEARING APPAREL
- A41D—OUTERWEAR; PROTECTIVE GARMENTS; ACCESSORIES
- A41D31/00—Materials specially adapted for outerwear
- A41D31/04—Materials specially adapted for outerwear characterised by special function or use
- A41D31/30—Antimicrobial, e.g. antibacterial
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D39/00—Filtering material for liquid or gaseous fluids
- B01D39/14—Other self-supporting filtering material ; Other filtering material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0435—Electret
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
- B01D2239/04—Additives and treatments of the filtering material
- B01D2239/0442—Antimicrobial, antibacterial, antifungal additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2296—Oxides; Hydroxides of metals of zinc
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/08—Stabilised against heat, light or radiation or oxydation
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Textile Engineering (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- General Health & Medical Sciences (AREA)
- Physical Education & Sports Medicine (AREA)
- Respiratory Apparatuses And Protective Means (AREA)
- Filtering Materials (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a method for modifying polypropylene by combining ZnO/chitosan/ZIF-8, a filter material and an anti-virus mask, which comprises the following steps: s1, mixing a soluble zinc salt aqueous solution and an acetic acid aqueous solution, and then adding chitosan to obtain a mixed solution; s2, adding a strong alkali aqueous solution; s3, immersing the polypropylene in the solution, standing, taking out and drying; s4, adding imidazole salt and soluble zinc salt into the mixed solution of methanol and water; and S5, immersing the product obtained in the S3 into the mixed solution of S4, standing, taking out and drying to obtain the target product. By the method for jointly modifying the polypropylene, the reusable filter material with high-efficiency filtering efficiency and sterilization effect is prepared by a simple means, the problems existing in the application of the existing ZIF-8 are solved, the antivirus mask prepared by the filter material has the functions of blocking dust and microorganisms, resisting bacteria and sterilizing, hydrophobicity and high-temperature stability, can be cleaned and sterilized by high-temperature virus, and is reused.
Description
Technical Field
The invention relates to the technical field of protective masks, in particular to a method for modifying polypropylene by combining ZnO/chitosan/ZIF-8, a filter material and an anti-virus mask.
Background
With the acceleration of industrialization process, the problem of air environmental pollution in China is increasingly prominent in recent years. Effective control of airborne pollutants, pests, aerosol particles has long been a social concern. The mask can effectively prevent the spread of virus when being worn correctly, however, the N95 mask with the best filtering effect has serious defects of poor productivity due to complex manufacturing process and high manufacturing cost, and in addition, the mask cannot be reused and has short service life, and a large amount of solid garbage can be brought after the mask is used. Therefore, it is very important to develop a protective mask with low cost, simple manufacturing process, high filtration capability, and even virus inhibition and inactivation, and the key point is to develop a novel reusable filter material.
The reason why the filter layer adopted in the current mask is melt-blown non-woven fabric woven by polypropylene (filter material) and cannot be reused through high-temperature disinfection is that the material is not heat-resistant and can deform and lose efficacy after high-temperature treatment, and the material needs to be further modified to improve the thermal stability. Metal-Organic Frameworks (MOFs) have high hydrophobicity, chemical stability and thermal stability, and in addition, the MOFs has shown potential in the antibacterial and antiviral application field, and becomes the first choice of a reusable novel sterilization filter material modification method. Among many MOFs, zinc-based zeolite imidazole framework (ZIF-8) is the most studied MOFs membrane material, and has been applied to sterilization mask filter materials. MOFs represented by ZIF-8 are mainly composed of Zn2+Formed by reaction with imidazole ligands, Zn2+Has oxidation-reduction property, can puncture membrane protein structure of bacteria to make it lose activity, and has a certain antiviral action. However, since ZIF-8 is expensive to prepare, the preparation method needs to be adjusted to balance its performance and cost. In addition, ZIF-8 is prone to agglomeration due to high surface energy, resulting in uneven distribution, and further modification is required for practical application.
Therefore, researchers in the field are dedicated to developing a reusable filter material with high-efficiency filtration efficiency and sterilization effect, and a low-cost high-efficiency reusable anti-virus mask made of the filter material.
Disclosure of Invention
The first invention of the present invention is directed to: aiming at the existing problems, the polypropylene filter material which can be repeatedly used and has high-efficiency filtration efficiency and sterilization efficacy is provided, and the defects that the common antibacterial bactericide is not heat-resistant, has poor compatibility with a polypropylene melt-blown non-woven fabric substrate and is not resistant to soaking, washing and high-temperature sterilization treatment are overcome by providing a method for growing the antibacterial inorganic zinc oxide and the metal organic framework ZIF-8 composite material with the sterilization efficacy on polypropylene in situ. Meanwhile, the natural organic antibacterial agent chitosan with excellent degradability is used for further modifying the modified polypropylene, so that the mask polymer filter material prepared from the material is improved to have broad-spectrum antibacterial property and biocompatibility, and the antibacterial and antiviral properties of the mask polymer filter material are improved.
The technical scheme adopted by the invention is as follows: a method for modifying polypropylene by combining ZnO/chitosan/ZIF-8 is characterized by comprising the following steps:
s1, uniformly mixing a designed amount of soluble zinc salt aqueous solution and acetic acid aqueous solution, adding a certain amount of chitosan, and uniformly stirring and reacting at 50-70 ℃ for 4-8h to obtain a mixed solution;
s2, adding a strong base aqueous solution into the mixed solution, and uniformly stirring for 0.5-2h at 50-70 ℃;
s3, completely immersing the polypropylene in the mixed solution of S2, standing for a certain time at 50-70 ℃, taking out, washing with an organic solvent and deionized water respectively, and drying at 100-130 ℃ for 8-15h to obtain ZnO/chitosan modified polypropylene;
s4, adding imidazole salt and soluble zinc salt with designed amount into the mixed solution of methanol and water, and uniformly stirring for 1-3 h at 50-70 ℃;
s5, completely immersing the ZnO/chitosan modified polypropylene in the mixed solution of S4, standing for a certain time at 50-70 ℃, taking out, washing with an organic solvent, and drying at 70-100 ℃ for 8-15h to obtain the ZnO/chitosan/ZIF-8 combined modified polypropylene.
In the above method, the organic solvent is used mainly for washing away the reactant such as acetic acid attached to the product, and therefore, washing with a commonly used organic solvent is sufficient, and for example, absolute ethanol may be used without particular limitation. By the method for jointly modifying polypropylene and the method for preparing the polypropylene mask filter material, the reusable filter material with high-efficiency filtering efficiency and sterilization effect is prepared by a simple means. In the filter material, the ZIF-8 microporous structure has very high gas permeation and screening functions, the coating of bacterial cells or viruses is damaged by strong catalytic capacity, the agglomeration problem of the ZIF-8 can be effectively solved by ZnO, the thermal stability of the mask filter material is improved, and the problems existing in the application of the existing ZIF-8 can be solved by performing antibacterial sterilization through oxidation reaction. Meanwhile, the invention also introduces chitosan to modify polypropylene together, the amino group contained in the chitosan interacts or chelates with zinc to form an effective filter medium, and further performs antibacterial sterilization through the interaction of electrostatic attraction and the surface residue of the negatively charged microbial cell, so that the antibacterial and antiviral performances of the filter material are improved, and the finally obtained filter material can be sterilized at high temperature or can be reused after being washed.
Preferably, the soluble zinc salt is zinc acetate dihydrate, zinc nitrate hexahydrate or zinc chloride.
Preferably, the imidazolium salt is benzimidazole or 2-methylimidazole.
Further, in S1, the concentration of the soluble zinc salt aqueous solution is 0.5 to 5mmol/L, the volume percentage of acetic acid in the acetic acid aqueous solution is 0.5 to 1.5%, and the specific concentration is selected according to actual needs.
Further, in S2, the aqueous alkali solution is an aqueous sodium hydroxide solution having a concentration of 1 to 10 mmol/L. Of course, other strong alkaline aqueous solutions may be used, such as potassium hydroxide, lithium hydroxide, and the like, with sodium hydroxide being preferred.
Further, the standing time in S3 and S5 is 6-18 h.
Further, in S4, the mass ratio of the imidazolium salt to the soluble zinc salt is (0.5-5): (0.2-2).
The invention also comprises a reusable polypropylene mask filter material which comprises the polypropylene material obtained by the ZnO/chitosan/ZIF-8 combined modified polypropylene method, and the polypropylene material is used as a polypropylene non-woven fabric mask filter material.
The second invention of the present invention is directed to: aiming at the problem that the existing mask can not be used repeatedly, the reusable antiviral mask is provided, the antiviral mask is made of a modified polypropylene filter material containing ZnO/chitosan/ZIF-8, has the functions of blocking dust and microorganisms, can be used for performing antibacterial sterilization by destroying the envelope of bacterial cells or viruses, has hydrophobicity and high-temperature stability, can be used for cleaning and sterilizing high-temperature viruses, realizes repeated use, and overcomes the problems of the existing mask.
The technical scheme adopted by the invention is as follows: a reusable antiviral mask, wherein the filter layer of said antiviral mask is made of the polypropylene mask filter of claim 8.
Further, antiviral gauze mask includes gauze mask main part and accessory component, gauze mask main part is formed by the non-woven fabrics layer stack combination of outer non-woven fabrics layer, filter layer and inlayer, accessory component includes nose clip and ear area, the upper end of gauze mask main part is located to the nose clip, the both sides department of gauze mask main part is located to the ear area.
In summary, due to the adoption of the technical scheme, the invention has the beneficial effects that:
1. by the method for jointly modifying polypropylene and the method for preparing the polypropylene mask filter material, the reusable filter material with high-efficiency filtering efficiency and sterilization effect is prepared by a simple means. In the filter material, the ZIF-8 microporous structure has very high gas permeation and screening functions, the coating of bacterial cells or viruses is damaged by strong catalytic capacity, the agglomeration problem of the ZIF-8 can be effectively solved by ZnO, the thermal stability of the mask filter material is improved, and the problems existing in the application of the existing ZIF-8 can be solved by performing antibacterial sterilization through oxidation reaction. Meanwhile, the invention also introduces chitosan to modify polypropylene together, the amino group contained in the chitosan interacts or chelates with zinc to form an effective filter medium, and further performs antibacterial sterilization through the interaction of electrostatic attraction and the surface residue of the negatively charged microbial cell, thereby improving the antibacterial and antiviral performances of the filter material.
2. The reusable antiviral mask provided by the invention is made of the ZnO/chitosan/ZIF-8-containing modified polypropylene filter material, has the functions of blocking dust and microorganisms, can be used for performing antibacterial sterilization by destroying bacterial cells or virus envelopes, has hydrophobicity and high-temperature stability, can be used for cleaning and sterilizing high-temperature viruses, realizes repeated use, and overcomes the problems of the existing masks.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of the ZnO/chitosan/ZIF-8 mask filter prepared in example 1 of the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) image of the ZnO/chitosan/ZIF-8 mask filter prepared in example 2 of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the ZnO/chitosan/ZIF-8 mask filter prepared in example 3 of the present invention;
FIG. 4 is a Fourier Infrared Spectroscopy (FTIR) chart of the ZnO/chitosan/ZIF-8 mask filter prepared in example 3 of the present invention;
FIG. 5 is a schematic cross-sectional view of a reusable antiviral mask of the present invention;
fig. 6 is a schematic view of the front structure of the reusable antiviral mask of the present invention.
The labels in the figure are: 1 is an outer non-woven fabric layer, 2 is a middle filter layer, 3 is an inner non-woven fabric layer, 4 is a nose clip, and 5 is an ear band.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings.
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
A method for modifying polypropylene by combining ZnO/chitosan/ZIF-8 is characterized by comprising the following steps:
s1, uniformly mixing a designed amount of soluble zinc salt aqueous solution and acetic acid aqueous solution, adding a certain amount of chitosan, and uniformly stirring and reacting at 50-70 ℃ for 4-8h to obtain a mixed solution;
s2, adding a strong base aqueous solution into the mixed solution, and uniformly stirring for 0.5-2h at 50-70 ℃;
s3, completely immersing the polypropylene in the mixed solution of S2, standing for a certain time at 50-70 ℃, taking out, washing with an organic solvent and deionized water respectively, and drying at 100-130 ℃ for 8-15h to obtain ZnO/chitosan modified polypropylene;
s4, adding imidazole salt and soluble zinc salt with designed amount into the mixed solution of methanol and water, and uniformly stirring for 1-3 h at 50-70 ℃;
s5, completely immersing the ZnO/chitosan modified polypropylene in the mixed solution of S4, standing for a certain time at 50-70 ℃, taking out, washing with an organic solvent, and drying at 70-100 ℃ for 8-15h to obtain the ZnO/chitosan/ZIF-8 combined modified polypropylene.
In the above method, the soluble zinc salt is preferably zinc acetate dihydrate, hexahydrate, and zinc nitrate or zinc chloride, and the imidazolium salt is preferably benzimidazole or 2-methylimidazole. In S1, the concentration of the soluble zinc salt aqueous solution is 0.5-5mmol/L, the volume percentage of acetic acid in the acetic acid aqueous solution is 0.5-1.5%, and the specific concentration is selected according to actual needs. In S2, the aqueous solution of a strong alkali is preferably an aqueous solution of sodium hydroxide, and the concentration thereof is1 to 10 mmol/L. In S4, the mass ratio of the imidazole salt to the soluble zinc salt is (0.5-5): (0.2-2), wherein the volume ratio of the methanol to the water in the mixed solution of the methanol and the water is (5-9) to 1.
To better illustrate and practice the invention, specific examples are set forth below, and the filter characterization analysis methods used in the following examples are as follows:
1. scanning Electron Microscope (SEM) testing: a Hitachi S-4800 type scanning electron microscope manufactured by Hitachi, Japan;
2. fourier infrared spectroscopy (FTIR) test: the Nicolet IS10 infrared spectrometer manufactured by Nicol corporation of NyGao USA IS used;
in example 4, the mask recycling performance test method was as follows:
the used masks are subjected to high-temperature virus killing treatment (at 130 ℃ for 12 h). And (3) respectively testing the filtration efficiency, the airflow resistance, the total bacterial colony count and the total fungal colony count by taking the mask which is not worn with a new mask, worn for 1 time after high-temperature sterilization and the mask worn for 2 times after high-temperature sterilization.
Example 1
A preparation method of a ZnO/chitosan/ZIF-8 combined modified polypropylene melt-blown non-woven fabric mask filter material comprises the following steps:
s1, uniformly mixing 30mL of zinc acetate dihydrate water solution with the concentration of 3mmol/L and 30mL of acetic acid water solution with the volume percentage of 1%, adding 0.1g of chitosan, and uniformly stirring and reacting at 60 ℃ for 6 hours;
s2, adding 50mL of sodium hydroxide aqueous solution with the concentration of 6mmol/L into the mixed solution of S1 by using a dropper, keeping stirring in the process, and uniformly stirring for 1h at 60 ℃ by magnetic stirring;
s3, completely immersing the commercial polypropylene melt-blown non-woven fabric into the mixed solution of S2, standing at 60 ℃ for 16 hours, taking out, washing with absolute ethyl alcohol and deionized water for three times respectively, and drying at 120 ℃ for 12 hours to obtain the ZnO/chitosan modified polypropylene melt-blown non-woven fabric mask filter material;
s4, adding 0.6g of 2-methylimidazole and 0.3g of zinc acetate dihydrate into 50mL of mixed solution with the volume ratio of methanol to water being 7:1, keeping stirring in the process, and uniformly stirring for 2 hours at 60 ℃ by magnetic force;
s5, completely immersing the ZnO/chitosan modified polypropylene melt-blown non-woven fabric mask filter material obtained in the step S3 in the mixed solution of S4, standing at 60 ℃ for 8 hours, taking out, washing with methanol for three times, and drying at 80 ℃ for 12 hours to obtain the ZnO/chitosan/ZIF-8 combined modified polypropylene melt-blown non-woven fabric mask filter material.
The mask filter obtained as described above was subjected to Scanning Electron Microscope (SEM) test to obtain the results shown in fig. 1, and as can be seen from fig. 1, the mask filter of the present invention was composed of fibers having an average diameter of 10 μm, and the fiber surface was unevenly coated with much ZnO due to the long first immersion time.
Example 2
A preparation method of a ZnO/chitosan/ZIF-8 combined modified polypropylene melt-blown non-woven fabric mask filter material comprises the following steps:
s1, uniformly mixing 30mL of zinc acetate dihydrate water solution with the concentration of 2mmol/L and 30mL of acetic acid water solution with the volume percentage of 1%, adding 0.1g of chitosan, and uniformly stirring and reacting at 60 ℃ for 6 hours;
s2, adding 50mL of sodium hydroxide aqueous solution with the concentration of 6mmol/L into the mixed solution of S1 by using a dropper, keeping stirring in the process, and uniformly stirring for 1h at 60 ℃ by magnetic stirring;
s3, completely immersing the commercial polypropylene melt-blown non-woven fabric into the mixed solution of S2, standing at 60 ℃ for 8 hours, taking out, washing with absolute ethyl alcohol and deionized water for three times respectively, and drying at 120 ℃ for 12 hours to obtain the ZnO/chitosan modified polypropylene melt-blown non-woven fabric mask filter material;
s4, adding 2g of 2-methylimidazole and 1g of zinc acetate dihydrate into 50mL of mixed solution with the volume ratio of methanol to water being 7:1, keeping stirring in the process, and uniformly stirring for 2 hours at 60 ℃ by magnetic stirring;
s5, completely immersing the ZnO/chitosan modified polypropylene melt-blown non-woven fabric mask filter material obtained in the step S3 in the mixed solution of S4, standing at 60 ℃ for 12 hours, taking out, washing with methanol for three times, and drying at 80 ℃ for 12 hours to obtain the ZnO/chitosan/ZIF-8 combined modified polypropylene melt-blown non-woven fabric mask filter material.
The mask filter obtained as described above was subjected to Scanning Electron Microscope (SEM) tests to obtain the results shown in fig. 2, and as can be seen from fig. 2, the mask filter of the present invention was composed of fibers having an average diameter of 10 μm, and the surfaces of the fibers were unevenly coated with ZIF-8 due to the long secondary soaking time.
Example 3
A preparation method of a ZnO/chitosan/ZIF-8 combined modified polypropylene melt-blown non-woven fabric mask filter material comprises the following steps:
s1, uniformly mixing 30mL of zinc acetate dihydrate water solution with the concentration of 2.5mmol/L and 30mL of acetic acid water solution with the volume percentage of 1%, adding 0.2g of chitosan, and uniformly stirring and reacting at 60 ℃ for 6 hours;
s2, adding 50mL of sodium hydroxide aqueous solution with the concentration of 5mmol/L into the mixed solution of S1 by using a dropper, keeping stirring in the process, and uniformly stirring for 1h at 60 ℃ by magnetic stirring;
s3, completely immersing the commercial polypropylene melt-blown non-woven fabric into the mixed solution of S2, standing at 60 ℃ for 12 hours, taking out, washing with absolute ethyl alcohol and deionized water for three times respectively, and drying at 120 ℃ for 12 hours to obtain the ZnO/chitosan modified polypropylene melt-blown non-woven fabric mask filter material;
s4, adding 2g of 2-methylimidazole and 0.5g of zinc acetate dihydrate into 50mL of mixed solution with the volume ratio of methanol to water being 8:1, keeping stirring in the process, and uniformly stirring for 2 hours at 60 ℃ by magnetic stirring;
s5, completely immersing the ZnO/chitosan modified polypropylene melt-blown non-woven fabric mask filter material obtained in the step S3 in the mixed solution of S4, standing at 60 ℃ for 12 hours, taking out, washing with methanol for three times, and drying at 80 ℃ for 12 hours to obtain the ZnO/chitosan/ZIF-8 combined modified polypropylene melt-blown non-woven fabric mask filter material.
The mask filter material obtained above was tested by Scanning Electron Microscope (SEM) to obtain the results shown in fig. 3, and as can be seen from fig. 3, the mask filter material of the present invention is composed of fibers having an average diameter of 10 μm, and since the concentrations of the first and second soaking reactants and the soaking time are appropriate, the fiber surfaces are uniformly coated with ZnO and ZIF-8. Fourier infrared spectroscopy (FTIR) tests are shown in FIG. 4, and further show that ZnO, chitosan and ZIF-8 are uniformly distributed on the surface of the modified polypropylene melt-blown non-woven fabric fibers.
Example 4
The utility model provides a repeatedly usable's anti-virus gauze mask, as shown in fig. 5 and fig. 6, anti-virus gauze mask includes gauze mask main part and accessory component, gauze mask main part is formed by the 3 stack combinations of the non-woven fabrics layer of outer non-woven fabrics layer 1, filter layer 2 and inlayer, the accessory component includes nose clip 4 and ear belt 5, the upper end of gauze mask main part is located to nose clip 4, the both sides department of gauze mask main part is located to ear belt 5. Further, a non-woven fabric layer of an inner layer and a non-woven fabric layer of an outer layer are prepared from polypropylene, the ZnO/chitosan/ZIF-8 combined modified polypropylene melt-blown non-woven fabric mask filter material obtained in example 3 is used for preparing the filter layer 2, the functional layers are cut into the same size and then are sequentially overlapped, then a nose clip is placed above the inside of the overlapped layer, the periphery of each functional layer is pressed or connected by ultrasonic electric welding, so that the functional layers are combined to form a mask main body part, and then ear bands are sewn or bonded on two sides of the mask main body part, so that the reusable antivirus mask is obtained.
The mask was subjected to a performance test, and the test results are shown in table 1:
TABLE 1 anti-virus mask Performance test results
As shown in Table 1, when the anti-virus mask is used for the first time, the filtering efficiency reaches 97.35%, the total number of bacterial colonies and the total number of fungal colonies are only 18cfu/g, the anti-virus mask has excellent antibacterial filtering performance, and meanwhile, as the filter material contains ZIF-8, the anti-virus performance of the anti-virus mask is higher than that of a common anti-virus mask. Furthermore, after 1 and 2 times of sterilization, although the filtering effect is reduced and the total number of bacterial colonies and the total number of fungal colonies are increased, the filtering efficiency is more than 95%, the total number of bacterial colonies is less than 200cfu/g, and the total number of fungal colonies is less than 100cfu/g, the mask still has excellent antibacterial filtering performance, in addition, after more than 3 times of sterilization (data not shown), the filtering efficiency of the mask is not obviously reduced, the total number of bacterial colonies is always less than 200cfu/g, and the total number of fungal colonies is always less than 100 cfu/g. Therefore, the antivirus mask can be repeatedly used after being sterilized, and the defect that the traditional mask cannot be repeatedly used is overcome.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.
Claims (10)
1. A method for modifying polypropylene by combining ZnO/chitosan/ZIF-8 is characterized by comprising the following steps:
s1, uniformly mixing a designed amount of soluble zinc salt aqueous solution and acetic acid aqueous solution, adding a certain amount of chitosan, and uniformly stirring and reacting at 50-70 ℃ for 4-8h to obtain a mixed solution;
s2, adding a strong base aqueous solution into the mixed solution, and uniformly stirring for 0.5-2h at 50-70 ℃;
s3, completely immersing the polypropylene in the mixed solution of S2, standing for a certain time at 50-70 ℃, taking out, washing with an organic solvent and deionized water respectively, and drying at 100-130 ℃ for 8-15h to obtain ZnO/chitosan modified polypropylene;
s4, adding imidazole salt and soluble zinc salt with designed amount into the mixed solution of methanol and water, and uniformly stirring for 1-3 h at 50-70 ℃;
s5, completely immersing the ZnO/chitosan modified polypropylene in the mixed solution of S4, standing for a certain time at 50-70 ℃, taking out, washing with an organic solvent, and drying at 70-100 ℃ for 8-15h to obtain the ZnO/chitosan/ZIF-8 combined modified polypropylene.
2. The method of co-modifying polypropylene with ZnO/chitosan/ZIF-8 of claim 1, wherein the soluble zinc salt is zinc acetate dihydrate, zinc nitrate hexahydrate, or zinc chloride.
3. The method for the ZnO/chitosan/ZIF-8 co-modified polypropylene of claim 1, wherein the imidazolium salt is benzimidazole or 2-methylimidazole.
4. The method for co-modifying polypropylene according to claim 1, wherein the concentration of the aqueous solution of soluble zinc salt in S1 is 0.5 to 5mmol/L, and the volume percentage of acetic acid in the aqueous solution of acetic acid is 0.5 to 1.5%.
5. The method for co-modifying polypropylene with ZnO/chitosan/ZIF-8 as set forth in claim 1, wherein the aqueous solution of a strong base is an aqueous solution of sodium hydroxide with a concentration of 1 to 10mmol/L in S2.
6. The method for co-modifying polypropylene with ZnO/chitosan/ZIF-8 according to claim 1, wherein the standing time in S3 and S5 is 6-18 h.
7. The method for jointly modifying polypropylene according to claim 1, wherein the mass ratio of imidazole salt to soluble zinc salt in S4 is (0.5-5): (0.2-2).
8. A reusable polypropylene mask filter material, which is characterized by comprising a polypropylene material obtained by the ZnO/chitosan/ZIF-8 combined polypropylene modification method according to any one of claims 1 to 7, and using the polypropylene material as a polypropylene non-woven mask filter material.
9. A reusable antiviral mask, wherein the filter layer of said antiviral mask is made of the polypropylene mask filter of claim 8.
10. The antiviral mask as claimed in claim 9, wherein said antiviral mask comprises a mask body part formed by stacking an outer non-woven fabric layer, a filter layer and an inner non-woven fabric layer, and attachment members comprising a nose clip provided at an upper end of the mask body part and ear bands provided at both sides of the mask body part.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011001876.XA CN112126154B (en) | 2020-09-22 | 2020-09-22 | Method for modifying polypropylene by combining ZnO/chitosan/ZIF-8, filter material and anti-virus mask |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011001876.XA CN112126154B (en) | 2020-09-22 | 2020-09-22 | Method for modifying polypropylene by combining ZnO/chitosan/ZIF-8, filter material and anti-virus mask |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN112126154A true CN112126154A (en) | 2020-12-25 |
| CN112126154B CN112126154B (en) | 2022-11-08 |
Family
ID=73842217
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202011001876.XA Active CN112126154B (en) | 2020-09-22 | 2020-09-22 | Method for modifying polypropylene by combining ZnO/chitosan/ZIF-8, filter material and anti-virus mask |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN112126154B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778647A (en) * | 2021-01-27 | 2021-05-11 | 南京西利泰克实验科技有限公司 | High polymer material prepared from tailings sand of iron ore and copper ore and preparation method thereof |
| CN112973277A (en) * | 2021-03-17 | 2021-06-18 | 济南大学 | Preparation and application of hyperbranched high-molecular polymer filter pad |
| CN113774506A (en) * | 2021-08-26 | 2021-12-10 | 东华大学 | Preparation method of antiviral micro-nano fiber |
| CN115011037A (en) * | 2022-06-16 | 2022-09-06 | 太原理工大学 | Polypropylene-based photocatalytic antibacterial master batch and preparation method and application thereof |
| CN118065055A (en) * | 2024-03-18 | 2024-05-24 | 广东标典无纺布科技有限公司 | Non-woven fabric for high-filterability air conditioner and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103704908A (en) * | 2014-01-16 | 2014-04-09 | 青岛海百合生物技术有限公司 | Fine-particle-proof mask with chitosan and nano-zinc oxide and manufacturing method of fine-particle-proof mask |
| CN110777537A (en) * | 2019-11-04 | 2020-02-11 | 北京理工大学 | ZIF-8/non-woven fabric composite material and preparation method thereof |
-
2020
- 2020-09-22 CN CN202011001876.XA patent/CN112126154B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103704908A (en) * | 2014-01-16 | 2014-04-09 | 青岛海百合生物技术有限公司 | Fine-particle-proof mask with chitosan and nano-zinc oxide and manufacturing method of fine-particle-proof mask |
| CN110777537A (en) * | 2019-11-04 | 2020-02-11 | 北京理工大学 | ZIF-8/non-woven fabric composite material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| KRISHNAVENI RAJENDRAN, ET AL.: "Industrial method of cotton fabric finishing with chitosan-ZnO composite for anti-bacterial and thermal stability", 《INDUSTRIAL CROPS AND PRODUCTS》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112778647A (en) * | 2021-01-27 | 2021-05-11 | 南京西利泰克实验科技有限公司 | High polymer material prepared from tailings sand of iron ore and copper ore and preparation method thereof |
| CN112973277A (en) * | 2021-03-17 | 2021-06-18 | 济南大学 | Preparation and application of hyperbranched high-molecular polymer filter pad |
| CN112973277B (en) * | 2021-03-17 | 2022-06-14 | 济南大学 | Preparation and application of hyperbranched high-molecular polymer filter pad |
| CN113774506A (en) * | 2021-08-26 | 2021-12-10 | 东华大学 | Preparation method of antiviral micro-nano fiber |
| CN115011037A (en) * | 2022-06-16 | 2022-09-06 | 太原理工大学 | Polypropylene-based photocatalytic antibacterial master batch and preparation method and application thereof |
| CN115011037B (en) * | 2022-06-16 | 2023-09-26 | 太原理工大学 | Polypropylene-based photocatalytic antibacterial master batch and preparation method and application thereof |
| CN118065055A (en) * | 2024-03-18 | 2024-05-24 | 广东标典无纺布科技有限公司 | Non-woven fabric for high-filterability air conditioner and preparation method thereof |
| CN118065055B (en) * | 2024-03-18 | 2024-09-06 | 广东标典无纺布科技有限公司 | Non-woven fabric for high-filterability air conditioner and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN112126154B (en) | 2022-11-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN112126154B (en) | Method for modifying polypropylene by combining ZnO/chitosan/ZIF-8, filter material and anti-virus mask | |
| CN108425238B (en) | Preparation method of antibacterial graphene non-woven fabric with low resistance and high filtering efficiency for mask | |
| CN103566776B (en) | Photocatalytic inorganic nanoparticle/polydopamine/polymer self-cleaning composite film and preparation method thereof | |
| CN101362035B (en) | Expanded polytetrafluoroethylene bacteriostatic coated filter material and production method thereof | |
| CN108993167A (en) | A kind of preparation and application of the Electrospun nano-fibers air filting material of antibacterial | |
| CN110508163A (en) | A kind of MOF film of crosslinked polyethylenimine and preparation method thereof | |
| CN103410001B (en) | Preparation method of self-cleaning cotton fabric based on light-induced polymer free radicals for degrading pollutants | |
| CN112056313B (en) | Method for aqueous phase synthesis of nano Cu-MOF (copper-metal organic framework) bacteriostatic agent | |
| CN101070680A (en) | Binuclear metal phthalolyanin carrier fiber material for eliminating formaldehyde and preparing method | |
| CN111733596B (en) | Noble metal antibacterial disinfectant, noble metal-loaded antibacterial mask and preparation method thereof | |
| CN112808026A (en) | Nanofiber film and preparation method and application thereof | |
| CN111513388A (en) | Nano-silver non-woven fabric mask | |
| US20220034025A1 (en) | Coated substrates and articles with anti-viral properties, and fabrication processes | |
| CN212818617U (en) | Gas filtration structure and gas filtration article having a coating | |
| CN113663417A (en) | Gauze material, device containing gauze material, preparation method and application of gauze material | |
| CN113477262A (en) | Preparation method and application of silver chromate/zinc ferrite fibrous composite photocatalyst | |
| CN114849762A (en) | g-C 3 N 4 /BiOI/Ag 2 CrO 4 Preparation method and application of ternary heterojunction photocatalyst | |
| CN113769481A (en) | Organic-inorganic hybrid air filtration protective material with multilevel structure | |
| JP2011213719A (en) | Antiviral agent and method of manufacturing the same | |
| CN110250618A (en) | Universal mask | |
| CN114645375A (en) | Antibacterial silver salt/g-C3N4Application of composite nanofiber membrane | |
| CN114232341B (en) | Metal ion coordination and adsorption antibacterial and antiviral mask main body material, preparation method thereof and mask | |
| CN109092054A (en) | A kind of gas phase in-situ oxidation preparation method of Mn-Ce-Fe-Co quaternary catalytic function PPS filtrate | |
| CN112244384B (en) | Multifunctional reusable mask for efficient filtration, adsorption and sterilization and preparation method thereof | |
| CN117209781B (en) | High-performance photocatalytic metal organic framework antibacterial material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |