CN110694488B - Antibacterial filtering material and application thereof - Google Patents
Antibacterial filtering material and application thereof Download PDFInfo
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- CN110694488B CN110694488B CN201910886302.6A CN201910886302A CN110694488B CN 110694488 B CN110694488 B CN 110694488B CN 201910886302 A CN201910886302 A CN 201910886302A CN 110694488 B CN110694488 B CN 110694488B
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/02—Inorganic material
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
Abstract
The invention belongs to the technical field of antibacterial filter materials, and particularly relates to an antibacterial filter material which comprises a filter base material and an antibacterial agent connected to the surface of the filter base material, wherein the antibacterial agent is a quaternary ammonium salt monomer, and the quaternary ammonium salt monomer at least contains an alkyl group with the carbon atom number larger than 8. The antibacterial filter material provided by the invention has excellent antibacterial performance and filtering performance, can filter particle impurities and bacteria, can control the increase of the number of bacteria by killing the bacteria attached to the filter base material, and effectively solves the problem of filter material and water quality pollution caused by enrichment of bacteria on the filter material.
Description
Technical Field
The invention belongs to the technical field of antibacterial filter materials, and particularly relates to an antibacterial filter material and application thereof.
Background
Along with the rapid development of society and the improvement of living standard of people, people gradually discover that harmful microorganisms such as bacteria and mold seriously harm the health, the living quality and the living environment of people, the requirements of people on health consciousness and medical standard are higher and higher, and the resistance and the prevention to bacteria and viruses in daily production and life are also more and more emphasized, so that the safety of the lives and properties of people is better guaranteed. The water quality and the air quality are two most close environmental factors for production and life of people, have great practical significance for the research of the purification treatment technology of the water quality and the air, and are one of the hot spots of the research. At present, impurity filtering technology and antibacterial technology are separately implemented in water purification and air purification processes and apparatuses, and materials and processes applied thereto are also distinguished from each other. Wherein, the impurity filtering technology mainly uses polymer fiber membrane and polypropylene fiberThe filter materials with the pore diameters of micron to nanometer levels, such as a cotton swab (PP cotton), an ultrafiltration membrane and the like, realize the physical filtration of colloid, suspended matters, microorganisms, bacteria and other impurity particles in water or the physical blocking of particles and bacteria in air. Any impurity filtering process has an obvious defect that the impurities are enriched on the filter material along with the increase of the filtered impurities, and microorganisms enriched on the filter material can reproduce by taking the enriched impurities as nutrients, so that more pollutants are generated, and the water quality safety or the air quality is finally influenced. The antibacterial technology is to inhibit the propagation of microbes such as bacteria in water or air by physical and chemical methods, so as to achieve the purpose of effectively controlling the number of microbes. At present, the common antibacterial technology is heavy metal cation (Ag)+、Cu2+Etc.) sterilization and Ultraviolet (UV) sterilization. Among them, the antibacterial principle of heavy metal cations is to inhibit the proliferation of bacteria by destroying cell membranes. Ultraviolet sterilization is to kill bacteria by destroying the double helix structure of DNA of bacteria or destroying proteins in the body of bacteria using ultraviolet rays having high photon energy. However, the existing antibacterial technologies have the disadvantages that: heavy metal cations are also toxic to human cells and can destroy the metabolism of the human body while sterilizing; the ultraviolet disinfection process has high requirements on equipment and devices and is limited in application places.
At present, the research of organically combining the filtering technology and the antibacterial technology is relatively few, excellent antibacterial effect and interception filtering effect cannot be achieved, and the material with the impurity filtering function and the antibacterial function has a wide application prospect and practical significance.
Disclosure of Invention
The invention aims to provide an antibacterial filter material, and aims to solve the technical problem that the conventional filter material cannot have both excellent antibacterial effect and interception filter effect.
Another object of the present invention is to provide a water purifying apparatus.
It is still another object of the present invention to provide an air cleaning apparatus.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
the antibacterial filtering material comprises a filtering base material and an antibacterial agent connected to the surface of the filtering base material, wherein the antibacterial agent is a quaternary ammonium salt monomer, and the quaternary ammonium salt monomer at least contains an alkyl group with the carbon atom number larger than 8.
Preferably, the quaternary ammonium salt monomer at least contains one alkyl with 8-20 carbon atoms.
Preferably, the quaternary ammonium salt monomers include: at least one of 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride and/or octadecyl dimethyl chloramine 3, 4, 4' -trichlorobiphenyl ketone diamine quaternary ammonium salt; and/or the presence of a gas in the gas,
the filtration substrate comprises: one or more of polypropylene material, polyester material, nylon, polytetrafluoroethylene, cellulose, glass fiber, silicate fiber and alumina fiber membrane.
Preferably, the filter substrate is an activated substrate.
Preferably, the mass percentage of the quaternary ammonium salt monomer is more than 1.0% based on 100% of the total mass of the antibacterial filter material.
Preferably, the interception aperture of the antibacterial filtering material is 1-5 microns.
Preferably, the antibacterial filter material comprises: the polypropylene filter membrane and the 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride connected to the surface of the polypropylene filter membrane; the mass percentage of the 3- (trimethoxysilyl) propyl dimethyl octadecyl ammonium chloride in the antibacterial filter material is more than 1.0%; the rejection rate of the antibacterial filter material to impurities with the particle size not less than 2 microns is more than 80%. Preferably, the antimicrobial agent is attached to the filtration substrate by means of coupling grafting; and/or the rejection rate of the antibacterial filter material to impurities with the particle size not less than 2 microns is greater than 90%.
Correspondingly, a water purifying device comprises the antibacterial filtering material.
Correspondingly, the air purification device comprises the antibacterial filter material.
The antibacterial filter material provided by the invention comprises a filter substrate and a quaternary ammonium salt monomer which is connected to the surface of the substrate and at least contains one alkyl group with the carbon atom number larger than 8, wherein the quaternary ammonium salt monomer containing an alkane chain with the carbon atom number larger than 8 has more excellent antibacterial performance relative to the quaternary ammonium salt of a short-chain alkane chain, and is connected to the surface of the filter substrate; moreover, the quaternary ammonium salt antibacterial monomer is connected to the filtering substrate, so that health concerns caused by non-fixed quaternary ammonium salt antibacterial molecules can be effectively avoided. On the other hand, the quaternary ammonium salt antibacterial monomer is connected to the surface of the filtering base material, and the quaternary ammonium salt antibacterial monomer is grafted on the surface of the base material to form the fiber filtering material loaded with long molecular chains, so that the filtering aperture of the filtering base material is thinned, and the interception and filtering effects of the antibacterial filtering material are improved. On the other hand, compared with the filtering base material without the quaternary ammonium salt connection, the filtering base material with the surface connected with the quaternary ammonium salt monomer can better adsorb bacteria due to the positive potential effect on the surface, and can destroy the bacterial membrane by containing the alkane chain with the carbon atom number more than 8 so as to achieve the effect of killing the bacteria. Therefore, the antibacterial filter material provided by the embodiment of the invention has excellent antibacterial performance and filtering performance, can filter impurities, can control the increase of the number of bacteria by killing bacteria attached to the filter substrate, and effectively solves the problems of filter material pollution and water quality pollution caused by enrichment of bacteria on the filter material.
The water purifying device provided by the invention comprises the antibacterial filtering material with excellent antibacterial performance and filtering performance, so that impurities in water can be effectively filtered, the growth of bacteria in the water and on the filtering material can be controlled, and the problems of filter material pollution and water quality pollution caused by enrichment of the bacteria on the filtering material are effectively solved.
The air purification device provided by the invention comprises the antibacterial filtering material with excellent antibacterial performance and filtering performance, so that the air is purified and sterilized while particulate impurities in the air are trapped and filtered, and the problem of filter material pollution caused by bacteria enrichment on the filtering material can be effectively avoided.
Drawings
FIG. 1 is a scanning electron microscope photograph of an antibacterial filtration membrane of example 1 of the present invention and a general inorganic fiber nonwoven fabric of comparative example 1.
FIG. 2 is a Fourier transform infrared spectrum of the antibacterial filtering membrane of example 1 of the present invention and a general inorganic fiber nonwoven membrane of comparative example 1.
FIG. 3 is an X-ray photoelectron spectrum of the antibacterial filtering membrane of example 1 of the present invention and the conventional inorganic fiber nonwoven membrane of comparative example 1.
FIG. 4 is a thermogravimetric analysis of the antibacterial filtering membrane of example 1 of the present invention and the common inorganic fiber nonwoven fabric membrane of comparative example 1.
FIG. 5 is a zeta potential diagram of the antibacterial filtering membrane of example 1 of the present invention and the ordinary inorganic fiber nonwoven membrane of comparative example 1.
FIG. 6 is a graph showing the antibacterial properties of the antibacterial filtration membranes of examples 1 and 2 of the present invention and the common inorganic fiber nonwoven membranes of comparative examples 1 to 3.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The embodiment of the invention provides an antibacterial filter material which comprises a filter base material and an antibacterial agent connected to the surface of the filter base material, wherein the antibacterial agent is a quaternary ammonium salt monomer, and the quaternary ammonium salt monomer at least contains an alkyl group with the carbon atom number larger than 8.
The antibacterial filter material provided by the embodiment of the invention comprises a filter substrate and a quaternary ammonium salt monomer which is connected to the surface of the substrate and at least contains one alkyl group with the carbon atom number larger than 8, wherein the quaternary ammonium salt monomer containing an alkane chain with the carbon atom number larger than 8 has more excellent antibacterial performance relative to the quaternary ammonium salt of a short-chain alkane chain, and is connected to the surface of the filter substrate; moreover, the quaternary ammonium salt antibacterial monomer is connected to the filtering substrate, so that health concerns caused by non-fixed quaternary ammonium salt antibacterial molecules can be effectively avoided. On the other hand, the quaternary ammonium salt antibacterial monomer is connected to the surface of the filtering base material, and the quaternary ammonium salt antibacterial monomer is grafted on the surface of the base material to form the fiber filtering material loaded with long molecular chains, so that the filtering aperture of the filtering base material is thinned, and the interception and filtering effects of the antibacterial filtering material are improved. On the other hand, compared with the filtering base material without the quaternary ammonium salt connection, the filtering base material with the surface connected with the quaternary ammonium salt monomer can better adsorb bacteria due to the positive potential effect on the surface, and can destroy the bacterial membrane by containing the alkane chain with the carbon atom number more than 8 so as to achieve the effect of killing the bacteria. Therefore, the antibacterial filter material provided by the embodiment of the invention has excellent antibacterial performance and filtering performance, can filter impurities, can control the increase of the number of bacteria by killing bacteria attached to the filter substrate, and effectively solves the problems of filter material pollution and water quality pollution caused by enrichment of bacteria on the filter material.
The antibacterial filter material provided by the embodiment of the invention can be directly used as a filter material alone, and can also be used in a composite way with other filter materials according to requirements, so that the filter effect and the application flexibility are further enhanced. The application form of the antibacterial filtering material in the embodiment of the invention is not particularly limited, and the antibacterial filtering material can be any form meeting the actual application requirements, such as an antibacterial filtering membrane, antibacterial filtering particles, an antibacterial filtering wire rod, an antibacterial filtering pipe, an antibacterial filtering block and the like, and can be applied to the fields of filtering and antibacterial treatment of water quality and air and the like. In addition, the antibacterial filter material of the embodiment of the invention can also be prepared by processing the filter base material particles with the antibacterial agent connected on the surface into any shape meeting the practical application requirements, such as a filter membrane, a filter block, a filter pipe and the like.
In a preferred embodiment, the quaternary ammonium salt monomer contains at least one alkyl group with 8-20 carbon atoms. According to the embodiment of the invention, the antibacterial agent is a quaternary ammonium salt monomer, wherein the quaternary ammonium salt monomer at least contains one alkyl group with 8-20 carbon atoms, quaternary ammonium salt molecules are adsorbed on a bacterial cell membrane with negative charges under the interaction of coulomb force, then the quaternary ammonium salt molecules are fixed on the bacterial cell membrane through cations, and hydrophobic lipophilic groups (alkyl) of the quaternary ammonium salt can enter the bacterial cell membrane and permeate into bacteria to release potassium ions and other cytoplasmic inclusions in the bacteria body, so that the bacteria die. The quaternary ammonium salt antibacterial agent enters the interior of bacterial cells and is related to the lipophilicity (alkyl length) of quaternary ammonium salt, when the length of the alkyl is 8-20, the quaternary ammonium salt antibacterial agent has the most appropriate lipophilicity, and the quaternary ammonium salt antibacterial agent is most likely to enter a cell lipid layer, so that the cell permeability is damaged, the substance in the cell is caused to exosmose, and the cell death is caused. Therefore, the quaternary ammonium salt bactericide containing the alkyl with the carbon atom number of 8-20 has the best bactericidal performance, and is connected to the base material of the filter material, so that the filter material has excellent interception and filtration performance and can endow the filter material with the best antibacterial performance. In some embodiments, the antimicrobial agent is a quaternary ammonium salt monomer containing an alkyl group of 10, 12, 14, 16, or 18 carbon atoms.
As a preferred embodiment, the quaternary ammonium salt monomer includes: 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride and/or octadecyl dimethyl chloramine 3, 4, 4' -trichlorobiphenyl ketone diamine quaternary ammonium salt. The quaternary ammonium salts adopted by the embodiment of the invention all contain octadecyl chains, and the hydrophobic and lipophilic octadecyl chains can better enter bacterial cell membranes and permeate into bacteria to release potassium ions and other cytoplasmic inclusions in the bacteria, so that the bacteria die, and the quaternary ammonium salts have higher damage and killing effects on the bacteria. In some embodiments, the quaternary ammonium salt monomer comprises 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride. In some embodiments, the quaternary ammonium salt monomer comprises octadecyl dimethyl chloramine 3, 4, 4' -trichlorobiphenyl ketone diamine quaternary ammonium salt. In some embodiments, the quaternary ammonium salt monomers include: 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride and octadecyl dimethyl chloramine 3, 4, 4' -trichlorobiphenyl ketone diamine quaternary ammonium salt.
As a preferred embodiment, the filtration substrate comprises: one or more of polypropylene material, polyester material, nylon, polytetrafluoroethylene, cellulose, glass fiber, silicate fiber and alumina fiber membrane. The filter substrate of the embodiment of the invention comprises one or more of inorganic oxide fiber membranes such as polypropylene materials, polyester materials, nylon, polytetrafluoroethylene, cellulose, glass fibers, silicate fibers, alumina fiber membranes and the like, and the quaternary ammonium salt antibacterial monomer can be connected to any filter material according to actual requirements to endow the filter material with antibacterial performance.
In some embodiments, the filter substrate comprises an inorganic fiber non-woven fabric, the inorganic fiber non-woven fabric is one of polypropylene filter substrates, and the filter substrate has the advantages of good chemical and physical stability, low material cost and the like, and has wide application prospects in the fields of water purification and air purification.
In a preferred embodiment, the mass percentage of the quaternary ammonium salt monomer is 1.0% or more, based on 100% of the total mass of the antibacterial filter material. The mass percentage of the quaternary ammonium salt in the antibacterial filter material is more than 1.0%, so that the density of the quaternary ammonium salt monomer connected to the filter material is effectively ensured, the antibacterial performance of the filter material is further ensured, and the antibacterial filter material has excellent antibacterial performance and interception filtering performance.
As a preferred embodiment, the interception aperture of the antibacterial filter material is 1-5 microns. The quaternary ammonium salt antibacterial monomer is connected to the surface of the filtering base material, and the quaternary ammonium salt antibacterial monomer is grafted on the surface of the base material to form the fiber filtering material loaded with long molecular chains, so that the filtering aperture of the filtering base material is thinned, the interception and filtering effects of the antibacterial filtering material are improved, the interception aperture of the antibacterial filtering material is 1-5 microns, and the excellent interception and filtering effects are achieved.
In some embodiments, the antimicrobial filter material comprises: the polypropylene filter membrane and the 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride connected to the surface of the polypropylene filter membrane; the mass percentage of the 3- (trimethoxysilyl) propyl dimethyl octadecyl ammonium chloride connected in the antibacterial filter material is more than 1.0%; the rejection rate of the antibacterial filter material to impurities with the particle size not less than 2 microns is more than 80%. The antibacterial filtering membrane provided by the embodiment of the invention has excellent antibacterial performance and interception filtering performance. In a further preferred embodiment, the antibacterial filter material has a rejection rate of more than 90% for impurities with the particle size of not less than 2 microns.
As a preferred embodiment, the attachment of the antimicrobial agent to the filter substrate comprises: and after the filtering substrate is subjected to plasma treatment, the antibacterial agent is connected to the surface of the substrate in a coupling grafting mode. The connection mode of the antibacterial agent on the filter substrate comprises the following steps: the filtering base material is subjected to plasma treatment, the surface of the filtering base material is activated on the premise of not influencing the mechanical property and the micro-morphology of the base material, reactive functional groups such as-OH and-COOH are generated, and the base material has wide selectivity. And then the antibacterial agent is connected to the surface of the filtering base material in a dehydration, condensation, coupling and grafting manner, the filtering base material after plasma treatment is firmly combined with the quaternary ammonium salt antibacterial agent, the usage amount of the antibacterial agent is small, the distribution density is controllable and uniform, and the prepared quaternary ammonium salt antibacterial material has more lasting and stable antibacterial performance.
As a preferred embodiment, the step of plasma treating the filter substrate comprises: under the conditions that the radio frequency power is 500-1000W/50 Hz, the atmospheric pressure is 0.2-0.4 MPa, the distance between a plasma spray gun and the surface of the filter substrate is 0.5-2.5 cm, and working gas is selected from: ar, N2、O2And under the condition of at least one of compressed air, carrying out normal pressure plasma treatment on the filter substrate at the treatment speed of 1-20 cm/s to obtain the surface activated filter substrate. The embodiment of the invention carries out normal pressure plasma treatment on the filtering base material, the normal pressure plasma treatment has low requirements on the shape and the specification of the base material, batch treatment can be realized, the treatment efficiency is high, and the cost is lower. In the embodiment of the invention, when the radio frequency power is 500-1000W/50 Hz, the atmospheric pressure is 0.2-0.4 MPa, and the working gas is selected from: ar, N2、O2And under at least one condition of compressed air, carrying out normal pressure plasma treatment on the base material, wherein the treatment speed is 1-20 cm/s, and the best treatment effect is achieved on the base material. The working gas has high selection flexibility and wide range.
As a preferred embodiment, the step of plasma treating the filter substrate comprises: under the conditions that the radio frequency power is 500-1000W/40 Hz, the working pressure is 10-100 pa, and the working gas is selected from: ar, N2、O2And (3) performing vacuum plasma treatment on the substrate for 1-60 minutes under the condition that the flow rate of the working gas is 70-200 sccm to obtain the surface-activated substrate. According to the embodiment of the invention, the vacuum plasma treatment is carried out on the filtering base material, the activation degree of the vacuum plasma treatment on the surface of the base material is higher, and because the vacuum plasma treatment is carried out in the vacuum environment of non-polymeric gas, other elements such as nitrogen elements and the like are not easy to introduce in the activation process and after the activation of the surface of the base material, and the purification purity is high. In the embodiment of the invention, when the radio frequency power is 500-1000W/40 Hz, the working pressure is 10-100 pa, and the working gas is selected from: ar, N2、O2At least one of the operationsAnd performing vacuum plasma treatment on the substrate for 1-60 minutes under the condition that the gas flow is 70-200 sccm, so that the optimal treatment effect on the filtering substrate is achieved.
In some embodiments, the step of attaching the antimicrobial agent to the surface of the filtration substrate by way of dehydration condensation comprises: according to the volume ratio of 1: (2-5) mixing a quaternary ammonium salt antibacterial agent and a tetraethyl orthosilicate coupling agent to obtain a first mixed solution; according to the mass ratio of 1: (10-30) mixing the first mixed solution with an ethanol solution with the concentration of 80% -90%, and reacting in a water bath at the temperature of 25-50 ℃ for 3-8 hours to obtain a reactive quaternary ammonium salt solution. And soaking the surface-activated base material in a reactive quaternary ammonium salt solution for more than 1 minute, reacting for at least 2 hours at the temperature of 100-120 ℃, and cleaning and drying to obtain the antibacterial filtering material.
In some embodiments, the quaternary ammonium salt antimicrobial agent is hydrolyzed and then directly connected with the surface plasma treated filter substrate to obtain the antimicrobial filter material.
The embodiment of the invention also provides a water purifying device which comprises the antibacterial filtering material.
According to the water purifying device provided by the embodiment of the invention, as the water purifying device comprises the antibacterial filtering material with excellent antibacterial performance and filtering performance, not only can impurities in water be effectively filtered, but also the growth of bacteria in the water and on the filtering material can be controlled, and the problems of filter material pollution and water quality pollution caused by enrichment of bacteria on the filtering material are effectively avoided.
The embodiment of the invention also provides an air purification device, which comprises the antibacterial filtering material.
The air purification device provided by the embodiment of the invention comprises the antibacterial filtering material with excellent antibacterial performance and filtering performance, so that the air is purified and sterilized while particulate impurities in the air are trapped and filtered, and the problem of filter material pollution caused by bacteria enrichment on the filtering material can be effectively avoided.
In order to clearly understand the details of the above-mentioned implementation and operation of the present invention for those skilled in the art and to clearly show the advanced performance of the antibacterial filter material according to the embodiment of the present invention, the technical solution is illustrated by the following examples.
Example 1
An antibacterial filter material, the preparation method comprises:
s10, obtaining an inorganic glass fiber non-woven fabric membrane with the thickness of 0.5 mm, and performing normal-pressure plasma treatment for 1 time under the conditions that the power is 850W, the treatment speed is 6cm/s, the treatment height is 2.0cm, and the working gas is dry compressed air to obtain the inorganic glass fiber non-woven fabric membrane with the activated surface.
S20, obtaining a reactive quaternary ammonium salt solution: mixing 3- (trimethoxysilyl) propyl dimethyl octadecyl ammonium chloride and tetraethyl orthosilicate according to the volume ratio of 1:3 to obtain a first mixed solution; and mixing the first mixed solution with an ethanol solution with the concentration of 85% according to the mass ratio of 1:10, and reacting for 4 hours at the temperature of 30 ℃ to obtain a reactive quaternary ammonium salt solution.
S30, soaking the non-woven fabric membrane with the activated surface in a reactive quaternary ammonium salt solution for 2 minutes, reacting for 2 hours at the temperature of 110 ℃, and cleaning and drying to obtain the antibacterial filtering membrane.
Example 2
An antibacterial filter material, the preparation method comprises:
s10, obtaining an inorganic glass fiber non-woven fabric membrane with the thickness of 0.5 mm, and performing normal-pressure plasma treatment for 1 time under the conditions that the power is 750W, the treatment speed is 4cm/s, the treatment height is 1.5cm, and the working gas is dry compressed air to obtain the non-woven fabric membrane with the activated surface.
S20, obtaining a reactive quaternary ammonium salt solution: mixing 3- (trimethoxysilyl) propyl dimethyl octadecyl ammonium chloride and tetraethyl orthosilicate according to the volume ratio of 1:4 to obtain a first mixed solution; and mixing the first mixed solution with an ethanol solution with the concentration of 85% according to the mass ratio of 1:5, and reacting for 4 hours at the temperature of 30 ℃ to obtain a reactive quaternary ammonium salt solution.
S30, soaking the non-woven fabric membrane with the activated surface in a reactive quaternary ammonium salt solution for 2 minutes, reacting for 2 hours at the temperature of 110 ℃, and cleaning and drying to obtain the antibacterial filtering membrane.
Comparative example 1
Common inorganic glass fiber non-woven fabric membranes.
Comparative example 2
The common inorganic glass fiber non-woven fabric membrane is grafted with quaternary ammonium salt non-woven fabric without plasma treatment.
Comparative example 3
The quaternary ammonium salt non-woven fabric grafted by the common inorganic glass fiber non-woven fabric membrane through acid-base treatment, wherein the acid-base treatment method comprises the following steps:
alkali pretreatment: preparing 8% sodium hydroxide solution, and heating to 50 ℃ in a constant-temperature water bath kettle. The raw films are respectively put into the reaction kettle and reacted for 60 minutes.
Cleaning and drying: taking out the membrane, namely putting the membrane into a funnel together, and pumping and washing the membrane to be neutral by using pure water; taking out, placing on a glass culture dish, timing when the temperature of the oven rises to 120 ℃ again, and drying for 30 min. An alkali pretreated film was obtained.
Acid pretreatment: preparing 12% glacial acetic acid solution, and heating to 50 ℃ in a constant-temperature water bath kettle. The membranes were placed in alkaline pretreatment and reacted for 60 minutes.
Cleaning and drying: taking out the membrane, namely putting the membrane into a funnel together, and pumping and washing the membrane to be neutral by using pure water; taking out, placing on a glass culture dish, timing when the temperature of the oven rises to 120 ℃ again, and drying for 30 min. An acid pretreated membrane was obtained.
Then, quaternary ammonium salt was grafted to the acid-pretreated film by the steps of S20 and S30 in example 2, and the ordinary inorganic glass fiber nonwoven fabric film was subjected to acid-base treatment of the grafted quaternary ammonium salt nonwoven fabric.
Further, in order to verify the improvement of the antibacterial filter material of the example 1 of the present invention, the example of the present invention was subjected to the relevant experimental tests.
Test example 1
According to the embodiment of the invention, the surface morphology structures of the common non-woven fabric film in the comparative example 1 and the antimicrobial filter membrane prepared from the common non-woven fabric in the embodiment 1 are tested by a scanning electron microscope, and the common inorganic fiber non-woven fabric film and the antimicrobial filter membrane are both of fiber structures with the axial size of more than 100 micrometers and the radial size of less than 5 micrometers. The experimental results are shown in figure 1, and the pore size formed between the fibers is about 1-5 microns, and the fiber structure is beneficial to the filtration of bacteria. The fiber surface of the common inorganic fiber non-woven fabric shows a clear boundary, but the fiber boundary of the antibacterial filter membrane is slightly fuzzy and is obviously not as obvious as the fiber interface of the common inorganic fiber non-woven fabric. Even, because the quaternary ammonium salt is coupled and grafted on the non-woven fabric, some fibers of the antibacterial filtering membrane are adhered together, as shown in the area in the circle in the attached figure 1, the pore structure of the filtering base material is refined, and the antibacterial filtering membrane has a better interception effect.
Test example 2
Comparative qualitative analysis was performed on the antibacterial filter membrane prepared in example 1 and the filter membrane of comparative example 1 by fourier transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS).
As shown in the Fourier transform Infrared Spectroscopy (FTIR) chart of FIG. 2, since both nonwoven fabrics contained an acrylic binder, the C ═ O stretching peak was shown to be 1727cm in the FTIR chart-1. At 458cm-1And 1008cm-1The two strong peaks at (a) represent bending vibration and asymmetric vibration of Si-O-Si of the main component silicon oxide of the nonwoven fabric substrate, respectively. 2850cm-1And 2920cm-1Peak at 1452cm corresponding to C-H stretch-1And 1490cm-1The peak at (a) is associated with the C-H bend. These four peaks are produced by the binder and the quaternary ammonium salt antimicrobial agent. The quaternary ammonium salt antibacterial agent was present only in the fiber nonwoven fabric sample after the plasma graft treatment in example 1. Accordingly, only 1564cm of the antibacterial filtration membrane of example 1 subjected to the treatment is shown in FIG. 2-1And 1534cm-1Two characteristic peaks of C-N vibration.
As shown in FIG. 3, X-ray photoelectron spectroscopy (XPS) shows that the conventional nonwoven film of comparative example 1 does not show N1sThe peak of (a) indicates that no N element is present in the sample. N in the treated antibacterial Filtering Membrane of example 11sThe peak can be divided into two sub-peaks. The first sub-peak is located at399.7eV, because nitrogen gas is ionized during the plasma treatment and then sputtered into the nonwoven fabric matrix material, forming interstitial nitrogen atoms that are doped into the fiber material. The second sub-peak is at 402.3eV, which is typical of the nitrogen peak of quaternary ammonium salts, which demonstrates the grafting of quaternary ammonium salts onto nonwoven fabrics.
The two spectra of FTIR and XPS together show that the treated quaternary ammonium salt is grafted to a common non-woven fabric to form a non-woven fabric filtering membrane loaded with the quaternary ammonium salt.
Test example 3
In the embodiment of the present invention, the mass percentage of the quaternary ammonium salt in the antibacterial filtering membrane prepared in example 1 was measured by a thermogravimetric analysis (TGA). Test structures as shown in fig. 4, the weight loss of the samples was about 2.5 wt.% from ambient temperature to 150 ℃, due to moisture adsorbed on the fibers. In the production process of the non-woven fabric, acrylic acid is used as a small molecular adhesive to be applied to the fiber, so that the non-woven fabric is convenient to manufacture. Thus, a weight loss of about 1% from 150 ℃ to 380 ℃ may be a small amount of volatilization of the small molecule acrylic acid. Most of the weight loss occurred between 380 ℃ and 450 ℃. This is a mixing process involving thermal decomposition of the binder and quaternary ammonium salt antimicrobial agent, volatilization of small molecules resulting from the decomposition, and the like. The reaction mainly takes place between 450 ℃ and 650 ℃. Finally, both materials are mineralized at high temperature, and the weight curve from 650 ℃ to 800 ℃ is relatively flat. Wherein, after complete high-temperature mineralization (>650 ℃), the weight difference between the common fiber non-woven fabric film and the inorganic fiber non-woven fabric film subjected to plasma grafting treatment is 1.3 wt.%. This indicates that the amount of quaternary ammonium salt grafted to the surface of the plain fiber is 1.3% by weight based on the total weight of the nonwoven fabric
Test example 4
Inventive example zeta potential patterns of the antibacterial filtering membrane prepared in example 1 and the common nonwoven fabric membrane of comparative example 1 were tested. As shown in fig. 5, the zeta potential of the general nonwoven fabric was significantly lower than that of the antibacterial filtering membrane prepared in example 1 in the test pH range (pH 4-10). In the case of a neutral aqueous solution having a pH of 7, the zeta potential of the ordinary nonwoven fabric was-63.9 mV, whereas the zeta potential of the antibacterial filtration membrane prepared in example 1 was 65.1 mV. The zeta potential result shows that after the cationic quaternary ammonium salt is grafted with the quaternary ammonium salt, positively charged quaternary ammonium salt molecules are introduced, so that the zeta potential of the filtering substrate is obviously increased, and the adsorption of bacteria with negative electricity characteristics can be enhanced.
Test example 5
The antibacterial patch method of the embodiment of the present invention was used to evaluate the antibacterial performance of the antibacterial filter membranes provided in examples 1 and 2, the quaternary ammonium salt nonwoven fabric grafted to the common nonwoven fabric membrane provided in comparative example 1, the common inorganic fiber nonwoven fabric membrane of comparative example 2 without plasma treatment, and the quaternary ammonium salt nonwoven fabric grafted to the common inorganic glass fiber nonwoven fabric membrane of comparative example 3 with acid and alkali treatment.
The antibacterial filtration membranes provided in examples 1 and 2 and the nonwoven fabrics of comparative examples 1, 2 and 3 were cut into disks having a diameter of 45mm, sterilized, and then placed in sterilized Buchner funnels, respectively, 600mL of bacteria-containing water containing 4000-5000CFU/mL of bacteria was suction-filtered through the samples of examples and comparative examples using a vacuum suction filtration apparatus, and the samples of examples and comparative examples were taken out on a solidified nutrient agar medium. The medium was inverted and cultured in an incubator at 37 ℃ for 48 hours. Observing the growth of bacteria around the surfaces of the samples of the examples and the comparative examples, the less bacteria grown on and around the surfaces of the samples indicates that the antibacterial effect of the material is better. The test results are shown in fig. 6, and the antibacterial filter membranes of examples 1 and 2 after plasma grafting treatment show significantly superior antibacterial performance to the quaternary ammonium salt nonwoven fabric grafted by the acid-base treatment of the common nonwoven fabric of comparative example 1, the common inorganic fiber nonwoven fabric of comparative example 2 without plasma treatment and the common inorganic glass fiber nonwoven fabric of comparative example 3.
Test example 6
The examples of the present invention evaluated the particle interception effect of the antibacterial filtering membrane provided in example 1 and the general non-woven fabric provided in comparative example 1 using the interception rate of 2 μm particles in an aqueous solution.
The particles having an average diameter of 2 μm are prepared to a concentration of 1000 to 4000 particles/ml. The antibacterial filtration membrane provided in example 1 and the ordinary nonwoven fabric provided in comparative example 1 were cut into a circular piece having a diameter of 45mm, and then fixed in a membrane test jig having a sealed edge. The prepared aqueous solution containing 2 μm particles was pumped by a water pump and forced through the filter membrane to be tested under the water pressure generated by the water pump, and the particle concentration in the raw water and the particle concentration in the aqueous solution filtered through the nonwoven fabric were measured by a particle counter. The retention rate of the non-woven fabric to 2 μm particles is the ratio of the concentration of the particles in the aqueous solution filtered by the non-woven fabric to the concentration of the particles in the raw water. Tests show that the retention rate of the common non-woven fabric membrane on 2 mu m particles is only 54.5 percent, while the retention rate of the antibacterial filter membrane provided by the example 1 after plasma grafting treatment on 2 mu m particles reaches 97.56 percent, so that the retention rate of the filter membrane on 2 mu m particles is greatly improved after plasma treatment and coupling of the grafted quaternary ammonium salt.
Test example 7
The examples of the present invention evaluated the particle interception effect of the antibacterial filtering membrane provided in example 2 and the acid-base treated inorganic fiber nonwoven fabric provided in comparative example 3 using the interception rate of 2 μm particles in an aqueous solution.
The particles having an average diameter of 2 μm are prepared to a concentration of 1000 to 4000 particles/ml. The antibacterial filtration membrane provided in example 2 and the acid-base treated inorganic fiber nonwoven fabric provided in comparative example 3 were cut into a circular piece having a diameter of 45mm, and then fixed in a membrane test jig having an edge sealed. The prepared aqueous solution containing 2 μm particles was pumped by a water pump and forced through the filter membrane to be tested under the water pressure generated by the water pump, and the particle concentration in the raw water and the particle concentration in the aqueous solution filtered through the nonwoven fabric were measured by a particle counter. The retention rate of the non-woven fabric to 2 μm particles is the ratio of the concentration of the particles in the aqueous solution filtered by the non-woven fabric to the concentration of the particles in the raw water. Tests show that the interception rate of the common inorganic fiber non-woven fabric membrane subjected to acid and alkali treatment in the comparative example 3 to 2 mu m particles is 80%, while the interception rate of the antibacterial filter membrane provided by the example 1 subjected to plasma grafting treatment to 2 mu m particles is 98.5%, so that the interception rate of the filter membrane to 2 mu m particles is obviously improved by coupling the inorganic glass fiber non-woven fabric subjected to plasma treatment with the grafted quaternary ammonium salt compared with the inorganic fiber non-woven fabric subjected to acid and alkali treatment with the grafted quaternary ammonium salt.
Test example 8
The antibacterial filter membrane of example 1 was placed in a mold to simulate the use scene of an actual filter element, and washed with tap water, and after the antibacterial filter membrane of the same area (per square centimeter) was tested to filter 0L, 1L, 2L and 3L of tap water (0L/cm)2，1L/cm2，2L/cm2，3L/cm2) And stability of antibacterial effect. 0.75 g of the antibacterial filter membrane after being filtered by different water amounts is taken out, and the antibacterial filter membrane is respectively put into containers containing the same amount of bacteria and culture solution, and is subjected to vibration sterilization treatment for 20 minutes at 35 ℃. After the vibration is finished, the solution is taken out, the culture is carried out for 48 hours, and then the antibacterial effect of the antibacterial filtering membrane washed by different water amounts in the contrast filtering treatment is observed.
The control group was prepared by shaking-sterilizing the same number of bacteria and culture medium in a container without adding a filter at 35 ℃ for 20 minutes. After the shaking was completed, the solution was taken out, cultured for 48 hours, and then the number of bacteria in the culture dish was measured.
The survival rate of bacteria can be calculated according to the formula: the survival rate is 100% of the number of bacteria in the solution after shaking/the number of bacteria in the original solution before shaking, and the calculation results are shown in table 1 below:
TABLE 1
| Amount of Water flushed (L/cm)2) | 0 | 1 | 2 | 3 | Control group (without adding sterilizing filter) |
| Bacterial survival Rate (%) | 4.1 | 3.0 | 5.5 | 3.7 | 163.4％ |
According to the test results, the survival rate of bacteria in the culture dish without the antibacterial filter membrane under the same treatment condition reaches 163.4 percent and is increased by 63.4 percent, and the antibacterial performance of the antibacterial filter membrane subjected to the plasma grafting treatment is not attenuated and maintained at about 4 percent after the antibacterial filter membrane is used for treating tap water with different water amounts, so that the antibacterial effect of the antibacterial filter membrane is good, and the antibacterial performance stability is good.
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 (11)
1. An antibacterial filter material is characterized by comprising a filter substrate and an antibacterial agent connected to the surface of the filter substrate, wherein the antibacterial agent is a quaternary ammonium salt monomer, the quaternary ammonium salt monomer at least contains an alkyl group with the carbon atom number of more than or equal to 8, the quaternary ammonium salt monomer is connected to the surface of the filter substrate subjected to plasma treatment in a coupling grafting manner of dehydration condensation, and the filter substrate is subjected to plasma treatment in a vacuum environment or a normal pressure environment of non-polymerizable gas;
wherein the step of attaching to the surface of the filter substrate treated with plasma by means of coupling grafting by dehydration condensation comprises: according to the volume ratio of 1: (2-5) mixing a quaternary ammonium salt antibacterial agent and a tetraethyl orthosilicate coupling agent to obtain a first mixed solution; according to the mass ratio of 1: (10-30) mixing the first mixed solution with an ethanol solution with the concentration of 80% -90%, and reacting in a water bath at the temperature of 25-50 ℃ for 3-8 hours to obtain a reactive quaternary ammonium salt solution; and soaking the surface-activated base material in a reactive quaternary ammonium salt solution for more than 1 minute, reacting for at least 2 hours at the temperature of 100-120 ℃, and cleaning and drying to obtain the antibacterial filtering material.
2. The antibacterial filtering material of claim 1, wherein during the atmospheric pressure plasma treatment, the radio frequency power is 500-1000W/50 Hz, the atmospheric pressure is 0.2-0.4 MPa, and the working gas is selected from: ar, N2、O2And the processing speed is 1-20 cm/s under at least one of the conditions of compressed air.
3. The antibacterial filter material of claim 1, wherein the vacuum environment plasma treatment comprises: under the conditions that the radio frequency power is 500-1000W/40 Hz, the working pressure is 10-100 pa, and the working gas is selected from: ar, N2、O2At least one of the above, and performing vacuum plasma treatment on the substrate for 1-60 minutes under the condition that the flow rate of the working gas is 70-200 sccm.
4. The antibacterial filter material of claim 1, wherein the quaternary ammonium salt monomer contains at least one alkyl group having 8 to 20 carbon atoms.
5. The antimicrobial filter material of claim 4, wherein the quaternary ammonium salt monomer comprises: at least one of 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride and/or octadecyl dimethyl chloramine 3, 4, 4' -trichlorobiphenyl ketone diamine quaternary ammonium salt; and/or the presence of a gas in the gas,
the filtration substrate comprises: one or more of polypropylene material, polyester material, nylon, polytetrafluoroethylene, cellulose, glass fiber, silicate fiber and alumina fiber membrane.
6. The antibacterial filter material according to claim 1, wherein the quaternary ammonium salt monomer is contained in an amount of 1.0% by mass or more based on 100% by mass of the total mass of the antibacterial filter material.
7. The antibacterial filter material as claimed in any one of claims 1 to 6, wherein the antibacterial filter material has a cut-off pore size of 1 to 5 μm.
8. The antimicrobial filter material of claim 7, wherein the antimicrobial filter material comprises: a polypropylene filter membrane and the 3- (trimethoxysilyl) propyldimethyloctadecyl ammonium chloride connected to the surface of the polypropylene filter membrane; the mass percentage of the 3- (trimethoxysilyl) propyl dimethyl octadecyl ammonium chloride in the antibacterial filter material is more than 1.0%; the rejection rate of the antibacterial filter material to impurities with the particle size not less than 2 microns is more than 80%.
9. The antimicrobial filter material of claim 8 wherein said antimicrobial filter material has a rejection rate of greater than 90% for impurities having a particle size of not less than 2 microns.
10. A water purification apparatus, comprising the antibacterial filter material according to any one of claims 1 to 9.
11. An air cleaning device, characterized in that the air cleaning device comprises the antibacterial filter material as claimed in any one of claims 1 to 9.
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