CN113975901A - Preparation method of graphene composite antiviral powder and antibacterial and antiviral air filter material - Google Patents

Preparation method of graphene composite antiviral powder and antibacterial and antiviral air filter material Download PDF

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CN113975901A
CN113975901A CN202111411632.3A CN202111411632A CN113975901A CN 113975901 A CN113975901 A CN 113975901A CN 202111411632 A CN202111411632 A CN 202111411632A CN 113975901 A CN113975901 A CN 113975901A
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antiviral
powder
graphene composite
graphene
antibacterial
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CN113975901B (en
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徐荣
张春明
冉伟
李章鹏
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Juzhi Suzhou Nano Technology Co ltd
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Juzhi Suzhou Nano Technology Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0001—Making filtering elements
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
    • A01N59/16—Heavy metals; Compounds thereof
    • A01N59/20—Copper
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/08—Filter cloth, i.e. woven, knitted or interlaced material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • 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

Abstract

The invention provides a preparation method of graphene composite antiviral powder and an antibacterial and antiviral air filter material, which comprises the following steps: preparing oxidized and reduced graphene oxide suspension liquid in sequence; preparing activated reduced graphene oxide; preparing silver-copper loaded graphene composite powder; in-situ symbiosis is carried out on the prepared Zn compound mother liquor and the silver-copper-loaded graphene composite powder to obtain graphene composite antiviral powder; secondly, the method comprises the following steps: adding a dispersing agent and a surface modifier into the powder to prepare graphene composite antiviral slurry; vacuumizing, melting and extruding the slurry and PP resin powder to prepare the high-concentration graphene composite antiviral master batch; and finally: carrying out high-temperature spinning on the high-concentration graphene composite antiviral master batch, PP resin and electret master batch to prepare graphene composite antibacterial antiviral melt-blown fabric; and carrying out modular composite design on the melt-blown cloth and the framework cloth, and assembling to obtain the graphene composite antibacterial and antiviral air filter material. The antibacterial and antiviral air filter material has good interception and killing effects on bacteria, mites and viruses.

Description

Preparation method of graphene composite antiviral powder and antibacterial and antiviral air filter material
Technical Field
The invention belongs to the technical field of bacteriostasis and antivirus, and particularly relates to graphene composite antivirus powder and a preparation method of a bacteriostasis and antivirus air filter material.
Background
Graphene (Graphene) is sp2The hybridized and connected carbon atoms are tightly stacked to form a new material with a single-layer two-dimensional honeycomb lattice structure, and the new material has excellent optical, electrical and mechanical properties. Generally, the size of the small bacteria is only 0.2 micrometer, which is about 600 times that of graphene, the bacteria can be cut through cell walls to die when moving on the sharp nanoscale two-dimensional material, and the graphene can also destroy the cell membranes by directly extracting phospholipid molecules on the cell membranes on a large scale so as to kill the bacteria.
Silver antibacterial agents have been used since ancient times, and people have long recognized that silver has an antibacterial effect. The nano silver causes the common components of the microorganisms to be damaged or generate functional disorder through contact reaction, and silver ions can also damage electronic transmission systems, respiratory systems and substance transmission systems of the microorganisms. Copper also has a strong bactericidal function, and when the copper surface directly interacts with the bacterial outer membrane, the bacterial outer membrane is broken through two ways of 'short circuit effect' to destroy the 'membrane potential' of the bacteria and 'oxidation destruction' formed by 'aerobic impact' of free single copper ions or copper molecules on the cell membrane. Moreover, copper ions can destroy viral DNA \ RNA and prevent their metabolism. The nano zinc oxide particles have large specific surface area, can utilize absorbed ultraviolet light or visible light to carry out photocatalytic degradation on organic matters adsorbed to the surface, and simultaneously have strong bactericidal activity. However, a simple graphene structure or a simple silver, copper or zinc system has a very good antibacterial function, but has a limited antiviral ability. Obviously, the high requirements of the modern society on both antibacterial and antiviral functions are difficult to meet, and a more efficient novel material with both antibacterial and antiviral functions is urgently needed in the market.
In addition, with the improvement of living standard, people have higher and higher requirements on air quality. The traditional air filter material only has a partial interception function on bacterial viruses, and the intercepted bacterial viruses still have activity to cause secondary pollution. Therefore, some antibacterial and antiviral finishing liquids containing organic antibacterial agents, inorganic antibacterial agents or organic-inorganic composite antibacterial agents appear on the market, and the antibacterial and antiviral functions are endowed to the filter materials by carrying out after-finishing processing on the after-finishing liquids and PET or PA in the air filter materials. However, the post-finishing filter material has the inherent defect that the bacteriostatic and antiviral components are easy to fall off, and has poor weather resistance and unstable bacteriostatic and antiviral properties. An air filter material with more stable and reliable antibacterial and antiviral performances and good weather resistance is urgently needed in the market.
In order to solve the two problems, the method firstly controls the current and the energy of an electron accelerator to emit electron beams so as to excite hydrated electrons, and the hydrated electrons and oxygen-containing groups on the surface layer of the graphene oxide perform chemical reaction so as to prepare the reduced graphene oxide; then anchoring silver and copper ions to the activated reduced graphene oxide (rGO) through pi bonds to form rGO-silver/copper composite materials, wherein the materials strongly interact with negatively charged bacteria to greatly improve antibacterial activity; simultaneously, zinc ions, 2, 6-pyridinedicarboxylic acid and 4-aminopyridine are used to form C by controlling certain conditions52H38N10O24Zn2The novel complex ligand reduces the polarity through the chelation of zinc and organic ligand, increases the lipophilicity, and greatly increases the capability of the novel complex ligand to permeate cell membranes, thereby enhancing the antibacterial activity of the material. Moreover, the novel complex can also be compounded with silver/copper ions and the like on the activated reduced graphene oxide to form a synergistic enhancementThe antibacterial and antiviral activity of the graphene composite powder is further improved, and finally the efficient graphene composite antiviral powder composite material is obtained. And secondly, further dispersing and carrying out surface modification on the basis of the graphene composite antiviral powder to prepare slurry, then extruding the slurry and a PP (polypropylene) base material screw to obtain a graphene composite antiviral master batch through wet granulation, carrying out high-temperature melt-blowing on the master batch and carrying out composite processing with a framework, and finally obtaining the air filter material with more stable antibacterial and antiviral properties, more reliability and good weather resistance.
Disclosure of Invention
The invention provides graphene composite antiviral powder and a preparation method thereof, and simultaneously provides an antibacterial and antiviral air filter material and a preparation method thereof, so as to solve the problem that the market urgently needs a more efficient antibacterial and antiviral material and an air filter material with more stable antibacterial and antiviral properties, more reliability and good weather resistance, which are provided by the background technology, and the preparation method comprises the following steps:
1) graphene oxide suspension: and mixing the graphene oxide powder with deionized water, and stirring at a high speed for 30-60 min to prepare a uniformly dispersed graphene oxide suspension.
2) Reducing the graphene oxide suspension: mixing the graphene oxide suspension with acetone, putting the mixed solution into a sealed bag filled with nitrogen, controlling beam intensity and energy of an electron accelerator, irradiating within a certain range of dose, then centrifugally washing with deionized water, and adding deionized water according to the mass ratio of graphene oxide powder to deionized water of 0.5:100 to prepare the reduced graphene oxide suspension.
3) Activating the stock solution: the preparation concentration is 1-2 g/L PdCl2，15～20g/LSnCl260-100 ml/L HClO mixed activation stock solution.
4) Activating, reducing and oxidizing a graphene suspension: ultrasonically mixing the reduced graphene oxide suspension and the activation stock solution according to a certain mass ratio, aging, centrifugally separating, and finally adding deionized water to prepare the activated reduced graphene oxide suspension with a certain concentration.
5) Cetyl trimethyl ammonium bromide dispersion of chitosan: preparing a methanol aqueous solution of 2 wt% of hexadecyl trimethyl ammonium bromide (wherein the mass ratio of methanol to deionized water is 1: 2), adding chitosan under ultrasonic stirring to prepare a hexadecyl trimethyl ammonium bromide dispersion liquid of 1 wt% of chitosan, and continuing to perform ultrasonic stirring for 30-60 min.
6) Silver-copper composite urea solution: silver nitrate (AgNO) with the preparation concentration of 0.75-1.5 mol/L3) 1.5 to 2mol/L copper nitrate (Cu (NO)3)2·6H2O) and 1.5-2.5 mol/L urea (CH)4N2O), and stirring for 30-60 min.
7) The preparation method comprises the following steps of (1) activating and reducing graphene dispersion liquid by silver-copper composite urea: mixing the activated reduced graphene oxide suspension and the hexadecyl trimethyl ammonium bromide dispersion liquid of chitosan according to a certain mass ratio for 15min under ultrasonic, then adding the silver-copper composite urea solution under high-speed stirring, and mixing for 4 h.
8) Loading silver-copper graphene composite powder: and transferring the mixed solution into a high-pressure reaction kettle, controlling the hydrothermal reaction temperature to be 150-220 ℃ and the hydrothermal reaction time to be 6-48 h, cooling, performing vacuum filtration, alternately washing with absolute ethyl alcohol and deionized water, and drying at 105 ℃.
9) Zn complex formulation mother liquor: preparing a mixed aqueous solution of 2, 6-pyridinedicarboxylic acid and 4-aminopyridine with a certain concentration, heating and stirring for a certain time, and then adding the mixed solution into ZnCl with a certain concentration2In aqueous solution, and then refluxed at 100 ℃ for a certain period of time.
10) Graphene composite antiviral powder: mixing the silver-copper-loaded graphene composite powder with a Zn compound mother liquor according to a mass ratio of 1-2: 10, mixing and stirring at room temperature for 2-4 h, standing for 7-28 h, then carrying out vacuum filtration, washing with deionized water, and carrying out vacuum drying at 80 ℃.
11) Graphene composite antiviral slurry: and (3) adding the powder prepared in the step (10) into an aqueous or alcoholic solution of a dispersing agent and a surface modifier, and grinding to prepare the graphene composite antiviral slurry.
12) Graphene composite antiviral master batch: and (3) pumping the graphene composite antiviral slurry prepared in the step (11) into a screw extruder through a metering pump, carrying out melt extrusion with PP resin powder at 220-260 ℃, and vacuumizing to prepare the graphene composite antiviral master batch.
13) Compounding, namely, graphene composite antibacterial antiviral melt-blown fabric: and (3) uniformly mixing the master batch prepared in the step (12) with PP resin and electret master batch, and performing high-temperature melt spinning to obtain the graphene composite antibacterial antiviral melt-blown fabric.
14) Graphene composite antibacterial and antiviral air filter material: and carrying out compound processing on the graphene compound antibacterial and antiviral melt-blown cloth and the PET framework to obtain the graphene compound antibacterial and antiviral air filter material.
Preferably, in the step (1), the graphene oxide powder: the mass ratio of the deionized water is 0.1-3: 100.
preferably, the mass ratio of the graphene oxide suspension to acetone in the step (2) is 1: 1-2; the beam intensity of the electron accelerator is 0.5-1.0 mA, and the energy is 1.0-2.0 MeV; the irradiation dose at room temperature is 2.5-7.5 kGy.
Preferably, the mass ratio of the reduced graphene oxide suspension to the activation stock solution in the step (4) is 1: 1-2, ultrasonically mixing for 2-4 h, and then aging for 6-12 h, wherein the concentration of the prepared activated reduced graphene oxide suspension is 0.1-0.2%.
Preferably, the mass ratio of the graphene oxide suspension subjected to activation reduction in the step (7), the cetyl trimethyl ammonium bromide dispersion liquid of the polysaccharide and the silver-copper composite urea solution is 2.5-3.5: 0.5-1.5: 0.5 to 1.5.
Preferably, in the step (9), 0.1-0.2 mol/L2, 6-pyridinedicarboxylic acid aqueous solution and 0.1-0.2 mol/L4-aminopyridine aqueous solution are heated and stirred at 40-90 ℃ for 1-2 h, and then 0.1-0.2 mol/L ZnCl is added2The aqueous solution is refluxed for 12 to 100 hours at the temperature of 100 ℃.
Preferably, in the step (11), the mass ratio of the graphene composite antiviral powder to the deionized water or alcohol to the dispersant to the surface modifier is 20-60: 40-80: 0.2-0.5%: 0.2-0.5%; the dispersing agent is sodium polyacrylate or carboxymethyl cellulose; the surface modifier is vinyl triethoxysilane or vinyl trimethoxysilane.
Preferably, the mass ratio of the graphene composite antiviral slurry to the PP resin powder in the step (12) is 5-30: 100.
preferably, in the step (13), the mass ratio of the graphene composite antiviral master batch to the PP resin to the electret master batch is 5-20: 100: 1-3, and the highest processing temperature range is 200-280 ℃.
Compared with the prior art, the invention has the following beneficial effects:
the invention aims to provide graphene composite antiviral powder and a preparation method thereof, and simultaneously provides an antibacterial antiviral air filter material and a preparation method thereof, compared with the prior art, the graphene composite antiviral air filter material has the following beneficial effects:
1) and the electron beam is adopted to excite hydrated electrons to control the reduction degree of the graphene surface layer, so that the fine modification of the surface is realized, and the chemical bond combination of metal ions is facilitated.
2) The antibacterial and antiviral capability of the composite material is improved by the synergistic enhancement effect formed by the activated and reduced graphene oxide, silver ions and copper ions.
3) C prepared simultaneously52H38N10O24Zn2The novel zinc ion complex ligand can also form a synergistic enhancement effect with silver and copper ions on the activated and reduced graphene oxide, so that the antibacterial and antiviral activity of the composite material is further enhanced, the using amount of the graphene composite antiviral material can be greatly reduced, and the antibacterial and antiviral efficiency is good at an extremely low concentration.
4) On the basis of synthesizing the graphene composite antiviral powder, the nano slurry prepared by grinding, dispersing and surface control can be applied to films with transparent requirements such as PET/PMMA/PVC and the like, and the application range is greatly expanded.
5) The graphene composite antibacterial and antiviral air filter material prepared by the high-temperature melt spraying of the graphene composite antiviral material is subjected to composite processing, and has better weather resistance and stability compared with antibacterial and antiviral air filter materials prepared by after-finishing, spraying and dipping processes on the market.
Drawings
FIG. 1 is an SEM image of a graphene composite antiviral powder according to an embodiment of the invention
FIG. 2 is a mapping chart of silver element in graphene composite antiviral powder according to an embodiment of the present invention
FIG. 3 is a mapping chart of zinc element in the graphene composite antiviral powder according to the embodiment of the invention
FIG. 4 is a mapping chart of copper element in the graphene composite antiviral powder according to the embodiment of the invention
FIG. 5 is a particle size distribution diagram of graphene-II composite antiviral slurry according to an embodiment of the present invention
FIG. 6 is an SEM image of a three-graphene composite antiviral paste according to an embodiment of the invention
FIG. 7 is a particle size distribution diagram of a three-graphene composite antiviral slurry according to an embodiment of the present invention
FIG. 8 is a particle size distribution diagram of a four-graphene composite antiviral slurry according to an embodiment of the present invention
FIG. 9 is a SEM image of the cross section of the four-graphene composite antiviral master batch in the embodiment of the invention
FIG. 10 is an SEM image of a tetra-graphene composite bacteriostatic and antiviral air filter material according to an embodiment of the invention
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example one
In this embodiment, the steps of the present invention are as follows:
1) graphene oxide suspension: and mixing the graphene oxide powder and deionized water according to the mass ratio of 0.1:100, and stirring at a high speed for 30min to prepare the uniformly dispersed graphene oxide suspension.
2) Reducing the graphene oxide suspension: mixing a graphene oxide suspension and acetone in a mass ratio of 1:1, mixing, putting the mixed solution into a sealed bag filled with nitrogen, controlling the beam intensity of an electron accelerator to be 0.5mA and the energy to be 1.0MeV, controlling the irradiation dose to be 2.5kGy, then centrifugally washing with deionized water, adding deionized water according to the mass ratio of graphene oxide powder to the deionized water of 0.5:100, and preparing reduced graphene oxide suspension.
3) Activating the stock solution: the preparation concentration is 1g/L PdCl2，15g/LSnCl260ml/L HClO mixed activation stock solution.
4) Activating, reducing and oxidizing a graphene suspension: and (3) mixing the reduced graphene oxide suspension and the activation stock solution in a mass ratio of 1:1 ultrasonic mixing for 2h, aging for 12h, centrifugal separation, and finally adding deionized water to prepare activated reduced graphene oxide suspension with the concentration of 0.1%.
5) Cetyl trimethyl ammonium bromide dispersion of chitosan: preparing a methanol aqueous solution of 2 wt% of hexadecyl trimethyl ammonium bromide (wherein the mass ratio of methanol to deionized water is 1: 2), adding chitosan under ultrasonic stirring to prepare a hexadecyl trimethyl ammonium bromide dispersion liquid of 1 wt% of chitosan, and continuing ultrasonic stirring for 30 min.
6) Silver-copper composite urea solution: silver nitrate (AgNO) with the preparation concentration of 0.75mol/L3) 1.5mol/L copper nitrate (Cu (NO)3)2·6H2O) and 1.5mol/L Urea (CH)4N2O), stirring for 30 min.
7) The preparation method comprises the following steps of (1) activating and reducing graphene dispersion liquid by silver-copper composite urea: activating reduction graphene oxide suspension with the concentration of 0.1% and hexadecyl trimethyl ammonium bromide dispersion liquid of chitosan are mixed according to the mass ratio of 2.5: mixing for 15min under the ultrasonic condition of 0.5 to obtain activated reduced graphene oxide mixed solution, then adding the silver-copper composite urea solution into the activated reduced graphene oxide mixed solution and the silver-copper composite urea solution in a mass ratio of 3:0.5 under the condition of high-speed stirring, and mixing for 4 h.
8) Loading silver-copper graphene composite powder: and transferring the mixed solution into a high-pressure reaction kettle, controlling the hydrothermal reaction temperature at 150 ℃ for 48 hours, cooling, performing vacuum filtration, alternately washing with absolute ethyl alcohol and deionized water, and drying at 105 ℃.
9) Zn complex formulation mother liquor: preparing 0.1 mol/L2, 6-pyridinedicarboxylic acid aqueous solution and 0.1 mol/L4-aminopyridine mixed aqueous solution, heating and stirring at 80 ℃ for 2h, then adding the mixed solution into 0.1mol/L ZnCl2In aqueous solution, and then refluxed at 100 ℃ for 12 hours.
10) Graphene composite antiviral powder: mixing the silver-copper-loaded graphene composite powder with Zn compound mother liquor in a mass ratio of 1:10, mixing and stirring at room temperature for 2 hours, standing for 7 hours, then carrying out vacuum filtration, washing with deionized water, and carrying out vacuum drying at 80 ℃.
Example two
In this embodiment, the steps of the present invention are as follows:
1) graphene oxide suspension: and mixing the graphene oxide powder and deionized water in a mass ratio of 1:100, and stirring at a high speed for 30min to prepare a uniformly dispersed graphene oxide suspension.
2) Reducing the graphene oxide suspension: mixing a graphene oxide suspension and acetone in a mass ratio of 1: 2, mixing, putting the mixed solution into a sealed bag filled with nitrogen, controlling the beam intensity of an electron accelerator to be 0.7mA and the energy to be 1.4MeV, controlling the irradiation dose to be 5.0kGy, then centrifugally washing with deionized water, adding deionized water according to the mass ratio of the graphene oxide powder to the deionized water of 0.5:100, and preparing the reduced graphene oxide suspension.
3) Activating the stock solution: the prepared concentration is 1.4g/L PdCl2，17g/LSnCl275ml/L HClO.
4) Activating, reducing and oxidizing a graphene suspension: and (3) mixing the reduced graphene oxide suspension and the activation stock solution in a mass ratio of 1: 2, ultrasonic mixing for 4 hours, aging for 6 hours, centrifugal separation, and finally adding deionized water to prepare activated reduced graphene oxide suspension with the concentration of 0.15%.
5) Cetyl trimethyl ammonium bromide dispersion of chitosan: preparing a methanol aqueous solution of 2 wt% of hexadecyl trimethyl ammonium bromide (wherein the mass ratio of methanol to deionized water is 1: 2), adding chitosan under ultrasonic stirring to prepare a hexadecyl trimethyl ammonium bromide dispersion liquid of 1 wt% of chitosan, and continuing to perform ultrasonic stirring for 60 min.
6) Silver-copper composite urea solution: silver nitrate (AgNO) with the preparation concentration of 1.5mol/L3) 1.5mol/L copper nitrate (Cu (NO)3)2·6H2O) and 2.5mol/L urea (CH)4N2O), stirring for 30 min.
7) The preparation method comprises the following steps of (1) activating and reducing graphene dispersion liquid by silver-copper composite urea: activating reduction graphene oxide suspension with the concentration of 0.15% and hexadecyl trimethyl ammonium bromide dispersion liquid of chitosan are mixed according to the mass ratio of 3.5: mixing for 15min under 1.5 ultrasonic waves to obtain an activated reduced graphene oxide mixed solution, then adding a silver-copper composite urea solution into the activated reduced graphene oxide mixed solution and the silver-copper composite urea solution in a mass ratio of 5:1 under high-speed stirring, and mixing for 4 h.
8) Loading silver-copper graphene composite powder: and transferring the mixed solution into a high-pressure reaction kettle, controlling the hydrothermal reaction temperature at 180 ℃ for 36 hours, cooling, performing vacuum filtration, alternately washing with absolute ethyl alcohol and deionized water, and drying at 105 ℃.
9) Zn complex formulation mother liquor: preparing 0.2 mol/L2, 6-pyridinedicarboxylic acid aqueous solution and 0.2 mol/L4-aminopyridine mixed aqueous solution, heating and stirring at 90 ℃ for 1h, then adding the mixed solution into 0.2mol/L ZnCl2In aqueous solution, and then refluxed at 100 ℃ for 50 h.
10) Graphene composite antiviral powder: mixing the silver-copper-loaded graphene composite powder with Zn compound mother liquor in a mass ratio of 2:10, mixing and stirring at room temperature for 2 hours, standing for 28 hours, then carrying out vacuum filtration, washing with deionized water and carrying out vacuum drying at 80 ℃.
11) Graphene composite antiviral slurry: adding the powder prepared in the step (10) into an ethanol solution of sodium polyacrylate and vinyl trimethoxy silane, and grinding to prepare the graphene composite antiviral slurry, wherein the mass ratio of the graphene composite antiviral powder to the ethanol to the sodium polyacrylate to the vinyl trimethoxy silane is 20: 80: 0.2%: 0.4 percent.
12) Graphene composite antiviral master batch: and (3) pumping the graphene composite antiviral slurry prepared in the step (11) into a screw extruder through a metering pump, and performing melt extrusion with PP resin powder at 260 ℃, wherein the mass ratio of the graphene composite antiviral slurry to the PP resin powder is 5: and (100) vacuumizing to obtain the graphene composite antiviral master batch.
13) Compounding, namely, graphene composite antibacterial antiviral melt-blown fabric: mixing the master batch prepared in the step (12) with PP resin and electret master batch according to a mass ratio of 20: 100: 3, uniformly mixing, and carrying out high-temperature melt spinning at 280 ℃ to obtain the graphene composite antibacterial antiviral melt-blown fabric.
14) Graphene composite antibacterial and antiviral air filter material: and carrying out compound processing on the graphene compound antibacterial and antiviral melt-blown cloth and the PET framework to obtain the graphene compound antibacterial and antiviral air filter material.
EXAMPLE III
In this embodiment, the steps of the present invention are as follows:
1) graphene oxide suspension: and mixing the graphene oxide powder and deionized water in a mass ratio of 2:100, and stirring at a high speed for 30-60 min to prepare a uniformly dispersed graphene oxide suspension.
2) Reducing the graphene oxide suspension: mixing a graphene oxide suspension and acetone in a mass ratio of 1: 2, mixing, putting the mixed solution into a sealed bag filled with nitrogen, controlling the beam intensity of an electron accelerator to be 0.8mA and the energy to be 1.8MeV, controlling the irradiation dose to be 5.0kGy, then centrifugally washing with deionized water, adding deionized water according to the mass ratio of the graphene oxide powder to the deionized water of 0.5:100, and preparing the reduced graphene oxide suspension.
3) Activating the stock solution: the prepared concentration is 1.8g/L PdCl2，19g/LSnCl290ml/L HClO.
4) Activating, reducing and oxidizing a graphene suspension: and (3) mixing the reduced graphene oxide suspension and the activation stock solution in a mass ratio of 1: 2 ultrasonic mixing for 2h, aging for 10h, centrifugal separation, and finally adding deionized water to prepare activated reduced graphene oxide suspension with the concentration of 0.15%.
5) Cetyl trimethyl ammonium bromide dispersion of chitosan: preparing a methanol aqueous solution of 2 wt% of hexadecyl trimethyl ammonium bromide (wherein the mass ratio of methanol to deionized water is 1: 2), adding chitosan under ultrasonic stirring to prepare a hexadecyl trimethyl ammonium bromide dispersion liquid of 1 wt% of chitosan, and continuing ultrasonic stirring for 30 min.
6) Silver-copper composite urea solution: silver nitrate (AgNO) with the preparation concentration of 1mol/L3) 1.5mol/L copper nitrate (Cu (NO)3)2·6H2O) and 1.5mol/L Urea (CH)4N2O), stirring for 30 min.
7) The preparation method comprises the following steps of (1) activating and reducing graphene dispersion liquid by silver-copper composite urea: activating reduction graphene oxide suspension with the concentration of 0.15% and hexadecyl trimethyl ammonium bromide dispersion liquid of chitosan are mixed according to the mass ratio of 3:1, mixing for 15min under ultrasonic waves to obtain an activated reduced graphene oxide mixed solution, then adding a silver-copper composite urea solution into the activated reduced graphene oxide mixed solution and the silver-copper composite urea solution in a mass ratio of 4:0.5 under high-speed stirring, and mixing for 4 h.
8) Loading silver-copper graphene composite powder: and transferring the mixed solution into a high-pressure reaction kettle, controlling the hydrothermal reaction temperature at 200 ℃ for 18h, cooling, performing vacuum filtration, alternately washing with absolute ethyl alcohol and deionized water, and drying at 105 ℃.
9) Zn complex formulation mother liquor: preparing 0.1 mol/L2, 6-pyridinedicarboxylic acid aqueous solution and 0.1 mol/L4-aminopyridine mixed aqueous solution, heating and stirring for 2h at 40 ℃, and then adding the mixed solution into 0.1mol/L ZnCl2In aqueous solution, and then refluxed at 100 ℃ for 12 hours.
10) Graphene composite antiviral powder: mixing the silver-copper-loaded graphene composite powder with Zn compound mother liquor in a mass ratio of 2:10, mixing and stirring at room temperature for 2 hours, standing for 7 hours, then carrying out vacuum filtration, washing with deionized water, and carrying out vacuum drying at 80 ℃.
11) Graphene composite antiviral slurry: adding the powder prepared in the step (10) into an aqueous solution of sodium polyacrylate and vinyl triethoxysilane, and grinding to obtain graphene composite antiviral slurry, wherein the mass ratio of the graphene composite antiviral powder to the deionized water to the sodium polyacrylate to the vinyl triethoxysilane is 60: 80: 0.35%: 0.35 percent.
12) Graphene composite antiviral master batch: and (3) pumping the graphene composite antiviral slurry prepared in the step (11) into a screw extruder through a metering pump, and performing melt extrusion with PP resin powder at 220 ℃, wherein the mass ratio of the graphene composite antiviral slurry to the PP resin powder is 20: and (100) vacuumizing to obtain the graphene composite antiviral master batch.
13) Compounding, namely, graphene composite antibacterial antiviral melt-blown fabric: mixing the master batch prepared in the step (12) with PP resin and electret master batch according to a mass ratio of 15: 100: 2, uniformly mixing, and performing melt spinning at the high temperature of 240 ℃ to obtain the graphene composite antibacterial antiviral melt-blown fabric.
14) Graphene composite antibacterial and antiviral air filter material: and carrying out compound processing on the graphene compound antibacterial and antiviral melt-blown cloth and the PET framework to obtain the graphene compound antibacterial and antiviral air filter material.
Example four
In this embodiment, the steps of the present invention are as follows:
1) graphene oxide suspension: and mixing the graphene oxide powder and deionized water in a mass ratio of 3:100, and stirring at a high speed for 60min to prepare a uniformly dispersed graphene oxide suspension.
2) Reducing the graphene oxide suspension: mixing a graphene oxide suspension and acetone in a mass ratio of 1: 2, mixing, putting the mixed solution into a sealed bag filled with nitrogen, controlling the beam intensity of an electron accelerator to be 1.0mA and the energy to be 2.0MeV, controlling the irradiation dose to be 7.5kGy, then centrifugally washing with deionized water, adding deionized water according to the mass ratio of the graphene oxide powder to the deionized water of 0.5:100, and preparing the reduced graphene oxide suspension.
3) Activating the stock solution: the preparation concentration is 2g/L PdCl2，20g/LSnCl2100ml/L HClO mixed activation stock solution.
4) Activating, reducing and oxidizing a graphene suspension: and (3) mixing the reduced graphene oxide suspension and the activation stock solution in a mass ratio of 1: 2, ultrasonic mixing for 4 hours, aging for 6 hours, centrifugal separation, and finally adding deionized water to prepare activated reduced graphene oxide suspension with the concentration of 0.2%.
5) Cetyl trimethyl ammonium bromide dispersion of chitosan: preparing a methanol aqueous solution of 2 wt% of hexadecyl trimethyl ammonium bromide (wherein the mass ratio of methanol to deionized water is 1: 2), adding chitosan under ultrasonic stirring to prepare a hexadecyl trimethyl ammonium bromide dispersion liquid of 1 wt% of chitosan, and continuing to perform ultrasonic stirring for 60 min.
6) Silver-copper composite urea solution: silver nitrate (AgNO) with the preparation concentration of 1.5mol/L3)，2mol/L copper nitrate (Cu (NO)3)2·6H2O) and 2.5mol/L urea (CH)4N2O) and stirring for 60 min.
7) The preparation method comprises the following steps of (1) activating and reducing graphene dispersion liquid by silver-copper composite urea: activating reduction graphene oxide suspension with the concentration of 0.2% and hexadecyl trimethyl ammonium bromide dispersion liquid of chitosan are mixed according to the mass ratio of 3.5: mixing for 15min under 1.5 ultrasonic waves to obtain an activated reduced graphene oxide mixed solution, then adding the silver-copper composite urea solution into the activated reduced graphene oxide mixed solution and the silver-copper composite urea solution in a mass ratio of 5.0:1.5 under high-speed stirring, and mixing for 4 h.
8) Loading silver-copper graphene composite powder: and transferring the mixed solution into a high-pressure reaction kettle, controlling the hydrothermal reaction temperature at 220 ℃ for 6 hours, cooling, performing vacuum filtration, alternately washing with absolute ethyl alcohol and deionized water, and drying at 105 ℃.
9) Zn complex formulation mother liquor: preparing 0.2 mol/L2, 6-pyridinedicarboxylic acid aqueous solution and 0.2 mol/L4-aminopyridine mixed aqueous solution, heating and stirring at 70 ℃ for 1h, and then adding the mixed solution into 0.2mol/L ZnCl2In aqueous solution, and then refluxed at 100 ℃ for 100 hours.
10) Graphene composite antiviral powder: mixing the silver-copper-loaded graphene composite powder with Zn compound mother liquor in a mass ratio of 2:10, mixing and stirring at room temperature for 4 hours, standing for 28 hours, then carrying out vacuum filtration, washing with deionized water and carrying out vacuum drying at 80 ℃.
11) Graphene composite antiviral slurry: adding the powder prepared in the step (10) into an aqueous solution of carboxymethyl cellulose and vinyl trimethoxy silane, and grinding to prepare graphene composite antiviral slurry, wherein the mass ratio of the graphene composite antiviral powder to the deionized water to the carboxymethyl cellulose to the vinyl trimethoxy silane is 50: 50: 0.5%: 0.5 percent.
12) Graphene composite antiviral master batch: and (3) pumping the graphene composite antiviral slurry prepared in the step (11) into a screw extruder through a metering pump, and performing melt extrusion with PP resin powder at 260 ℃, wherein the mass ratio of the graphene composite antiviral slurry to the PP resin powder is 30: and (100) vacuumizing to obtain the graphene composite antiviral master batch.
13) Compounding, namely, graphene composite antibacterial antiviral melt-blown fabric: mixing the master batch prepared in the step (12) with PP resin and electret master batch according to a mass ratio of 20: 100: 3, uniformly mixing, and carrying out high-temperature melt spinning at 280 ℃ to obtain the graphene composite antibacterial antiviral melt-blown fabric.
14) Graphene composite antibacterial and antiviral air filter material: and carrying out compound processing on the graphene compound antibacterial and antiviral melt-blown cloth and the PET framework to obtain the graphene compound antibacterial and antiviral air filter material.
The antibacterial rate and the antiviral activity rate of the graphene composite antiviral powder prepared in the embodiments 1-4 are detected according to the standards GB/T20944.3-2008 and ISO 18184-2019, and the detection results are shown in Table 1.
TABLE 1 antibacterial and antiviral activity rates of graphene composite antiviral powder
Figure BDA0003374331310000171
The graphene composite antibacterial and antiviral filter material prepared in the embodiment 2-4 is used for detecting the antibacterial rate, the mite repelling rate and the antiviral activity rate of a sample according to the standards GB/T20944.3-2008, GB/T24253-2009 and ISO 18184-.
Table 2 bacteriostatic rate, mite repelling rate and antiviral activity rate of the graphene composite bacteriostatic and antiviral filter material
Figure BDA0003374331310000172
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 present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (9)

1. A preparation method of graphene composite antiviral powder and an antibacterial antiviral air filter material is characterized by comprising the following specific steps:
graphene oxide suspension: mixing graphene oxide powder with deionized water, and stirring at a high speed for 30-60 min to prepare a uniformly dispersed graphene oxide suspension;
reducing the graphene oxide suspension: mixing the graphene oxide suspension with acetone, putting the mixed solution into a sealed bag filled with nitrogen, controlling beam intensity and energy of an electron accelerator, irradiating the solution within a certain range of dose, then centrifugally washing the solution with deionized water, and adding deionized water according to the mass ratio of graphene oxide powder to deionized water of 0.5:100 to prepare a reduced graphene oxide suspension;
activating the stock solution: the preparation concentration is 1-2 g/L PdCl2，15~20g/LSnCl260-100 ml/L HClO mixed activation stock solution;
activating, reducing and oxidizing a graphene suspension: ultrasonically mixing the reduced graphene oxide suspension and the activation stock solution according to a certain mass ratio, aging, centrifugally separating, and finally adding deionized water to prepare an activated reduced graphene oxide suspension with a certain concentration;
cetyl trimethyl ammonium bromide dispersion of chitosan: preparing a methanol aqueous solution of 2 wt% of hexadecyl trimethyl ammonium bromide (wherein the mass ratio of methanol to deionized water is 1: 2), adding chitosan under ultrasonic stirring to prepare a hexadecyl trimethyl ammonium bromide dispersion solution of 1 wt% of chitosan, and continuing to perform ultrasonic stirring for 30-60 min;
silver-copper composite urea solution: silver nitrate (AgNO) with the preparation concentration of 0.75-1.5 mol/L3) 1.5 to 2mol/L copper nitrate (Cu (NO)3)2·6H2O) and 1.5-2.5 mol/L urea (CH)4N2O), stirring the mixed solution for 30-60 min;
the preparation method comprises the following steps of (1) activating and reducing graphene dispersion liquid by silver-copper composite urea: mixing activated reduced graphene oxide suspension and hexadecyl trimethyl ammonium bromide dispersion liquid of chitosan in a certain mass ratio for 15min under ultrasonic, adding silver-copper composite urea solution under high-speed stirring, and mixing for 4 h;
loading silver-copper graphene composite powder: transferring the mixed solution into a high-pressure reaction kettle, controlling the hydrothermal reaction temperature to be 150-220 ℃ and the hydrothermal reaction time to be 6-48 h, cooling, performing vacuum filtration, alternately washing with absolute ethyl alcohol and deionized water, and drying at 105 ℃;
zn complex formulation mother liquor: preparing a mixed aqueous solution of 2, 6-pyridinedicarboxylic acid and 4-aminopyridine with a certain concentration, heating and stirring for a certain time, and then adding the mixed solution into ZnCl with a certain concentration2Refluxing in water solution at 100 deg.C for a certain time;
graphene composite antiviral powder: mixing the silver-copper-loaded graphene composite powder with a Zn compound mother solution according to a mass ratio of 1-2: 10, mixing and stirring at room temperature for 2-4 h, standing for 7-28 h, then carrying out vacuum filtration, washing with deionized water, and carrying out vacuum drying at 80 ℃;
graphene composite antiviral slurry: adding the powder prepared in the step (10) into an aqueous or alcoholic solution of a dispersing agent and a surface modifier, and grinding to prepare graphene composite antiviral slurry;
graphene composite antiviral master batch: pumping the graphene composite antiviral slurry prepared in the step (11) into a screw extruder through a metering pump, carrying out melt extrusion with PP resin powder at 220-260 ℃, and vacuumizing to prepare graphene composite antiviral master batch;
compounding, namely, graphene composite antibacterial antiviral melt-blown fabric: uniformly mixing the master batch prepared in the step (12) with PP resin and electret master batch, and performing high-temperature melt spinning to prepare graphene composite antibacterial and antiviral melt-blown fabric;
graphene composite antibacterial and antiviral air filter material: and carrying out compound processing on the graphene compound antibacterial and antiviral melt-blown cloth and the PET framework to obtain the graphene compound antibacterial and antiviral air filter material.
2. The preparation method of the graphene composite antiviral powder and the antibacterial and antiviral air filter material according to claim 1, wherein the mass ratio of the graphene oxide powder to the deionized water in the step (1) is 0.1-3: 100.
3. the preparation method of the graphene composite antiviral powder and the antibacterial and antiviral air filter material according to claim 1, wherein the mass ratio of the graphene oxide suspension to acetone in the step (2) is 1: 1-2; the beam intensity of the electron accelerator is 0.5-1.0 mA, and the energy is 1.0-2.0 MeV; the irradiation dose at room temperature is 2.5-7.5 kGy.
4. The preparation method of the graphene composite antiviral powder and the antibacterial and antiviral air filter material according to claim 1, wherein the mass ratio of the reduced graphene oxide suspension to the activation stock solution in the step (4) is 1: 1-2, ultrasonically mixing for 2-4 h, and then aging for 6-12 h, wherein the concentration of the prepared activated reduced graphene oxide suspension is 0.1-0.2%.
5. The preparation method of the graphene composite antiviral powder and the antibacterial and antiviral air filter material according to claim 1, wherein the mass ratio of the graphene oxide suspension subjected to activation and reduction in the step (7), the cetyl trimethyl ammonium bromide dispersion of polysaccharide and the silver-copper composite urea solution is 2.5-3.5: 0.5-1.5: 0.5 to 1.5.
6. The preparation method of the graphene composite antiviral powder and the antibacterial and antiviral air filter material according to claim 1, wherein in the step (9), 0.1-0.2 mol/L2, 6-dipicolinic acid aqueous solution and 0.1-0.2 mol/L4-aminopyridine aqueous solution are heated and stirred at 40-90 ℃ for 1-2 h, and then 0.1-0.2 mol/L ZnCl is added2The aqueous solution is refluxed for 12 to 100 hours at the temperature of 100 ℃.
7. The preparation method of the graphene composite antiviral powder and the antibacterial and antiviral air filter material according to claim 1, wherein the mass ratio of the graphene composite antiviral powder, deionized water or alcohol, the dispersing agent and the surface modifier in the step (11) is 20-60: 40-80: 0.2-0.5%: 0.2-0.5%; the dispersing agent is sodium polyacrylate or carboxymethyl cellulose; the surface modifier is vinyl triethoxysilane or vinyl trimethoxysilane.
8. The preparation method of the graphene composite antiviral powder and the antibacterial and antiviral air filter material according to claim 1, wherein the mass ratio of the graphene composite antiviral slurry to the PP resin powder in the step (12) is 5-30: 100.
9. the preparation method of the graphene composite antiviral powder and the antibacterial and antiviral air filter material according to claim 1, wherein in the step (13), the mass ratio of the graphene composite antiviral master batch to the PP resin to the electret master batch is 5-20: 100: 1-3, and the highest processing temperature range is 200-280 ℃.
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