CN110665374B - Preparation method of quaternary ammonium salt antibacterial material and antibacterial material prepared by preparation method - Google Patents
Preparation method of quaternary ammonium salt antibacterial material and antibacterial material prepared by preparation method Download PDFInfo
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- CN110665374B CN110665374B CN201910886659.4A CN201910886659A CN110665374B CN 110665374 B CN110665374 B CN 110665374B CN 201910886659 A CN201910886659 A CN 201910886659A CN 110665374 B CN110665374 B CN 110665374B
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Abstract
The invention belongs to the technical field of antibacterial materials, and particularly relates to a preparation method of a quaternary ammonium salt antibacterial material, which comprises the following steps: obtaining a base material; carrying out activation treatment on the base material to obtain a surface-activated base material; and (3) obtaining a reactive quaternary ammonium salt solution, and reacting the reactive quaternary ammonium salt solution with the surface activated base material to obtain the quaternary ammonium salt antibacterial material. The base material activated by the preparation method of the quaternary ammonium salt antibacterial material provided by the invention is firmly combined with the quaternary ammonium salt antibacterial agent, the damage to the base material is small, the adaptability of the base material is wide, and the antibacterial effect is stable.
Description
Technical Field
The invention belongs to the technical field of antibacterial materials, and particularly relates to a preparation method of a quaternary ammonium salt antibacterial material and the prepared antibacterial material.
Background
Along with the development of society and the improvement of living standard of people, people pay more and more attention to the harm of harmful microorganisms such as bacteria to human health and living environment. Therefore, it is becoming more and more important to actively search for antibacterial materials that are effective for a long time. The antibacterial material can be divided into inorganic antibacterial material, natural antibacterial material, organic antibacterial material and high molecular antibacterial material according to different components. The macromolecular antibacterial agent has higher active functional group density and excellent antibacterial performance, can kill bacteria through direct contact with the bacteria, does not need to release active substances, and has lasting and stable antibacterial performance, lower residual toxicity and higher safety. The macromolecular antibacterial agents according to the active functional groups are mainly divided into quaternary ammonium salts, quaternary phosphonium salts, pyridinium salts, halogenated amines, guanidine salts, chitosan and the like. The quaternary ammonium salt is typical of high molecular antibacterial agent and features its positive quaternary ammonium nitrogen ion as the center and 4 substituents and counter anions around it. The antibacterial principle of the quaternary ammonium salt high-molecular antibacterial agent is that long carbon chain groups connected with quaternary ammonium nitrogen ions can pierce bacterial lipid cell membranes to achieve the effect of killing bacteria.
At present, the method for fixing the quaternary ammonium salt high-molecular antibacterial agent on the base material has the problems of high destructiveness to the base material, high requirements on the type of the base material, unstable antibacterial effect and the like.
Disclosure of Invention
The invention aims to provide a preparation method of a quaternary ammonium salt antibacterial material, and aims to solve the technical problems that the existing preparation method of the quaternary ammonium salt antibacterial material is high in substrate destructiveness, high in substrate type requirement and unstable in antibacterial effect.
The invention also aims to provide a quaternary ammonium salt antibacterial material.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of a quaternary ammonium salt antibacterial material comprises the following preparation steps:
obtaining a base material;
carrying out activation treatment on the base material to obtain a surface-activated base material;
and (3) obtaining a reactive quaternary ammonium salt solution, and reacting the reactive quaternary ammonium salt solution with the surface activated base material to obtain the quaternary ammonium salt antibacterial material.
Preferably, the activation treatment is selected from plasma treatment; and/or the presence of a gas in the gas,
the step of reacting the reactive quaternary ammonium salt solution with the surface-activated substrate to obtain the quaternary ammonium salt antibacterial material comprises: soaking the surface-activated substrate in the reactive quaternary ammonium salt solution to obtain a soaked substrate; and then, reacting the soaked base material for 0.5-5 hours at the temperature of 80-120 ℃ to graft the reactive quaternary ammonium salt onto the surface of the base material to obtain the quaternary ammonium salt antibacterial material.
Preferably, the step of plasma treating the substrate comprises:
with Ar, N2、O2And at least one of the compressed air is working gas, and under the conditions that the processing power is 0-1000W/25 KHz, the gas pressure is 0.07-0.30 MPa and the distance between a plasma spray gun and the surface of the base material is 0.5-2.5 cm, the base material is subjected to normal-pressure plasma processing at the processing speed of 1-20 cm/s, so that the surface-activated base material is obtained.
Preferably, the step of plasma treating the substrate comprises:
with Ar, N2、O2And at least one of the compressed air is working gas, the processing power is 0-1000W/40 KHz, the gas pressure is 0-100 pa, and the flow of the working gas is 0-5 slm, the substrate is subjected to vacuum plasma processing for 0.1-30 minutes, so that the surface-activated substrate is obtained.
Preferably, the step of obtaining a reactive quaternary ammonium salt solution comprises:
obtaining quaternary ammonium salt and a coupling agent, and mixing the quaternary ammonium salt and the coupling agent to obtain a first mixed solution;
obtaining an ethanol water solution, and mixing the first mixed solution and the ethanol water solution to obtain a second mixed solution;
and reacting the second mixed solution at the temperature of 20-50 ℃ for 3-8 hours to obtain a reactive quaternary ammonium salt solution.
Preferably, the step of mixing the quaternary ammonium salt and the coupling agent comprises: according to the volume ratio of 1: (2-6) mixing the quaternary ammonium salt and the coupling agent to obtain a first mixed solution; and/or the presence of a gas in the gas,
the concentration of the ethanol water solution is 70-99%; and/or the presence of a gas in the gas,
the step of mixing the first mixed solution and the ethanol water solution comprises the following steps: according to the mass ratio of 1: (10-30) mixing the first mixed solution and the ethanol water solution to obtain a second mixed solution.
Preferably, the quaternary ammonium salts include: at least one of trimethoxysilyl-propyl dimethyl octadecyl quaternary ammonium salt, methacryloyloxyethyl-benzyl-dimethyl ammonium chloride quaternary ammonium salt, octadecyl dimethyl chloramine 3, 4, 4' -trichloro biphenyl ketone diamine quaternary ammonium salt and chitosan quaternary ammonium salt; and/or the presence of a gas in the gas,
the coupling agent is an organosilane coupling agent.
Preferably, the substrate comprises: at least one of silica glass, ceramics, stainless steel, aluminum alloy, polypropylene, polyester, nylon, polyvinyl chloride, polytetrafluoroethylene and cellulose; and/or the presence of a gas in the gas,
the shape of the substrate is selected from: at least one of strip, flat, hollow, spherical and tubular.
Preferably, the step of immersing the surface-activated substrate in the reactive quaternary ammonium salt solution comprises: soaking the surface-activated substrate in the reactive quaternary ammonium salt solution for at least 10 seconds.
Correspondingly, the quaternary ammonium salt antibacterial material is prepared by the preparation method of the quaternary ammonium salt antibacterial material.
The preparation method of the quaternary ammonium salt antibacterial material provided by the invention comprises the following steps of firstly carrying out activation treatment on the base material, activating the surface of the base material on the premise of not influencing the mechanical property of the base material, and enabling the material on the surface of the base material to generate reactive functional groups, so that the surface of the base material has reaction activity, and the selection range of the types of the base material is wide. And then, reacting the reactive quaternary ammonium salt solution with the surface activated substrate to ensure that the reactive quaternary ammonium salt attached to the substrate reacts with the activated functional group of the substrate so as to firmly combine the quaternary ammonium salt on the surface of the substrate, thereby obtaining the quaternary ammonium salt antibacterial material. The preparation method of the quaternary ammonium salt antibacterial material provided by the invention has the advantages of small damage to the base material, wide adaptability of the base material and stable antibacterial effect.
The quaternary ammonium salt antibacterial material provided by the invention is prepared by the method, and the quaternary ammonium salt antibacterial molecules are firmly combined on the surface of the base material, are uniformly distributed, have proper density, have stable and lasting antibacterial performance and good antibacterial effect.
Drawings
FIG. 1 is a graph showing the antibacterial performance test of the filters provided in examples 1 to 5 and comparative examples 1 to 4 of the present invention.
FIG. 2 is a Fourier transform infrared spectrum of the filter of example 1 of the present invention and the filter of comparative example 1.
FIG. 3 is an X-ray photoelectron spectrum of the filter of example 1 of the present invention and the filter of comparative example 1.
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 a preparation method of a quaternary ammonium salt antibacterial material, which comprises the following preparation steps:
s10, obtaining a base material;
s20, activating the base material to obtain a surface-activated base material;
s30, obtaining a reactive quaternary ammonium salt solution, and reacting the reactive quaternary ammonium salt solution with the surface activated base material to obtain the quaternary ammonium salt antibacterial material.
According to the preparation method of the quaternary ammonium salt antibacterial material provided by the embodiment of the invention, the base material is activated at first, the surface of the base material is activated on the premise of not influencing the mechanical property of the base material, and the material on the surface of the base material generates a reactive functional group, so that the surface of the base material has reaction activity, and the selection range of the type of the base material is wide. And then, reacting the reactive quaternary ammonium salt solution with the surface activated substrate to ensure that the reactive quaternary ammonium salt attached to the substrate reacts with the activated functional group of the substrate so as to firmly combine the quaternary ammonium salt on the surface of the substrate, thereby obtaining the quaternary ammonium salt antibacterial material. The preparation method of the quaternary ammonium salt antibacterial material provided by the invention has the advantages of small damage to the base material, wide adaptability of the base material and stable antibacterial effect
In a further embodiment, the preparation method of the quaternary ammonium salt antibacterial material comprises the following preparation steps:
s11, obtaining a base material;
s21, carrying out plasma treatment on the base material to obtain a surface-activated base material;
s31, obtaining a reactive quaternary ammonium salt solution, and soaking the surface-activated base material in the reactive quaternary ammonium salt solution to obtain a soaked base material; and (3) reacting the soaked base material for 0.5-5 hours at the temperature of 80-120 ℃ to graft the reactive quaternary ammonium salt onto the surface of the base material, so as to obtain the quaternary ammonium salt antibacterial material.
According to the preparation method of the quaternary ammonium salt antibacterial material provided by the embodiment of the invention, firstly, the base material is subjected to plasma treatment, the chemical structure of the material on the surface of the base material is changed by bombarding the surface of the base material by using plasma, and reactive functional groups are generated, so that the surface of the base material has reactivity. And the plasma treatment mode is adopted, so that the surface of the base material can be activated on the premise of not influencing the mechanical property of the base material, excellent conditions are provided for the surface modification of the base material, and the selection range of the type of the base material is wide. And then, fully soaking the surface-activated base material in a reactive quaternary ammonium salt solution, reacting for 0.5-5 hours at the temperature of 80-120 ℃ to enable the reactive quaternary ammonium salt attached to the base material and the activated functional group of the base material to have a grafting reaction, and after dehydration and condensation, firmly bonding the quaternary ammonium salt on the surface of the base material in a chemical bond manner to obtain the quaternary ammonium salt antibacterial material. According to the preparation method of the quaternary ammonium salt antibacterial material provided by the embodiment of the invention, the base material after plasma treatment is firmly combined with the quaternary ammonium salt antibacterial agent, the accurate customization of the molecular structure of the quaternary ammonium salt grafted on the base material and the adjustment of the antibacterial property are facilitated, the usage amount of the antibacterial agent is small, the distribution density is controllable and uniform, and the prepared quaternary ammonium salt antibacterial material is more durable and stable in antibacterial property.
Specifically, the substrate is obtained in the above step. The preparation method of the quaternary ammonium salt antibacterial material provided by the embodiment of the invention carries out plasma activation treatment on the base material, so that the surface of the base material is activated to generate the reactive functional group, therefore, the selection range of the base material provided by the embodiment of the invention is wide, and the limitation of the conventional quaternary ammonium salt antibacterial material on the type and the material of the base material is broken through.
As a preferred embodiment, the substrate comprises: at least one of silica glass, ceramic, stainless steel, aluminum alloy, polypropylene, polyester, nylon, polytetrafluoroethylene, or cellulose. The embodiment of the invention has wide selectivity for the types of the base materials, and the types of the base materials which can be treated are multiple, so long as the surface can be activated in the subsequent plasma treatment process, and the base materials include but are not limited to materials such as silica glass, ceramics, stainless steel, aluminum alloy, polypropylene, polyester, nylon, polyvinyl chloride, polytetrafluoroethylene or cellulose. The substrate may be selected as appropriate for the particular application.
As a preferred embodiment, the shape of the substrate includes: at least one of strip, flat, hollow, spherical and tubular. The embodiment of the invention has no specific requirements on the form of the base material, can be in at least one of strip, flat, hollow, spherical and tubular forms, can select the base materials with different shapes and sizes according to the application scene of the antibacterial material, and has high selection flexibility and wide adaptability.
In some embodiments, the substrate comprises: at least one of silica glass, ceramic, stainless steel, aluminum alloy, polypropylene, polyester, nylon, polyvinyl chloride, polytetrafluoroethylene, or cellulose, and the shape of the substrate comprises: at least one of strip, flat, hollow, spherical and tubular.
Specifically, in the above step, the substrate is subjected to plasma activation treatment to obtain a surface-activated substrate. According to the embodiment of the invention, the active center is directly generated on the surface of the material through plasma activation treatment, so that the base material generates reactive functional groups such as-OH and-COOH, the base material has surface activity, excellent conditions are provided for subsequent grafting of quaternary ammonium salt, the quaternary ammonium salt can be firmly grafted on the surface of the base material, and the base material is endowed with excellent antibacterial performance. In addition, the embodiment of the invention adopts plasma treatment to activate the surface of the substrate, which can not only enhance the grafting effect of the quaternary ammonium salt, but also increase the application range of the quaternary ammonium salt to the type of the substrate, namely, the quaternary ammonium salt antibacterial agent can be grafted to various material matrixes with different properties, such as silica glass, ceramics, metals, organic polymers and the like through the plasma treatment.
As a preferred embodiment, the step of plasma treating the substrate comprises: with Ar, N2、O2And taking at least one of the compressed air as a working gas, and carrying out normal-pressure plasma treatment on the substrate under the conditions that the treatment power is 0-1000W/25 KHz, the gas pressure is 0.07-0.30 MPa and the distance between a plasma spray gun and the surface of the substrate is 0.5-2.5 cm, wherein the treatment speed is 1-20 cm/s, so as to obtain the surface-activated substrate. The embodiment of the invention carries out the atmospheric plasma treatment on the base material, the atmospheric plasma treatment has low requirements on the shape and the specification of the base material, the batch treatment can be realized, the treatment efficiency is high, and the cost is lower. In the embodiment of the invention, when the processing power is 0-1000W/25 KHz, the gas pressure is 0.07-0.30 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. If the processing power is too low, the plasma density (concentration) is low and the substrate is treatedThe activation effect of the surface is not significant. If the distance between the plasma spray gun and the surface of the base material is too far, the plasma density is low, and the activation effect is poor; if the distance between the plasma spray gun and the surface of the base material is too close, the plasma density is high, the temperature is also high, the surface of the material which cannot resist high temperature can be damaged, the temperature resistance requirement of the base material is correspondingly improved, and therefore the selection of the base material is limited. If the treatment speed is too fast, the activation on the surface of the base material is insufficient; if the processing speed is too slow, the plasma density is high and the temperature is high, so that the surface of the material is easily damaged.
As a preferred embodiment, the step of subjecting the substrate to vacuum plasma treatment comprises: with Ar, N2、O2And taking at least one of the compressed air as a working gas, and carrying out vacuum plasma treatment on the substrate for 0.1-30 minutes under the conditions that the treatment power is 0-1000W/40 KHz, the gas pressure is 0-100 pa and the flow of the working gas is 0-5 slm, so as to obtain the surface-activated substrate. The embodiment of the invention carries out vacuum plasma treatment on the base material, the vacuum plasma treatment has higher activation degree on the surface of the base material, 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 be introduced in the activation process and after the activation of the surface of the base material, and the activation purity is high. In the embodiment of the invention, when the processing power is 0-1000W/40 KHz, the gas pressure is 0-100 pa, and the working gas is selected from: ar, N2、O2And at least one of compressed air and compressed air, wherein the working gas flow is 0-5 slm, the substrate is subjected to vacuum plasma treatment for 0.5-60 minutes, and the best treatment effect is achieved on the substrate. If the processing power is too low, the plasma density (concentration) is low and the activation effect on the substrate surface is insignificant. The active etching effect is increased along with the increase of the ion density caused by the increase of the working gas flow, when the ion density reaches saturation, the etching rate is not increased continuously, and when the gas flow is increased continuously, the surface activation of the material is enhanced, so that the surface roughness is increased. In addition, the material surface activation etching rate increases and then decreases with the increase of the gas pressure. If the air pressure is too small, the plasma density is reduced, and the activated etching rate is low; if the air pressure is too large, at oneUnder the condition of fixed power and gas flow, the larger the discharge impedance is, the plasma generating capability can be weakened, and even the adverse effects of no plasma generation and plasma power damage can be caused. Thus, the vacuum plasma processing conditions provided by the embodiments of the present invention have the best activation effect on the substrate surface.
Specifically, in the above steps, a reactive quaternary ammonium salt solution is obtained, and the reactive quaternary ammonium salt solution reacts with the surface-activated substrate to obtain the quaternary ammonium salt antibacterial material. In a further embodiment, the step of reacting the reactive quaternary ammonium salt solution with the surface-activated substrate to obtain the quaternary ammonium salt antibacterial material comprises: soaking the surface-activated substrate in the reactive quaternary ammonium salt solution to obtain a soaked substrate; and then, reacting the soaked base material for 0.5-5 hours at the temperature of 80-120 ℃ to graft the reactive quaternary ammonium salt onto the surface of the base material to obtain the quaternary ammonium salt antibacterial material.
Specifically, in the above steps, a reactive quaternary ammonium salt solution is obtained, and the surface-activated substrate is soaked in the reactive quaternary ammonium salt solution to obtain a soaked substrate. In the embodiment of the invention, the surface-activated base material is soaked in the reactive quaternary ammonium salt solution, so that the base material can fully adsorb the reactive quaternary ammonium salt solution. Provides a material basis for the subsequent dehydration condensation coupling reaction between the active groups on the surface of the base material and the active groups of the quaternary ammonium salt.
As a preferred embodiment, the step of obtaining a reactive quaternary ammonium salt solution comprises:
s31, obtaining a quaternary ammonium salt and a coupling agent, and mixing the quaternary ammonium salt and the coupling agent to obtain a first mixed solution;
s32, obtaining an ethanol water solution, and mixing the first mixed solution with the ethanol water solution to obtain a second mixed solution;
s33, reacting the second mixed solution at the temperature of 20-50 ℃ for 3-8 hours to obtain a reactive quaternary ammonium salt solution.
The reactive quaternary ammonium salt solution is prepared by mixing a mixed solution of quaternary ammonium salt and a coupling agent with an ethanol aqueous solution and then reacting for 3-8 hours at the temperature of 20-50 ℃, and because the quaternary ammonium salt is hydrolyzed to generate active groups such as silanol, -OH, -COOH and the like and simultaneously has dehydration condensation reaction among molecules of the quaternary ammonium salt, wherein the hydrolysis reaction and the condensation reaction are in a competitive state, the coupling agent is added and mixed with the quaternary ammonium salt, on one hand, the coupling agent can improve the bonding strength of the quaternary ammonium salt and a matrix interface, on the other hand, the effect of regulating the distribution density of the quaternary ammonium salt molecules on the matrix surface can be achieved, and the spatial effect of alkyl chain segments of the quaternary ammonium salt is enhanced, so that the antibacterial activity of the quaternary ammonium salt is improved.
Specifically, in step S31, a quaternary ammonium salt and a coupling agent are obtained, and the quaternary ammonium salt and the coupling agent are mixed to obtain a first mixed solution. According to the embodiment of the invention, the quaternary ammonium salt and the coupling agent are mixed, so that the dehydration polymerization among hydroxyl molecules after the hydrolysis of the quaternary ammonium salt can be effectively prevented, the hydrolysis of the quaternary ammonium salt is facilitated to generate a large amount of silanol, -OH, -COOH and other active groups, and the grafting efficiency of the quaternary ammonium salt and the base material can be improved more favorably through the mutual competition relationship of the coupling agent, the quaternary ammonium salt and the surface grafting reaction of the base material.
As a preferred embodiment, the step of mixing the quaternary ammonium salt and the coupling agent comprises: according to the volume ratio of 1: (2-6) mixing the quaternary ammonium salt and the coupling agent to obtain a first mixed solution. The embodiment of the invention comprises the following components in percentage by volume of 1: (2-6) mixing the quaternary ammonium salt and the coupling agent according to a mixing ratio which enables the quaternary ammonium salt to have an optimal grafting effect on the base material. If the addition proportion of the coupling agent is too high, the concentration of the quaternary ammonium salt antibacterial agent grafted on the surface of the material is reduced, and the antibacterial effect is weakened; if the addition ratio of the quaternary ammonium salt is too high, dehydration polymerization reaction between quaternary ammonium salt molecules in the hydrolysis process of the quaternary ammonium salt is enhanced, and the grafting efficiency of the antibacterial quaternary ammonium salt molecules on the substrate is also reduced, so that the antibacterial effect is reduced and the quaternary ammonium salt antibacterial agent is wasted.
As a preferred embodiment, the quaternary ammonium salt includes: at least one of trimethoxysilyl-propyl dimethyl octadecyl quaternary ammonium salt, methacryloyloxyethyl-benzyl-dimethyl ammonium chloride quaternary ammonium salt, octadecyl dimethyl chloramine 3, 4, 4' -trichloro biphenyl ketone diamine quaternary ammonium salt and chitosan quaternary ammonium salt. The quaternary ammonium salt antibacterial agent selected by the embodiment of the invention is a contact type but not a dissolution type antibacterial agent, the quaternary ammonium salt group kills bacteria through direct contact with the bacteria and does not need to release dissolution type antibacterial substances, so that the antibacterial stability is excellent and the safety performance is high. In addition, the quaternary ammonium salt adopted by the embodiment of the invention contains chemical groups which can be hydrolyzed into silanol, hydroxyl or carboxyl and the like and can be grafted and polymerized with active groups on the surface of the base material, so that the combination efficiency of the quaternary ammonium salt and the base material is improved, and the antibacterial performance of the quaternary ammonium salt antibacterial material is further ensured.
As a preferred embodiment, the coupling agent is an organosilane coupling agent. The organosilane coupling agent used in the examples of the present invention contains a group such as a chloro group, a methoxy group, an ethoxy group, a methoxyethoxy group, or an acetoxy group, and when these groups are hydrolyzed, silanol (Si (OH) is produced3) The method not only can effectively prevent intermolecular dehydration polymerization after hydrolysis of the quaternary ammonium salt, but also plays a coupling role in the grafting reaction process, and couples the quaternary ammonium salt with a material matrix, so that stable chemical bonds are generated by grafting.
In some embodiments, the quaternary ammonium salts include: at least one of trimethoxysilyl-propyl dimethyl octadecyl quaternary ammonium salt, methacryloyloxyethyl-benzyl-dimethyl ammonium chloride quaternary ammonium salt, octadecyl dimethyl chloramine 3, 4, 4' -trichloro biphenyl ketone diamine quaternary ammonium salt and chitosan quaternary ammonium salt; the coupling agent is an organosilane coupling agent.
Specifically, in step S32, an ethanol aqueous solution is obtained, and the first mixed solution and the ethanol aqueous solution are mixed to obtain a second mixed solution. According to the embodiment of the invention, the first mixed solution and the ethanol aqueous solution are mixed through mixing treatment of the first mixed solution and the ethanol aqueous solution, wherein water in the solution provides a hydrolyzing agent for hydrolysis of quaternary ammonium salt and a coupling agent; the ethanol in the ethanol aqueous solution has extremely low hydrolysis capacity on the quaternary ammonium salt and the coupling agent, can effectively control the hydrolysis speed of the quaternary ammonium salt and the coupling agent, reduces dehydration condensation of active groups such as intermolecular silanol and the like, and enables the active groups generated by hydrolysis to keep a relatively stable state. According to the embodiment of the invention, the hydrolysis process of the quaternary ammonium salt is reasonably regulated and controlled through the ethanol water solution, and dehydration condensation of active groups such as intermolecular silanol and the like caused by too fast hydrolysis of the quaternary ammonium salt is prevented, so that the quaternary ammonium salt is fully hydrolyzed to obtain the active groups such as silanol, -OH, -COOH and the like.
In a preferred embodiment, the concentration of the ethanol aqueous solution is 70% to 99%. The 70-99% ethanol aqueous solution in the embodiment of the invention is most beneficial to hydrolysis of quaternary ammonium salt, ethanol is a weaker hydrolytic agent due to weaker molecular polarity, water is a stronger hydrolytic agent, and excessive ethanol content can cause the hydrolysis of quaternary ammonium salt antibacterial molecules to be slower, thus causing poor grafting effect; too much water content results in faster hydrolysis of the antimicrobial quaternary ammonium salt molecules and faster dehydration condensation reactions between the quaternary ammonium salt molecules. Therefore, excessive or insufficient proportion is not beneficial to fully hydrolyzing the quaternary ammonium salt to obtain active groups such as-OH, -COOH and the like, while the ethanol aqueous solution with the concentration of 70-99% is most beneficial to hydrolyzing the quaternary ammonium salt, so that the grafting effect of the quaternary ammonium salt and the base material is effectively ensured, and the antibacterial performance of the antibacterial material is ensured. In some embodiments, the concentration of the aqueous ethanol solution may be 70%, 75%, 80%, 85%, 90%, and 95%.
As a preferred embodiment, the step of mixing the first mixed solution with the aqueous ethanol solution includes: according to the mass ratio of 1: (10-30) mixing the first mixed solution and the ethanol water solution to obtain a second mixed solution. The embodiment of the invention comprises the following components in percentage by mass of 1: and (10-30) mixing the first mixed solution with the ethanol water solution for treatment, and providing an optimal hydrolysis system for hydrolysis of the quaternary ammonium salt and the coupling agent in the first mixed solution. If the mixing ratio is too low, the grafting reaction of the quaternary ammonium salt molecules caused by too slow hydrolysis reaction can be incomplete; if the mixing ratio is too high, the quaternary ammonium salt molecules are hydrolyzed too quickly, resulting in a rapid dehydration polymerization reaction between the quaternary ammonium salt molecules. Therefore, too large or too small a ratio results in a decrease in the grafting effect of the quaternary ammonium salt molecules on the substrate, resulting in a decrease in the antibacterial performance. And the improper mixing treatment proportion also influences the production and manufacturing cost, and is not economical and environment-friendly. As a more preferable example, the ratio by mass is 1: (15-25) mixing the first mixed solution and the ethanol water solution to obtain a second mixed solution.
Specifically, in the step S33, the second mixed solution is reacted at a temperature of 20 to 50 ℃ for 3 to 8 hours to obtain a reactive quaternary ammonium salt solution. According to the embodiment of the invention, the second mixed solution is reacted for 3-8 hours at the temperature of 20-50 ℃, so that the full hydrolysis of the quaternary ammonium salt antibacterial molecules is ensured. If the hydrolysis temperature is too low, the hydrolysis speed of the quaternary ammonium salt is slow, the hydrolysis rate is increased along with the increase of the temperature, but when the temperature exceeds a certain value, the self-condensation reaction of the coupling agent and silanol and other active groups generated by the hydrolysis of the quaternary ammonium salt can cause the content of the silanol and other active groups of the system to be reduced, and the subsequent grafting reaction with the base material is not facilitated, so that the antibacterial performance of the antibacterial material is reduced.
In some embodiments, the second mixed solution is reacted at a temperature of 30 ℃ for 4 hours to obtain a reactive quaternary ammonium salt solution.
As a preferred embodiment, the step of immersing the surface-activated substrate in the reactive quaternary ammonium salt solution comprises: soaking the surface-activated substrate in the reactive quaternary ammonium salt solution for at least 10 seconds. In the embodiment of the invention, the surface-activated substrate is soaked in the reactive quaternary ammonium salt solution for at least 10 seconds, so that quaternary ammonium salt molecules in the quaternary ammonium salt solution are fully attached to the substrate, and a material basis is provided for the subsequent grafting reaction of the quaternary ammonium salt and the substrate. As a more preferred embodiment, the surface-activated substrate is soaked in the reactive quaternary ammonium salt solution for at least 1 minute to allow the reactive quaternary ammonium salt solution to penetrate into and out of the substrate more sufficiently.
Specifically, in the above steps, the soaked base material is reacted for 0.5-5 hours at a temperature of 80-120 ℃ to obtain the quaternary ammonium salt antibacterial material. The grafting condition of the embodiment of the invention is most favorable for the grafting dehydration condensation reaction of the quaternary ammonium salt molecules and the base material under the condition that the temperature is 80-120 ℃ and the reaction time is 0.5-5 hours. The reaction temperature is a key factor for ensuring that the grafting reaction is carried out and controlling the grafting reaction rate within a certain range. The grafting can not be carried out due to the excessively low reaction temperature, the antibacterial performance of the material is improved along with the increase of the heat treatment temperature, which indicates that the grafting reaction tends to be complete, but if the temperature exceeds 120 ℃, thermal decomposition can occur, the molecular chain of the quaternary ammonium salt is damaged, and the antibacterial performance of the material is reduced. The reaction time ensures sufficient completion of the grafting reaction.
The embodiment of the invention also provides a quaternary ammonium salt antibacterial material, and the quaternary ammonium salt antibacterial material is prepared by the preparation method of the quaternary ammonium salt antibacterial material.
The quaternary ammonium salt antibacterial material provided by the embodiment of the invention is prepared by the method, and the quaternary ammonium salt antibacterial molecules are firmly combined on the surface of the base material, are uniformly distributed, have proper density, have stable and lasting antibacterial performance and have good antibacterial effect.
In order to make the above implementation details and operations of the present invention clearly understood by those skilled in the art and to make the progress of the quaternary ammonium salt antibacterial material and the preparation method thereof obvious, the above technical solutions are illustrated by the following examples.
Example 1
A preparation method of a quaternary ammonium salt antibacterial glass fiber filter membrane comprises the following steps:
s10, obtaining a 0.35 mm-thick glass fiber filter membrane, and performing 1-time normal-pressure plasma treatment on the glass fiber filter membrane under the conditions that the power is 750W/25HKz, the gas pressure is 0.2MPa, the treatment speed is 6cm/s, the treatment height is 1.5cm, and the working gas is dry compressed air to obtain the surface-activated substrate.
S20, obtaining a reactive quaternary ammonium salt solution: mixing the quaternary ammonium salt (3- (trimethoxysilyl) propyl dimethyloctadecyl ammonium chloride, the same below) and the coupling agent (tetraethyl orthosilicate, the same below) according to the volume ratio of 1:3 to obtain a first mixed solution; and mixing the first mixed solution with an ethanol water solution with the concentration of 90% according to the mass ratio of 1:19, and reacting for 4.5 hours at the temperature of 30 ℃ to obtain a reactive quaternary ammonium salt solution.
S30, soaking the surface-activated base material in a reactive quaternary ammonium salt solution for 2 minutes, reacting for 2 hours at the temperature of 120 ℃, and cleaning and drying to obtain the quaternary ammonium salt antibacterial glass fiber filter membrane.
FTIR and XPS tests show that the treated quaternary ammonium salt is grafted to common non-woven fabric to form the quaternary ammonium salt-loaded filter membrane (other embodiments test in the same way and all show that the quaternary ammonium salt-loaded filter membrane is formed).
As shown in FIG. 2, a Fourier transform Infrared Spectroscopy (FTIR) chart, in which the C ═ O stretching peak was 1727cm, since the filter membrane of example 1 and the filter membrane of comparative example 1 both contained an acrylic binder-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 at 399.7eV because nitrogen gas is ionized during plasma treatment and then sputtered into the nonwoven matrix material to form 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.
Example 2
A preparation method of a quaternary ammonium salt antibacterial glass fiber filter membrane comprises the following steps:
s10, obtaining a 0.35 mm-thick glass fiber filter membrane, and performing 1-time normal-pressure plasma treatment on the glass fiber filter membrane under the conditions that the power is 850W/25HKz, the gas pressure is 0.2MPa, the treatment speed is 6cm/s, the treatment height is 2.0cm, and the working gas is dry compressed air to obtain the surface-activated substrate.
S20, obtaining a reactive quaternary ammonium salt solution: mixing the quaternary ammonium salt and the coupling agent according to the volume ratio of 1:3 to obtain a first mixed solution; and mixing the first mixed solution with an ethanol water solution with the concentration of 90% according to the mass ratio of 1:19, and reacting for 4.5 hours at the temperature of 30 ℃ to obtain a reactive quaternary ammonium salt solution.
S30, soaking the surface-activated base material in a reactive quaternary ammonium salt solution for 2 minutes, reacting for 2 hours at the temperature of 120 ℃, and cleaning and drying to obtain the quaternary ammonium salt antibacterial glass fiber filter membrane.
Example 3
A preparation method of a quaternary ammonium salt antibacterial glass fiber filter membrane comprises the following steps:
s10, obtaining a 0.35 mm-thick glass fiber filter membrane, and performing 1-time normal-pressure plasma treatment on the glass fiber filter membrane under the conditions that the power is 550W/25HKz, the gas pressure is 0.2MPa, the treatment speed is 5cm/s, the treatment height is 2.5cm, and the working gas is dry compressed air to obtain the surface-activated substrate.
S20, obtaining a reactive quaternary ammonium salt solution: mixing the quaternary ammonium salt and the coupling agent according to the volume ratio of 1:3 to obtain a first mixed solution; and mixing the first mixed solution with an ethanol water solution with the concentration of 90% according to the mass ratio of 1:19, and reacting for 4.5 hours at the temperature of 30 ℃ to obtain a reactive quaternary ammonium salt solution. .
S30, soaking the surface-activated base material in a reactive quaternary ammonium salt solution for 2 minutes, reacting for 2 hours at the temperature of 120 ℃, and cleaning and drying to obtain the quaternary ammonium salt antibacterial glass fiber filter membrane.
Example 4
A quaternary ammonium salt antibacterial composite glass fiber filter membrane is prepared by the following steps:
s10, obtaining a 0.5 mm-thick glass fiber filter membrane wrapped with polyester non-woven fabric, and performing treatment at a power of 1000W/25HKz, a gas pressure of 0.15MPa, a treatment speed of 4cm/s, a treatment height of 2.0cm and a working gas: the dried 4 parts of argon gas and 1 part of oxygen gas were mixed and subjected to atmospheric pressure plasma treatment 1 time to obtain a surface-activated substrate.
S20, obtaining a reactive quaternary ammonium salt solution: mixing the quaternary ammonium salt and the coupling agent according to the volume ratio of 1:3 to obtain a first mixed solution; and mixing the first mixed solution with an ethanol water solution with the concentration of 90% according to the mass ratio of 1:19, and reacting for 4.5 hours at the temperature of 30 ℃ to obtain a reactive quaternary ammonium salt solution.
S30, soaking the surface-activated base material in a reactive quaternary ammonium salt solution for 2 minutes, reacting for 2 hours at the temperature of 120 ℃, and cleaning and drying to obtain the quaternary ammonium salt antibacterial composite glass fiber filter membrane.
Example 5
A quaternary ammonium salt antibacterial composite glass fiber filter membrane is prepared by the following steps:
s10, obtaining a polyester non-woven fabric glass fiber filter membrane with the thickness of 0.5 mm, and performing treatment at the power of 550W/25HKz, the gas pressure of 0.15MPa, the treatment speed of 3cm/s, the treatment height of 1.5cm and the working gas: and (3) carrying out 1 time of normal pressure plasma treatment on the dried compressed air under the condition that the working gas is the dried compressed air to obtain the surface activated substrate.
S20, obtaining a reactive quaternary ammonium salt solution: mixing the quaternary ammonium salt and the coupling agent according to the volume ratio of 1:3 to obtain a first mixed solution; and mixing the first mixed solution with an ethanol water solution with the concentration of 90% according to the mass ratio of 1:19, and reacting for 4.5 hours at the temperature of 30 ℃ to obtain a reactive quaternary ammonium salt solution.
S30, soaking the surface-activated base material in a reactive quaternary ammonium salt solution for 2 minutes, reacting for 2 hours at the temperature of 120 ℃, and cleaning and drying to obtain the quaternary ammonium salt antibacterial composite glass fiber filter membrane.
Comparative example 1
Glass fiber filter membrane without any treatment.
Comparative example 2
And (3) preparing the raw membrane of the composite glass fiber filter membrane without any treatment.
Comparative example 3
The modified glass fiber filter membrane is prepared by directly treating the reactive quaternary ammonium salt solution without any activation pretreatment. The other specific parameters are the same as those in example 1.
Comparative example 4
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 1, and the ordinary inorganic glass fiber nonwoven fabric film was subjected to acid-base treatment of the grafted quaternary ammonium salt nonwoven fabric.
In order to verify the advancement of the quaternary ammonium salt antibacterial glass fiber filter membranes prepared in the embodiments 1 to 3 and the quaternary ammonium salt antibacterial composite glass fiber filter membranes prepared in the embodiments 4 and 5, an antibacterial performance test is performed in the embodiments of the present invention.
Test example 1
And (4) adopting a filter membrane method to evaluate the antibacterial performance of the glass fiber filter membrane before and after treatment. Cutting the filter membranes of the embodiments 1-5 and the comparative examples 1-4 into disks with the diameter of 45mm, sterilizing, respectively placing the disks into a sterilized Buchner funnel, performing suction filtration on 600mL of bacteria-containing water containing 4000-. The medium was inverted and cultured in an incubator at 37. + -. 1 ℃ for 48 h. And observing the bacteria growing condition around the surface area of the membrane sample, wherein the less bacteria growing on the surface and around the sample indicates the better antibacterial effect.
The test results are shown in the attached figure 1, almost no obvious bacterial colony grows around the filter membranes prepared in the embodiments 1-5 of the invention, the antibacterial boundary is clear, and the surfaces and the surroundings of the membranes of the comparative examples 1-4 which are not treated completely grow bacterial colonies, which shows that the antibacterial material prepared by the method provided by the invention has excellent antibacterial performance and the performance of inhibiting the growth and the reproduction of bacteria. Compared with the glass fiber filter membrane which is not treated, the comparative example 3 and the comparative example 4 which are treated also have certain antibacterial effect.
Test example 2
Further, the stability of the quaternary ammonium salt antibacterial glass fiber filter membrane prepared in example 1 was tested.
The antibacterial filter membrane of the embodiment 1 is placed in a membrane pool to simulate the use scene of an actual filter element, tap water is used for filtering the antibacterial filter membrane, and the antibacterial filter membrane with the same area (per square centimeter) is quantitatively tested after 0L, 100L, 300L and 500L of tap water (0L/cm) are respectively filtered by the antibacterial filter membrane2，100L/m2，300L/m2，500L/m2) Stability of antibacterial property. 0.75 g of the filtered antibacterial filter membrane is taken out, and is respectively put into solution containers with the same bacteria concentration, and oscillation antibacterial treatment is carried out for 20 minutes at 35 ℃. After the oscillation is finished, the solution is taken out, cultured for 48 hours at 37 +/-1 ℃, the number of bacteria in the culture dish is counted, and the antibacterial effect of the antibacterial filtering membranes for filtering different water amounts is compared.
The control group was prepared by shaking-sterilizing at 35 ℃ for 20 minutes in a solution container of the same bacterial solution concentration without adding an antibacterial filter membrane. After the shaking was completed, the solution was taken out, incubated at 37. + -. 1 ℃ for 48 hours, and then the number of bacteria in the dish was counted.
The survival rate of bacteria can be calculated according to the formula: the survival rate of bacteria was 100% as the number of bacteria after shaking/the number of bacteria before shaking, and the calculation results are shown in table 1 below:
TABLE 1
| Amount of Water flushed (L/m)2) | 0 | 100 | 300 | 500 | Control group (without adding antibacterial 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 filtering membrane reaches 163.4% and is increased by 63.4% under the same test conditions, and after the antibacterial filtering membrane subjected to antibacterial treatment filters tap water with different water amounts, the antibacterial performance of the antibacterial filtering membrane is not attenuated, and the survival rate of bacteria is only about 4%, which shows that the antibacterial filtering membrane not only has a good antibacterial effect, but also has good stability of antibacterial performance.
Test example 3
Further, the surface Zeta potentials of the quaternary ammonium salt antibacterial glass fiber filter membranes prepared in the example 1 and the comparative example 3 after different water passing amounts are tested.
The method of example 1,The antibacterial filtering membrane of comparative example 3 was placed in a membrane tank to simulate the actual use of the filter, the antibacterial filtering membrane was filtered with tap water, and it was tested that the antibacterial filtering membrane filters 0L, 1L, 2L and 3L of tap water (0L/cm) respectively at the same area (per square centimeter)2，100L/m2，300L/m2，500L/m2) Surface Zeta potential of (2).
The Zeta potential on the surface of the solid can reflect the surface charge and the charge intensity of the material, and is an effective means for representing the antibacterial capability of the surface of the material. The membrane samples were tested for surface Zeta potential using a solid surface Zeta potential meter (surfass model 3) from austria apopa with KCl as the measurement medium and a measured pH of 7, the test results being shown in table 2 below:
TABLE 2
| Amount of Water flushed (L/m)2) | Example 1 | Comparative example 3 |
| 0 | 46.31mV | 35.94mV |
| 100 | 18.65mV | 12.055mV |
| 300 | 9.19mV | 4.025 |
| 500 | 10.5mV | 0.865mV |
From the test results, it is understood that the initial Zeta potential of example 1 is higher than that of comparative example 3 under the same test conditions, indicating that the antibacterial filtration membrane of example 1 has a stronger attraction to negatively charged bacteria and a higher antibacterial ability. The Zeta potential of the comparative example 3 is more obviously reduced along with the increase of the water washing amount, compared with the same water washing amount, the Zeta potential value of the comparative example 3 antibacterial film is lower than that of the example 1, and the Zeta potential value of the comparative example 3 antibacterial film is 500L/m at the water washing amount2In this case, the Zeta potential of comparative example 3 was almost decreased to be nearly negative, indicating that the antibacterial filtering membrane surface at this time almost lost the ability to attract bacteria. From the above analysis it follows that: comparative example 3 the antibacterial stability of the antibacterial film was lower than that of example 1.
Test example 4
Further, the quaternary ammonium salt antibacterial glass fiber filter membranes prepared in the example 1 and the comparative example 4 are subjected to a sanitation safety test and a stability evaluation.
The increase amounts of Total Organic Carbon (TOC) and oxygen Consumption (COD) in the immersion water of comparative example 1 and comparative example 4 were examined using GBT17219-2001 drinking water delivery and distribution equipment and protective material safety evaluation criteria as evaluation criteria, and the test results are shown in table 3 below:
TABLE 3
From the test results, under the same test conditions, the TOC and COD increases of the soaking water of the modified glass fiber filter membrane prepared by the acid-base surface activation pretreatment of the example 1 and the comparative example 4 and the chemical grafting treatment of the reactive quaternary ammonium salt solvent are less than or equal to 1 and meet the GBT17219-2001 standard, but the TOC and COD increases of the comparative example 4 are higher than the increases of the example 1. This reflects that comparative example 4 is also less stable in aqueous environments than example 1.
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 (14)
1. The preparation method of the quaternary ammonium salt antibacterial material is characterized by comprising the following preparation steps:
obtaining a base material;
carrying out plasma activation treatment on the base material to obtain a surface-activated base material;
obtaining a reactive quaternary ammonium salt solution, and reacting the reactive quaternary ammonium salt solution with the surface activated substrate to couple and graft quaternary ammonium salt on the surface of the substrate to obtain a quaternary ammonium salt antibacterial material, wherein a coupling agent and an antibacterial agent are mixed in ethanol to form the reactive quaternary ammonium salt solution;
the step of obtaining a reactive quaternary ammonium salt solution comprises: s1, obtaining a quaternary ammonium salt and a coupling agent, and mixing the quaternary ammonium salt and the coupling agent to obtain a first mixed solution; s2, obtaining an ethanol water solution, and mixing the first mixed solution with the ethanol water solution to obtain a second mixed solution; and S3, reacting the second mixed solution at the temperature of 20-50 ℃ for 3-8 hours to obtain a reactive quaternary ammonium salt solution.
2. The method according to claim 1, wherein the ethanol is an aqueous ethanol solution having a concentration of 70% to 99%.
3. The method according to claim 1, wherein the step of mixing the quaternary ammonium salt and the coupling agent comprises a step of mixing the quaternary ammonium salt and the coupling agent in a volume ratio of 1: (2-6) mixing the quaternary ammonium salt and the coupling agent to obtain a first mixed solution.
4. The method according to claim 2, wherein the ratio by mass of the components is 1: (10-30) mixing the first mixed solution with the ethanol water solution to obtain a second mixed solution.
5. The method according to claim 4, wherein the ratio by mass of the components is 1: (15-25) mixing the first mixed solution and the ethanol water solution to obtain a second mixed solution.
6. The method for preparing a quaternary ammonium salt antibacterial material according to claim 1, wherein the activation treatment is selected from the group consisting of plasma treatment; and/or the presence of a gas in the gas,
the step of reacting the reactive quaternary ammonium salt solution with the surface-activated substrate to obtain the quaternary ammonium salt antibacterial material comprises: soaking the surface-activated substrate in the reactive quaternary ammonium salt solution to obtain a soaked substrate; and then, reacting the soaked base material for 0.5-5 hours at the temperature of 80-120 ℃ to graft the reactive quaternary ammonium salt onto the surface of the base material to obtain the quaternary ammonium salt antibacterial material.
7. The method of preparing a quaternary ammonium salt antibacterial material according to claim 1, wherein the step of subjecting the substrate to plasma treatment comprises:
with Ar, N2、O2And at least one of the compressed air is working gas, and under the conditions that the processing power is 0-1000W/25 KHz, the gas pressure is 0.07-0.30 MPa and the distance between a plasma spray gun and the surface of the base material is 0.5-2.5 cm, carrying out plasma processing on the base material at the processing speed of 1-20 cm/s to obtain the surface-activated base material.
8. The method of preparing a quaternary ammonium salt antibacterial material according to claim 1, wherein the step of subjecting the substrate to plasma treatment comprises:
with Ar, N2、O2At least one of the compressed air is working gas, the processing power is 0-1000W/40 KHz, the gas pressure is 0-100 pa, and the flow of the working gas is 0-5 slAnd m, carrying out vacuum plasma treatment on the base material for 0.1-30 minutes to obtain the surface activated base material.
9. The method for preparing the quaternary ammonium salt antibacterial material according to any one of claims 1 to 8, wherein the step of obtaining the reactive quaternary ammonium salt solution comprises:
obtaining quaternary ammonium salt and a coupling agent, and mixing the quaternary ammonium salt and the coupling agent to obtain a first mixed solution;
obtaining an ethanol water solution, and mixing the first mixed solution and the ethanol water solution to obtain a second mixed solution;
and reacting the second mixed solution at the temperature of 20-50 ℃ for 3-8 hours to obtain a reactive quaternary ammonium salt solution.
10. The method for preparing a quaternary ammonium salt antibacterial material according to claim 9, wherein the step of mixing the quaternary ammonium salt and the coupling agent comprises: according to the volume ratio of 1: (2-6) mixing the quaternary ammonium salt and the coupling agent to obtain a first mixed solution; and/or the presence of a gas in the gas,
the concentration of the ethanol water solution is 70-99%; and/or the presence of a gas in the gas,
the step of mixing the first mixed solution and the ethanol water solution comprises the following steps: according to the mass ratio of 1: (10-30) mixing the first mixed solution and the ethanol water solution to obtain a second mixed solution.
11. The method for preparing a quaternary ammonium salt antibacterial material according to claim 9, wherein the quaternary ammonium salt comprises: at least one of trimethoxysilyl-propyl dimethyl octadecyl quaternary ammonium salt, methacryloyloxyethyl-benzyl-dimethyl ammonium chloride quaternary ammonium salt, octadecyl dimethyl chloramine 3, 4, 4' -trichloro biphenyl ketone diamine quaternary ammonium salt and chitosan quaternary ammonium salt; and/or the presence of a gas in the gas,
the coupling agent is an organosilane coupling agent.
12. The method for preparing a quaternary ammonium salt antibacterial material according to any one of claims 1 to 8 and 10 to 11, wherein the base material comprises: at least one of silica glass, ceramics, stainless steel, aluminum alloy, polypropylene, polyester, nylon, polyvinyl chloride, polytetrafluoroethylene and cellulose; and/or the presence of a gas in the gas,
the shape of the substrate includes: at least one of strip, flat, hollow, spherical and tubular.
13. The method for preparing a quaternary ammonium salt antibacterial material according to any one of claims 6 to 8, wherein the step of immersing the surface-activated base material in the reactive quaternary ammonium salt solution comprises: soaking the surface-activated substrate in the reactive quaternary ammonium salt solution for at least 10 seconds.
14. A quaternary ammonium salt antibacterial material, which is characterized by being prepared by the preparation method of the quaternary ammonium salt antibacterial material as claimed in any one of claims 1 to 13.
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