CN112225832A - Antibacterial agent, preparation method and antibacterial application in plastics, textiles and coatings - Google Patents
Antibacterial agent, preparation method and antibacterial application in plastics, textiles and coatings Download PDFInfo
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Abstract
The invention discloses an antibacterial agent, a preparation method and antibacterial application in plastics, textiles and coatings. The preparation method of the antibacterial agent comprises the following steps: mixing chitosan quaternary ammonium salt, grafting monomer, polymerization inhibitor, initiator and nano TiO2Dissolving in 10-30ml of deionized water, stirring uniformly, and heating to react at 110-150 ℃ for 5-20 min; and after the reaction is finished, washing and drying. The antibacterial agent prepared by the invention has good antibacterial performance, wear resistance and heat resistance. The antibacterial agent has complementary advantages, synergistic effect and effectively improved antibacterial property.
Description
Technical Field
The invention relates to the technical field of antibiosis, in particular to an antibacterial agent, a preparation method and antibacterial application in plastics, textiles and coatings.
Background
Along with the rapid development of economy, people pay more and more attention to their health, so that the requirements on cleanliness of clothes, articles for daily use, life and working environments and the like are higher and higher. Tools and appliances frequently touched by people, such as buses, office and room furniture, electrical equipment, toys and the like, are easy to breed bacteria and become a transmission way for pathogens to enter the human body to cause diseases. Therefore, antibacterial agents have been recently studied, and the growth and propagation of microorganisms such as bacteria have been greatly reduced.
Currently, antibacterial agents are classified into inorganic antibacterial agents, organic antibacterial agents, natural antibacterial agents, and other antibacterial agents. The inorganic antibacterial agent is mainly composed of metal ions and metal oxides, has good antibacterial properties, and has higher heat resistance than general antibacterial agents. The natural antibacterial agent is prepared from natural extract by extracting and modifying to obtain antibacterial agent, such as chitosan, chitin, hinokitiol, folium Artemisiae Argyi, Aloe, etc. with antibacterial activity. The chitosan is rich in natural storage capacity, widely exists in shells of lower animals and cell walls of lower plants and bacteria such as algae, fungi and fungi, has stable chemical properties, good biocompatibility, biodegradability, no toxicity and antibacterial activity, and is widely applied to various fields. The chitosan is insoluble in water and organic solvent, and only soluble in acid solution, so that the application range of the chitosan is greatly limited. Therefore, it is very important to modify chitosan to improve its water solubility, antibacterial property and heat resistance.
Disclosure of Invention
Based on the research background and thought, the complete technical scheme of the invention is formed as follows:
a method for preparing an antibacterial agent comprising the steps of:
1-3g of chitosan is dispersed in 100-300ml of isopropanol for ultrasonic treatment; then adding 5-9g of cross-linking agent, and reacting for 2-5h at 50-80 ℃; and (5) washing and drying.
Preferably, a method for preparing an antibacterial agent comprises the steps of:
dispersing 1-3g of chitosan in 100-300ml of isopropanol for ultrasonic treatment, wherein the ultrasonic power is 50-70W, and the ultrasonic time is 20-50 min; adding 5-9g of cross-linking agent, reacting at 50-80 ℃ for 2-5h, washing and drying.
The cross-linking agent is one or two of hexadecyl epoxy propyl dimethyl ammonium chloride and 2, 3-epoxy propyl trimethyl ammonium chloride.
According to the invention, chitosan quaternary ammonium salt is prepared by reacting chitosan with a cross-linking agent of hexadecyl epoxy propyl dimethyl ammonium chloride or 2, 3-epoxy propyl trimethyl ammonium chloride, and the problem of poor antibacterial effect of the existing antibacterial agent can be effectively improved by preparing the chitosan quaternary ammonium salt containing long chains.
The inventor further finds that although the antibacterial agent is resistant to nonionic surfactants and cationic surfactants, when anionic surfactants exist, the cationic quaternary ammonium salt is easy to combine with the anionic surfactants, and the antibacterial function is lost. The inventor finds that the grafting monomer is introduced to the long-chain chitosan quaternary ammonium salt, so that the prepared chitosan quaternary ammonium salt contains active groups and new antibacterial groups, and the antibacterial performance of the cationic chitosan quaternary ammonium salt can be improved while the antibacterial durability is maintained. The following protocol was further developed.
Preferably, a method for preparing an antibacterial agent comprises the steps of:
dispersing 1-3g of chitosan in 100-300ml of isopropanol for ultrasonic treatment, wherein the ultrasonic power is 50-70W, and the ultrasonic time is 20-50 min; adding 5-9g of cross-linking agent, stirring uniformly, and reacting for 2-5h at 50-80 ℃; after the reaction is finished, washing and drying to obtain chitosan quaternary ammonium salt;
dissolving 0.8-1.5g of the chitosan quaternary ammonium salt, 3-5g of the grafting monomer, 0.005-0.02g of the polymerization inhibitor and 0.25-0.7g of the initiator in 10-30ml of deionized water, uniformly stirring, and heating and reacting at 110-150 ℃ for 5-20 min; and after the reaction is finished, washing and drying.
The grafting monomer is one or a mixture of citric acid, dimethylaminopropylamine, acrylic acid, N-hydroxyethyl acrylamide and hydroxybenzoic acid. Preferably, the grafting monomer is citric acid and N-hydroxyethyl acrylamide in a mass ratio of (1-3): (1-3).
The initiator is one of ammonium persulfate, potassium sulfate, ammonium chloride and ferrous sulfate.
The polymerization inhibitor is one of 4-methoxyphenol and hydroquinone.
The cross-linking agent is one or two of hexadecyl epoxy propyl dimethyl ammonium chloride and 2, 3-epoxy propyl trimethyl ammonium chloride.
Based on the above, the inventors have further studied and improved the synthesized reactive chitosan quaternary ammonium salt, and found that the synthesized reactive chitosan quaternary ammonium salt and the nanometerTiO2The compounding can effectively improve the problems of heat resistance and antibacterial property. The possible reasons for this are: synthesized reactive chitosan quaternary ammonium salt and nano TiO2The compounding can make up for the deficiencies among various antibacterial agents, improve antibacterial property and wear resistance and endow uvioresistant performance. But nano TiO2The surface exposed atoms enable the surface of the particles to be very large and are very easy to be in a thermodynamic unstable state, and the particles are adhered and agglomerated by hydrogen bonds, intermolecular acting force and the like, so that the antibacterial performance is influenced. On the basis of the above, a modifier is added to the nano TiO2Can effectively improve the nano TiO by modification2Easy agglomeration and can improve the preparation of reactive chitosan quaternary ammonium salt/nano TiO2Stability of the composite reaction system.
Preferably, a method for preparing an antibacterial agent comprises the steps of:
dispersing 1-3g of chitosan in 100-300ml of isopropanol for ultrasonic treatment, wherein the ultrasonic power is 50-70W, and the ultrasonic time is 20-50 min; adding 5-9g of cross-linking agent, stirring uniformly, and reacting for 2-5h at 50-80 ℃; after the reaction is finished, washing and drying to obtain chitosan quaternary ammonium salt;
0.8-1.5g of the chitosan quaternary ammonium salt, 3-5g of grafting monomer, 0.005-0.02g of polymerization inhibitor, 0.25-0.7g of initiator and 0.01-0.03g of nano TiO2Dissolving in 10-30ml deionized water, stirring uniformly, and heating and reacting at 110-150 ℃ for 5-20 min; and after the reaction is finished, washing and drying.
Preferably, the nano TiO2For modifying nano TiO2The preparation method comprises the following steps: 0.3-0.5g of nano TiO2And 0.01-0.03g of hexadecyl epoxy propyl dimethyl ammonium chloride are placed in 80-100ml of deionized water for ultrasonic dispersion with the ultrasonic power of 50-70W and the ultrasonic time of 10-30min, and the modified nano TiO is obtained by centrifugal separation and drying2。
The invention also discloses an antibacterial agent prepared by the method.
The invention also discloses an antibacterial application of the antibacterial agent in plastics, textiles and coatings.
The invention has the beneficial effects that:
compared with the prior art, in the preparation method of the antibacterial agent, hexadecyl epoxy propyl dimethyl ammonium chloride is introduced into chitosan to prepare the chitosan quaternary ammonium salt, and then reactive groups are introduced into the chitosan quaternary ammonium salt molecules to synthesize the reactive chitosan quaternary ammonium salt. Meanwhile, synthesized reactive chitosan quaternary ammonium salt and nano TiO are adopted2Compounding to improve antibacterial property and endow anti-ultraviolet property.
The antibacterial agent is reactive chitosan quaternary ammonium salt/nano TiO2Good antibacterial properties are exhibited, which may be due to:
(1) the antibacterial activity of the N-long alkyl chitosan quaternary ammonium salt is influenced by the length of an alkyl chain due to the introduction of hexadecyl epoxy propyl dimethyl ammonium chloride, and the longer the length of the alkyl chain, the higher the antibacterial activity. The reason is that the quaternary ammonium salt molecules are positively charged, so that the adsorption of negatively charged bacteria is facilitated, and the long-chain quaternary ammonium salt enables the bacteria to be adsorbed on the surface of the antibacterial agent due to the existence of the long-chain alkyl structure, penetrates the interior of a cell body, and is leaked from the cytoplasm of the bacteria, so that the antibacterial performance is enhanced.
(2) The grafting monomer citric acid and N-hydroxyethyl acrylamide are introduced to the long-chain chitosan quaternary ammonium salt, so that the prepared chitosan quaternary ammonium salt contains active groups and new antibacterial groups, and the cationic chitosan quaternary ammonium salt can improve the antibacterial performance and keep the antibacterial durability under the synergistic action of the active groups and the new antibacterial groups.
(3) Is modified nano TiO2The reactive chitosan quaternary ammonium salt is introduced, so that the antibacterial property and the wear resistance are effectively improved, and the uvioresistant performance is endowed. Nano TiO modified by hexadecyl epoxy propyl dimethyl ammonium chloride2On the one hand, the easy-to-agglomerate nano TiO is improved2The dispersibility of the polymer is simultaneously to nano TiO2Modifying to endow the quaternary ammonium salt with antibacterial property and obtain antibacterial durability; on the other hand, the preparation of reactive chitosan quaternary ammonium salt/nano TiO can be improved2Stability of the composite reaction system.
(4) Is reactive chitosan quaternary ammonium salt/nano TiO2Nano TiO introduced therein2Reaction ofQuaternary ammonium salt of chitosan and nano TiO2the-OH on the surface generates hydrogen bonds to limit the nano TiO2By movement of (2) to make the nano TiO2The distribution is uniform on the whole system. At the same time, nano TiO2Irradiating TiO with light2The electrons break through the forbidden band limitation to form electron-hole pairs which are easy to be adsorbed on the nano TiO2O of the surface2、OH-、H2O is combined to form O2 -OH, these extremely active free radicals can effectively destroy the cell structure and inhibit the growth of the cell. Reactive chitosan quaternary ammonium salt and nano TiO2The synergistic effect can obviously improve the antibacterial property, improve the heat resistance and keep the antibacterial durability. The antibacterial agent has complementary advantages, synergia and effectively improved antibacterial property.
Detailed Description
In order to more clearly illustrate the technical solution of the present invention, the technical solution of the present invention will be further illustrated with reference to the following specific embodiments:
and (3) chitosan: the deacetylation degree is 90.5 percent, the relative molecular mass is 50.4 ten thousand, and the product is purchased from Yuhuan ocean biochemistry Co., Ltd, Zhejiang;
nano TiO 22Model number TTP-A10, primary particle size 10nm, available from Nanjing Tianxing New Material Co., Ltd.
The hexadecyl epoxypropyl dimethyl ammonium chloride in the embodiment can be prepared by referring to a 1.2 synthesis method of quaternary ammonium modification and application of hyperbranched polyester in terylene decrement (tomming, Shenli, chemmer & ltprinting & dyeing & gt 2012). The chemical structural formula is as follows:
| name of raw materials | CAS number |
| Isopropanol (I-propanol) | 67-63-0 |
| Citric acid | 77-92-9 |
| Ammonium persulfate | 7727-54-0 |
| 4-methoxyphenol | 150-76-5 |
| N-hydroxyethyl acrylamide | 7646-67-5 |
Example 1
A method for preparing an antibacterial agent comprising the steps of:
dispersing 1.5g of chitosan in 250ml of isopropanol for ultrasonic treatment, wherein the ultrasonic power is 65W, and the ultrasonic time is 30 min; adding 7g of cross-linking agent cetyl epoxypropyl dimethyl ammonium chloride, uniformly stirring, and reacting for 3h at 60 ℃; and (5) after the reaction is finished, washing and drying.
Example 2
A method for preparing an antibacterial agent comprising the steps of:
dispersing 1.5g of chitosan in 250ml of isopropanol for ultrasonic treatment, wherein the ultrasonic power is 65W, and the ultrasonic time is 30 min; adding 7g of cross-linking agent cetyl epoxypropyl dimethyl ammonium chloride, uniformly stirring, and reacting for 3h at 60 ℃; after the reaction is finished, washing and drying to obtain chitosan quaternary ammonium salt;
dissolving 1.5g of the chitosan quaternary ammonium salt, 4g of the grafting monomer, 0.01g of the polymerization inhibitor and 0.4g of the initiator in 20ml of deionized water, uniformly stirring, and heating and reacting at 130 ℃ for 5 min; and after the reaction is finished, washing and drying.
The grafting monomer is citric acid;
the initiator is ammonium persulfate;
the polymerization inhibitor is 4-methoxyphenol.
Example 3
A method for preparing an antibacterial agent comprising the steps of:
dispersing 1.5g of chitosan in 250ml of isopropanol for ultrasonic treatment, wherein the ultrasonic power is 65W, and the ultrasonic time is 30 min; adding 7g of cross-linking agent cetyl epoxypropyl dimethyl ammonium chloride, uniformly stirring, and reacting for 3h at 60 ℃; after the reaction is finished, washing and drying to obtain chitosan quaternary ammonium salt;
1.5g of the chitosan quaternary ammonium salt, 4g of the grafting monomer, 0.01g of the polymerization inhibitor, 0.4g of the initiator and 0.02g of nano TiO2Dissolving in 20ml deionized water, stirring, and heating at 130 deg.C for 5 min; and after the reaction is finished, washing and drying.
The grafting monomer is citric acid;
the initiator is ammonium persulfate;
the polymerization inhibitor is 4-methoxyphenol.
Example 4
A method for preparing an antibacterial agent comprising the steps of:
dispersing 1.5g of chitosan in 250ml of isopropanol for ultrasonic treatment, wherein the ultrasonic power is 65W, and the ultrasonic time is 30 min; adding 7g of cross-linking agent cetyl epoxypropyl dimethyl ammonium chloride, uniformly stirring, and reacting for 3h at 60 ℃; after the reaction is finished, washing and drying to obtain chitosan quaternary ammonium salt;
1.5g of the chitosan quaternary ammonium salt, 4g of the grafting monomer, 0.01g of the polymerization inhibitor, 0.4g of the initiator and 0.02g of the modified nano TiO2Dissolving in 20ml deionized water, stirring, and heating at 130 deg.C for 5 min; and after the reaction is finished, washing and drying.
The grafting monomer is citric acid;
the initiator is ammonium persulfate;
the polymerization inhibitor is 4-methoxyphenol;
the modified nano TiO2The preparation method comprises the following steps: 0.2g of nano TiO2And 0.02g of hexadecyl epoxy propyl dimethyl ammonium chloride is placed in 100ml of deionized water for ultrasonic dispersion, the ultrasonic power is 50W, the ultrasonic time is 20min, and the modified nano TiO is obtained by centrifugal separation and drying2。
Example 5
A method for preparing an antibacterial agent comprising the steps of:
dispersing 1.5g of chitosan in 250ml of isopropanol for ultrasonic treatment, wherein the ultrasonic power is 65W, and the ultrasonic time is 30 min; adding 7g of cross-linking agent cetyl epoxypropyl dimethyl ammonium chloride, uniformly stirring, and reacting for 3h at 60 ℃; after the reaction is finished, washing and drying to obtain chitosan quaternary ammonium salt;
1.5g of the chitosan quaternary ammonium salt, 4g of the grafting monomer, 0.01g of the polymerization inhibitor, 0.4g of the initiator and 0.02g of the modified nano TiO2Dissolving in 20ml deionized water, stirring, and heating at 130 deg.C for 5 min; and after the reaction is finished, washing and drying.
The grafting monomer is N-hydroxyethyl acrylamide;
the initiator is ammonium persulfate;
the polymerization inhibitor is 4-methoxyphenol;
the modified nano TiO2Comprises the following steps: 0.2g of nano TiO2And 0.02g of hexadecyl epoxy propyl dimethyl ammonium chloride is placed in 100ml of deionized water for ultrasonic dispersion, the ultrasonic power is 50W, the ultrasonic time is 20min, and the modified nano TiO is obtained by centrifugal separation and drying2。
Example 6
A method for preparing an antibacterial agent comprising the steps of:
dispersing 1.5g of chitosan in 250ml of isopropanol for ultrasonic treatment, wherein the ultrasonic power is 65W, and the ultrasonic time is 30 min; adding 7g of cross-linking agent cetyl epoxypropyl dimethyl ammonium chloride, uniformly stirring, and reacting for 3h at 60 ℃; after the reaction is finished, washing and drying to obtain chitosan quaternary ammonium salt;
1.5g of the chitosan quaternary ammonium salt, 4g of the grafting monomer, 0.01g of the polymerization inhibitor, 0.4g of the initiator and 0.02g of the modified nano TiO2Dissolving in 20ml deionized water, stirring, and heating at 130 deg.C for 5 min; and after the reaction is finished, washing and drying.
The grafting monomer is a mixture formed by mixing citric acid and N-hydroxyethyl acrylamide according to the mass ratio of 1: 1;
the initiator is ammonium persulfate;
the polymerization inhibitor is 4-methoxyphenol;
the modified nano TiO2Comprises the following steps: 0.2g of nano TiO2And 0.02g of hexadecyl epoxy propyl dimethyl ammonium chloride is placed in 100ml of deionized water for ultrasonic dispersion, the ultrasonic power is 50W, the ultrasonic time is 20min, and the modified nano TiO is obtained by centrifugal separation and drying2。
Comparative example 1
A method for preparing an antibacterial agent comprising the steps of:
dispersing 1.5g of chitosan in 250ml of isopropanol for ultrasonic treatment, wherein the ultrasonic power is 65W, and the ultrasonic time is 30 min; adding 7g of cross-linking agent cetyl epoxypropyl dimethyl ammonium chloride, uniformly stirring, and reacting for 3h at 60 ℃; after the reaction is finished, washing and drying to obtain chitosan quaternary ammonium salt;
1.5g of the chitosan quaternary ammonium salt, 4g of the grafting monomer, 0.01g of the polymerization inhibitor, 0.4g of the initiator and 0.02g of nano TiO2Dissolving in 20ml deionized water, stirring, and heating at 130 deg.C for 5 min; and after the reaction is finished, washing and drying.
The grafting monomer is N-hydroxyethyl acrylamide;
the initiator is ammonium persulfate;
the polymerization inhibitor is 4-methoxyphenol;
the modified nano TiO2Comprises the following steps: 0.2g of nano TiO2And 0.02g of sodium dodecyl sulfate is placed in 100ml of deionized water for ultrasonic dispersion with the ultrasonic power of 50W and the ultrasonic time of 20min, and the modified nano Ti is obtained by centrifugal separation and dryingO2。
Test example
The antibacterial properties of examples 1 to 6 and comparative example 1 were tested. The antibacterial performance test method is carried out according to an oscillation method, namely a powder antibacterial performance test method, in appendix A of GB/T21510-2008 nano inorganic material antibacterial performance test method. The detection bacteria are as follows: escherichia coli ATCC25922, staphylococcus aureus ATCC 6538. The specific test results are shown in table 1.
Table 1: testing of antimicrobial Properties of antimicrobial Agents
| Staphylococcus aureus (%) | Escherichia coli (%) | |
| Chitosan | 57.82 | 54.91 |
| Comparative example 1 | 70.35 | 69.42 |
| Example 1 | 73.41 | 72.11 |
| Example 2 | 83.66 | 81.87 |
| Example 3 | 93.45 | 91.69 |
| Example 4 | 95.23 | 93.78 |
| Example 5 | 89.12 | 87.36 |
| Example 6 | 99.85 | 99.45 |
Compared with chitosan, in example 1, hexadecyl epoxy propyl dimethyl ammonium chloride is introduced into chitosan, the antibacterial activity of the N-long alkyl chitosan quaternary ammonium salt is influenced by the alkyl chain length, and the longer the alkyl chain length is, the higher the antibacterial activity is. The reason is that the quaternary ammonium salt molecules are positively charged, so that the adsorption of negatively charged bacteria is facilitated, and the long-chain quaternary ammonium salt enables the bacteria to be adsorbed on the surface of the antibacterial agent due to the existence of the long-chain alkyl structure, penetrates the interior of a cell body, and is leaked from the cytoplasm of the bacteria, so that the antibacterial performance is enhanced. Example 1 also gives a factual confirmation of the antibacterial effect compared to the antibacterial performance test of pure chitosan.
Furthermore, grafting monomers of citric acid and N-hydroxyethyl acrylamide are introduced to the long-chain chitosan quaternary ammonium salt, so that the prepared chitosan quaternary ammonium salt contains active groups and new antibacterial groups, and the antibacterial performance of the cationic chitosan quaternary ammonium salt can be improved while the antibacterial durability is maintained. The antibacterial effect is also shown in the fact that example 2 is compared with the antibacterial performance test of example 1.
Nano TiO is introduced on the basis of the example 22On the one hand, grafting monomer on reactive chitosan quaternary ammonium salt and TiO2on-OH to generate hydrogenBonding, TiO reduction2Loss of the active chitosan quaternary ammonium salt and the nano TiO2the-OH on the surface generates hydrogen bonds to limit the nano TiO2Less nano TiO of2Loss of the catalyst. At the same time, nano TiO2Irradiating TiO with light2The electrons break through the forbidden band limitation to form electron-hole pairs which are easy to be adsorbed on the nano TiO2O of the surface2、OH-、H2O is combined to form O2 -·OH, and the free radicals with extremely strong activity can effectively destroy the cell structure, inhibit the growth of the cell structure and further improve the antibacterial property. On the other hand, nano TiO2Forming covalent bond, electrostatic attraction, intermolecular force and hydrogen bond with chitosan, and further improving antibacterial property. The antibacterial effect is also shown in the fact that the antibacterial performance test of example 2 is compared with that of example 3.
On the basis of example 3 for nano TiO2The modification is carried out, the adopted modifier is hexadecyl epoxy propyl dimethyl ammonium chloride, and the addition of the modifier keeps the solution system stable. The possible reasons for this are: the reactive chitosan quaternary ammonium salt is easy to ionize in the solution, so that macromolecular chain is positively charged, the action with the cationic dispersant is weaker, no precipitate is generated, and a solution system can exist stably. On the other hand, the modifier can improve the nano TiO2Easy agglomeration, thereby improving the antibacterial property. The antibacterial effect is also shown in the fact that the antibacterial performance test of example 3 is compared with that of example 4.
On the basis of the embodiment 4, the grafting monomer N-hydroxyethyl acrylamide is introduced, so that the prepared antibacterial agent has good antibacterial performance and heat resistance and keeps antibacterial durability. The introduction of the grafting monomers citric acid and N-hydroxyethyl acrylamide can provide active groups and introduce antibacterial groups, and the two groups have synergistic effect to obviously improve the antibacterial performance. The antibacterial performance tests of examples 4, 5 and 6 are compared, and the antibacterial effect is also proved. As described above, example 6 has a good antibacterial property.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (9)
1. A method for preparing an antibacterial agent, comprising the steps of: 1-3g of chitosan is dispersed in 100-300ml of isopropanol for ultrasonic treatment; then adding 5-9g of cross-linking agent, and reacting for 2-5h at 50-80 ℃; and (5) washing and drying.
2. A method for preparing an antibacterial agent, comprising the steps of: dispersing 1-3g of chitosan in 100-300ml of isopropanol for ultrasonic treatment, wherein the ultrasonic power is 50-70W, and the ultrasonic time is 20-50 min; adding 5-9g of cross-linking agent, stirring uniformly, and reacting for 2-5h at 50-80 ℃; after the reaction is finished, washing and drying to obtain chitosan quaternary ammonium salt;
dissolving 0.8-1.5g of the chitosan quaternary ammonium salt, 3-5g of the grafting monomer, 0.005-0.02g of the polymerization inhibitor and 0.25-0.7g of the initiator in 10-30ml of deionized water, uniformly stirring, and heating and reacting at 110-150 ℃ for 5-20 min; and after the reaction is finished, washing and drying.
3. A method for preparing an antibacterial agent, comprising the steps of: dispersing 1-3g of chitosan in 100-300ml of isopropanol for ultrasonic treatment, wherein the ultrasonic power is 50-70W, and the ultrasonic time is 20-50 min; adding 5-9g of cross-linking agent, stirring uniformly, and reacting for 2-5h at 50-80 ℃; after the reaction is finished, washing and drying to obtain chitosan quaternary ammonium salt;
0.8-1.5g of the chitosan quaternary ammonium salt, 3-5g of grafting monomer, 0.005-0.02g of polymerization inhibitor, 0.25-0.7g of initiator and 0.01-0.03g of nano TiO2Dissolving in 10-30ml deionized water, stirring uniformly, and heating and reacting at 110-150 ℃ for 5-20 min; and after the reaction is finished, washing and drying.
4. The method of claim 2 or 3, wherein the grafting monomer is one of citric acid, dimethylaminopropylamine, acrylic acid, N-hydroxyethyl acrylamide, hydroxybenzoic acid, or a mixture thereof.
5. The method of claim 2 or 3, wherein the initiator is one of ammonium persulfate, potassium sulfate, ammonium chloride, and ferrous sulfate.
6. The method of claim 2 or 3, wherein the cross-linking agent is one or both of cetylepoxypropyldimethylammonium chloride and 2, 3-epoxypropyltrimethylammonium chloride.
7. The method of claim 3, wherein the nano TiO is used as a raw material for the antibacterial agent2For modifying nano TiO2The preparation method comprises the following steps: 0.3-0.5g of nano TiO2And 0.01-0.03g of hexadecyl epoxy propyl dimethyl ammonium chloride is placed in 80-100ml of deionized water for ultrasonic dispersion with the ultrasonic power of 50-70W and the ultrasonic time of 10-30min, and the modified nano TiO is obtained by centrifugal separation and drying2。
8. An antibacterial agent produced by the method for producing an antibacterial agent according to any one of claims 1 to 7.
9. Use of the antimicrobial agent of claim 8 in plastics, textiles, coatings.
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