Cyanuric acid-containing halamine / quaternary ammonium salt copolymerization modified antibacterial material and application thereof

Abstract

The invention provides a cyanuric acid-containing halamine / quaternary ammonium salt copolymerization modified antibacterial material and application, and relates to the technical field of antibacterial materials. 1-allyl-s-triazine-2. 4.6-triketone potassium salt is synthesized from the cyanuric acid-containing halamine / quaternary ammonium salt copolymerization modified antibacterial material through nucleophilic substitution; the preparation method comprises the following steps: grafting a chlorinated halamine / quaternary ammonium salt copolymer to 3-chloropropyltrimethoxysilane pretreated natural fiber, copolymerizing the modified fiber and dimethyl ethyl methacrylate through continuous steps, reacting in ethanol with alkyl bromide, and substituting in a disinfectant to obtain the chlorinated halamine / quaternary ammonium salt copolymer modified material. The cyanuric acid-containing halamine / quaternary ammonium salt copolymerization modified antibacterial material prepared by the invention can quickly and efficiently kill escherichia coli and staphylococcus aureus, and has good recovery and regeneration capacity, ultraviolet radiation resistance and self-cleaning capacity.

Description

Technical Field

[0001] The present invention relates to the technical field of antibacterial materials, and particularly relates to a halogenamine quaternary ammonium salt copolymer-modified antibacterial material containing cyanuric acid and its application. Background Art

[0002] Fiber spun products are a common daily necessity, and at the same time they are also the main medium for pathogen transmission; mainly because of the criss-cross on the surface of fiber spun products, which have small pores and small grooves, these pores and grooves provide a good living environment for bacteria, so it is easy to cause a large number of bacteria to breed and reproduce; currently, the market has a large demand for disinfection and sterilization products. When the spun products are contaminated by bacteria, it will cause mildew of the spun products, produce peculiar smell, reduce its mechanical strength and shorten its service life. Most traditional antibacterial spun products combine the antibacterial agent with the spun product by physical adsorption through a post-treatment method. After multiple washing cycles, the antibacterial component will be washed off from the fabric surface, not only resulting in a decrease in antibacterial activity, but also causing an environmental burden. By means of chemical bonding, the bonding fastness of inorganic antibacterial agents, organic antibacterial agents and natural antibacterial agents with the fabric can be improved, significantly improving the long-term antibacterial performance of the fabric, increasing the service cycle and thus reducing the production and supply pressure.

[0003] Among many cotton fiber finishing antibacterial agents, the application of quaternary ammonium salts has a long history; however, due to the limited bactericidal effect of a single quaternary ammonium salt bactericide in some use environments and the generation of drug resistance after long-term use alone, the combined action of compound quaternary ammonium salts will have more excellent broad-spectrum bactericidal effects and many other advantages. Currently, heterocyclic halogenamine compounds are a relatively new type of antibacterial and disinfectant compound. Due to their broad-spectrum antibacterial and disinfectant properties, high efficiency and renewable availability, they are increasingly widely used. They graft heterocyclic halogenamine molecules onto polymer materials through relevant technologies. However, for fibers used in military and civilian medical protection and wound dressings, they need to have antibacterial and disinfectant properties while being able to resist ultraviolet rays and self-clean; therefore, in view of the above problems, we propose a halogenamine / quaternary ammonium salt copolymer-modified antibacterial material containing cyanuric acid, which can achieve high-efficiency antibacterial and disinfectant, renewable antibacterial and disinfectant, ultraviolet resistance and self-cleaning. Summary of the Invention

[0004] In view of this, the purpose of the present invention is to propose a halogenamine / quaternary ammonium salt copolymer-modified antibacterial material containing cyanuric acid and its application, which can achieve high-efficiency antibacterial and disinfectant, renewable antibacterial and disinfectant, ultraviolet resistance and self-cleaning, and can effectively solve the technical problems in the background art.

[0005] Technical effect: The cyanuric acid-containing haloamine / quaternary ammonium salt copolymer-modified antibacterial material prepared by the present invention synthesizes potassium 1-allyl-s-triazine-2,4,6-trione through nucleophilic substitution, mediates it onto the 3-chloropropyltrimethoxysilane-pretreated fiber, and copolymerizes the modified fiber with dimethylethyl methacrylate through a continuous process, reacts with bromoalkane in ethanol, and then performs substitution in a disinfectant solution to obtain a chloro-haloamine / quaternary ammonium salt copolymer-modified material. The cyanuric acid-containing haloamine / quaternary ammonium salt copolymer-modified antibacterial material prepared by the present invention can quickly and efficiently kill Escherichia coli and Staphylococcus aureus, and at the same time has good recovery and regeneration ability, ultraviolet light irradiation resistance, and self-cleaning ability.

[0006] The cyanuric acid-containing haloamine / quaternary ammonium salt copolymer-modified antibacterial material prepared by the present invention has the following structural formula:

[0007]

[0008] Among them, R is a straight-chain alkane with 12-18 carbon atoms, and X is chlorine or bromine.

[0009] As an improvement, the present invention relates to a preparation method of a cyanuric acid-containing haloamine / quaternary ammonium salt copolymer-modified antibacterial material, which includes the following steps:

[0010] S1, Immerse the fiber fabric in a weakly alkaline solution, perform ultrasonic cleaning, washing, and drying to obtain the cleaned fiber fabric; take an appropriate amount of ethanol / aqueous solution of 3-chloropropyltrimethoxysilane and perform oscillating stirring to obtain a mixed solution; immerse the cleaned fiber fabric in the mixed solution, cure at a high temperature for several hours, and then perform washing and drying to obtain CPTMO-modified fiber.

[0011] S2, Weigh an appropriate amount of cyanuric acid and stir it in an alkaline aqueous solution, and then slowly drop allyl bromide to obtain a 1-allyl-s-triazine-2,4,6-trione salt solution. Place the CPTMO-modified fiber fabric prepared in step S1 in the 1-allyl-s-triazine-2,4,6-trione salt solution, and then add a small amount of potassium iodide and tetrabutylammonium iodide to obtain VAC-modified fiber.

[0012] S3, Weigh an appropriate amount of dimethylethyl methacrylate and potassium persulfate, add them to the VAC-modified cotton fabric obtained in step S2, raise the temperature for polymerization, and then perform washing multiple times to obtain VAC / DMAEMA copolymer-modified fiber.

[0013] S4, Immerse the VAC / DMAEMA copolymer-modified fiber prepared in step S3 in an ethanol solution and a haloalkane for reflux soaking to obtain a QACs-modified fiber fabric; immerse the QACs-modified fiber fabric in a disinfectant solution and place it at room temperature for 1 hour to obtain a surface-modified fiber with a chloro-haloamine / quaternary ammonium salt structure.

[0014] As a further improvement, the present invention relates to the application of a cyanuric acid-containing haloamine / quaternary ammonium salt copolymer-modified antibacterial material in civil and military protection and wound dressing fibers.

[0015] The beneficial effects of the present invention are as follows:

[0016] (1) The haloamine functional group of the cyanuric acid-containing haloamine / quaternary ammonium salt copolymer-modified antibacterial material prepared by the present invention has a strong synergistic antibacterial effect on the quaternary ammonium salt. After chlorination, the chlorination can maintain good hydrophobic properties without destroying the material structure, indicating that the chlorination modification can endow the material with good self-cleaning properties; and chlorination can increase the UV protection index value, making it have good UV resistance.

[0017] (2) In the present invention, the cyanuric acid-containing haloamine / quaternary ammonium salt copolymer-modified antibacterial material is grafted onto CPTMO-modified fibers through a quantitative amount of VAC, and then the stock solution is subjected to free radical copolymerization, quaternization, and chlorination with DMAEMA aqueous solution to obtain a synergistic antibacterial modified fiber; its synthesis process is simple, the conditions are mild, the raw materials are cheap and easy to obtain, and the solvent can be reused after purification, which is green and environmentally friendly and suitable for industrial scale-up production.

[0018] (3) The method for preparing the synergistic antibacterial fiber of the present invention is applicable to various natural and natural cellulose fibers with hydroxyl groups on the surface, with a small addition amount, a long-lasting antibacterial effect, broad-spectrum and high efficiency, good antibacterial properties, capable of endowing hydrophilic fibers with hydrophobic characteristics, and having easy rinsability. At the same time, it has high-efficiency UV blocking ability and can be used for the preparation of wound dressings; it is a synergistic antibacterial fiber with triple functions of repeatable antibacterial, easy rinsing, and UV resistance.

[0019] (4) The method for preparing the antibacterial fiber coating adopted by the present invention is different from the traditional method for preparing antibacterial fibers. The traditional preparation method is to add quaternary ammonium salts, silver-based inorganic antibacterial materials or photocatalytic antibacterial agents by blending or physical adsorption, etc. However, the existing methods have various limitations, such as weak antibacterial effect, non-renewability, heavy metal leaching, difficult recovery, etc.; at the same time, the application range of haloamine antibacterial materials is usually limited to the surface modification of fiber fabrics, and the cost is relatively high, and the fibers prepared therefrom show uneven distribution of antibacterial agents and are easily worn to lose antibacterial functions; therefore, the present invention adopts a surface copolymerization grafting method to combine the haloamine structure with the quaternary ammonium salt structure to form a synergistic effect, expanding the use range of haloamine antibacterial materials. Description of the Drawings

[0020] To more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for the embodiments. It should be understood that the following drawings only show some embodiments of the present invention and should not be regarded as a limitation of the scope. For those of ordinary skill in the art, without creative efforts, other related drawings can also be obtained based on these drawings.

[0021] Figure 1 is the preparation flow chart of the halogenamine / quaternary ammonium salt copolymer modified antibacterial material containing cyanuric acid in the present invention;

[0022] Figure 2 is the ATR-FTIR spectrum of the halogenamine / quaternary ammonium salt copolymer modified antibacterial material containing cyanuric acid in the present invention;

[0023] Figure 3 is the X-ray photoelectron spectrum of the halogenamine / quaternary ammonium salt copolymer modified antibacterial material containing cyanuric acid in the present invention;

[0024] Figure 4 is the contact angle test data graph of the halogenamine / quaternary ammonium salt copolymer modified antibacterial material containing cyanuric acid in the present invention;

[0025] Figure 5 is the antibacterial performance test graph of the halogenamine / quaternary ammonium salt copolymer modified antibacterial material containing cyanuric acid in the present invention;

[0026] Figure 6 is the ultraviolet transmittance curve of the halogenamine / quaternary ammonium salt copolymer modified antibacterial material containing cyanuric acid in the present invention;

[0027] Figure 7 is the mouse wound infection test graph of the halogenamine / quaternary ammonium salt copolymer modified antibacterial material containing cyanuric acid in the present invention; Specific Embodiments

[0028] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the following will clearly and completely describe the technical solutions in the embodiments of the present invention with reference to the drawings in the embodiments of the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention. Therefore, the following detailed description of the embodiments of the present invention provided in the drawings is not intended to limit the scope of the claimed invention, but merely represents the selected embodiments of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention.

[0029] In the description of the present invention, the terms "first" and "second" are only used for descriptive purposes and cannot be construed as indicating or implying relative importance or implicitly specifying the quantity of the indicated technical features. Thus, the features defined with "first" and "second" may explicitly or implicitly include one or more of such features. In the description of the present invention, "a plurality" means two or more unless otherwise specifically defined.

[0030] The embodiment of the present invention provides a preparation method of a cyanuric acid-containing halogenamine / quaternary ammonium salt copolymer-modified antibacterial material, comprising the following steps:

[0031] S1, soaking a fiber fabric in a weakly alkaline solution, ultrasonic cleaning, washing and drying to obtain a cleaned fiber fabric; taking an appropriate amount of ethanol / aqueous solution of 3-chloropropyltrimethoxysilane and performing oscillating stirring to obtain a mixed solution; soaking the cleaned fiber fabric in the mixed solution, performing high-temperature curing for several hours, and then washing and drying to obtain CPTMO-modified fiber;

[0032] Preferably, the fiber fabric is cotton fiber, bacterial cellulose, linen, etc., which are natural cellulose, regenerated cellulose, rayon, etc. fibers containing a large amount of hydroxyl groups on their surfaces.

[0033] Preferably, the mass ratio of the ethanol / aqueous solution of 3-chloropropyltrimethoxysilane is 3 - 5:50:50, and the pH range of the ethanol / aqueous solution of 3-chloropropyltrimethoxysilane is 4 - 6, which can ensure a high grafting rate.

[0034] Preferably, the soaking time is 30 - 120 s, the high-temperature curing time is 5 - 30 min, and the temperature range is 60 - 95 °C; the high-temperature curing time depends on the curing temperature, and the surface grafting rate of CPTMO can be improved through repeated leaching / curing processes, and the number of times is 1 - 5 times. More preferably, the soaking time is 60 - 90 s, the high-temperature curing time is 10 - 20 min, the temperature range is 85 - 90 °C; the number of times is 2 - 3 times, which can make the surface grafting rate of CPTMO reach nearly 100%.

[0035] S2, weighing an appropriate amount of cyanuric acid and stirring it in an alkaline aqueous solution, then slowly dropping allyl bromide and reacting at room temperature to obtain a 1-allyl-s-triazine-2,4,6-trione salt solution (VAC); placing the CPTMO-modified fiber fabric prepared in step S1 in the 1-allyl-s-triazine-2,4,6-trione salt solution, and adding a small amount of potassium iodide and tetrabutylammonium iodide to obtain VAC-modified fiber;

[0036] Preferably, the selection of VAC is mainly to provide an ethylene chain site for surface polymerization and halogenamine antibacterial functional groups.

[0037] Preferably, the aqueous alkali solution is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate; the mass fraction of the alkali in the aqueous alkali solution is 10-15%, and the molar ratio of the aqueous alkali solution to cyanuric acid is 0.05-0.15 g: 100 mL; the control of the molar ratio is beneficial to the complete dissolution of cyanuric acid. Preferably, the aqueous alkali solution is potassium hydroxide.

[0038] Preferably, potassium iodide is used as a catalyst and tetrabutylammonium iodide is used as a surfactant. The addition amounts of potassium iodide and tetrabutylammonium iodide are 0.05-0.15 g / 100 mL. The control of the addition amounts is beneficial to increasing the hydrophobicity of the reaction system and the adsorption of reaction substrates, thereby accelerating the progress of the reaction.

[0039] S3, Weigh an appropriate amount of dimethylethyl methacrylate as the second comonomer and potassium persulfate as the initiator, add them to the VAC-modified fiber fabric obtained in step S2, carry out temperature-raising polymerization, and then carry out multiple washings to obtain the VAC / DMAEMA copolymer-modified fiber;

[0040] Preferably, the mass ratio of DMAEMA to VAC is 1-1.5:1, the density of potassium persulfate is 0.5-1.5 g / L, and the copolymerization time is 4-8 hours.

[0041] S4, Immerse the VAC / DMAEMA copolymer-modified fiber prepared in step S3 in an ethanol solution and a haloalkane for reflux immersion to obtain a fiber fabric modified with QACs; Immerse the fiber fabric modified with QACs in a disinfectant solution and place it at room temperature for 1 hour to obtain a surface-modified fiber with a chlorohaloamine / quaternary ammonium salt structure;

[0042] Preferably, the haloalkane is one or more of straight-chain alkanes substituted by monobromo or monochloro of C 12 -C 18 The molar ratio of the haloalkane to DMAEMA is 1-1.1:1. The control of the ratio is beneficial to saving raw materials and facilitating subsequent impurity removal.

[0043] Preferably, the disinfectant is sodium hypochlorite or household sodium hypochlorite disinfectant with a mass concentration of 0.1-3% and a pH value of 4-7.5. Preferably, the disinfectant is household sodium hypochlorite disinfectant, which is beneficial to cost savings and at the same time controls the concentration of the oxidant to prevent damage to the fiber structure.

[0044] The halogenated amine / quaternary ammonium salt copolymer-modified antibacterial material containing cyanuric acid provided by the embodiments of the present invention can be used as a protective article and applied in military and civilian medical protection and wound dressings.

[0045] Example 1:

[0046] Preparation method of cyanuric acid-containing haloamine / quaternary ammonium salt copolymer-modified antibacterial material, comprising the following steps:

[0047] (1) Immerse the cotton fabric in 1% sodium hydroxide solution for 2 hours, clean it completely with ultrasonic waves, wash it with water and dry it to obtain the pretreated cotton fabric; Immerse the pretreated cotton fabric in an ethanol / aqueous solution ((5 / 5 / 1), (v / v / v)) containing 3-chloropropyltrimethoxysilane, where the bath ratio is 1:25 (the ratio of the weight of the cotton fabric to the volume of the dyeing solution), and adjust the pH to 5. The sample is subjected to two soaking and clamping treatments, and its pickup rate (the weight ratio of the fiber to the dyeing solution) is 100%. Then cure it at 90 °C for 15 minutes, rinse it with water, and place it in a vacuum furnace at 45 °C for drying to obtain the CPTMO-modified cotton fabric; Dissolve 5.16 g of cyanuric acid in 200 mL of potassium hydroxide solution and stir until the cyanuric acid is completely dissolved. Then slowly drop 4.80 g of allyl bromide and react at room temperature for 12 hours. Adjust the pH value of the solution to 7.0 with acetic acid to produce a white precipitate. Rinse it several times with deionized water and then place it in a vacuum dryer at 60 °C to obtain a 1-allyl-s-triazine-2,4,6-trione potassium salt solution;

[0048] (2) Immerse 5 g of the CPTMO-modified cotton fabric in 100 mL of a transparent 1-allyl-s-triazine-2,4,6-trione potassium salt solution, then add 0.1 g of potassium iodide as a catalyst and 0.2 g of tetrabutylammonium iodide as a surface activator, and place it at 25 °C for reaction for 12 hours to obtain the VAC-modified cotton fabric; Add the VAC-modified cotton fabric to 2 g of dimethylaminoethyl methacrylate, use 0.1 g of K2S2O8 as an initiator, and copolymerize with VAC on the surface of the cotton fabric through free radical polymerization reaction. Under the protection of nitrogen, place it at 80 °C for polymerization for 6 hours. Wash the reacted cotton fabric several times with deionized water and ethanol to remove unreacted VAC, DMAEMA and other impurities, and then place it in a vacuum oven at 45 °C for drying to obtain the VAC / DMAEMA copolymer-modified cotton fabric. Immerse the VAC / DMAEMA copolymer-modified cotton fabric in 20 mL of ethanol solution and 3 g of 1-bromohexadecane for reflux soaking for 6 h to quaternize DMAEMA into quaternary ammonium salt (QACs) groups to obtain a surface-modified cotton fabric with a haloamine / quaternary ammonium salt structure. Then wash the surface-modified cotton fabric with a haloamine / quaternary ammonium salt structure and immerse it in 50 mL of 3 wt% household disinfectant for 1 hour at room temperature to convert the N-H bond into the N-Cl form, and obtain a surface-modified cotton fabric with a chlorinated haloamine / quaternary ammonium salt structure after drying.

[0049] Example 2

[0050] Preparation method of cyanuric acid-containing haloamine / quaternary ammonium salt copolymer-modified antibacterial material, comprising the following steps:

[0051] (1) Immerse the flax in a 1% sodium hydroxide solution for 2 hours, clean it completely with ultrasonic waves, wash it with water and dry it to obtain pretreated flax; Immerse the pretreated flax in an ethanol / water solution ((5 / 5 / 1), (v / v / v)) containing 3-chloropropyltrimethylsilane, where the bath ratio is 1:30 (the ratio of the weight of flax to the volume of the dyeing solution), and adjust the pH to 5. The sample is soaked and clamped twice, and the pickup rate is 100%. Then cure it at 90 °C for 15 minutes. After rinsing with water, place it in a vacuum furnace at 45 °C for drying to obtain CPTMO-modified flax; Dissolve 5.16 g of cyanuric acid in 200 mL of potassium hydroxide solution and stir until the cyanuric acid is completely dissolved. Then slowly drop 4.80 g of allyl bromide and react at room temperature for 12 hours. Adjust the pH value of the solution to 7.0 with acetic acid to produce a white precipitate. Wash it several times with deionized water and then place it in a vacuum drying at 60 °C to obtain a solution of 1-allyl-s-triazine-2,4,6-trione potassium salt;

[0052] (2) Immerse 10 g of CPTMO-modified flax into 200 mL of a transparent 1-allyl-s-triazine-2,4,6-trione potassium salt solution, then add 0.1 g of potassium iodide as a catalyst and 0.2 g of tetrabutylammonium iodide as a surfactant, and place it at 25 °C for reaction for 12 hours to obtain VAC-modified flax. Add the VAC-modified flax to 2.5 g of dimethylaminoethyl methacrylate, using 0.1 g of K2S2O8 as an initiator, and copolymerize with VAC on the surface of the flax through free radical polymerization reaction. Under the protection of nitrogen, place it at 80 °C for polymerization for 6.5 hours. Wash the reacted flax several times with deionized water and ethanol to remove unreacted VAC, DMAEMA and other impurities, and then place it in a vacuum oven at 45 °C for drying to obtain VAC / DMAEMA copolymer-modified fiber. Immerse the VAC / DMAEMA copolymer-modified fiber in an ethanol solution of 20 mL ethanol solution and 2.6 g of 1-bromododecane for reflux soaking for 6 h to quaternize DMAEMA into a quaternary ammonium salt (QACs) group to obtain a surface-modified flax with a haloamine / quaternary ammonium salt structure. Then wash the surface-modified flax with a haloamine / quaternary ammonium salt structure and immerse it in 50 mL of 3 wt% household disinfectant for 1 hour at room temperature to convert the N-H bond into the N-Cl form, and obtain a surface-modified flax with a chlorinated haloamine / quaternary ammonium salt structure after drying.

[0053] Comparative Example 1

[0054] (1) Comparative Example 1 is pure cotton cloth.

[0055] Characterization:

[0056] (1) Infrared spectroscopy test: The pure cotton cloth obtained in Comparative Example 1 and the CPTMO-modified cotton fabric, VAC-modified cotton fabric, VAC / DMAEMA copolymer-modified cotton fabric, surface-modified cotton fabric with haloamine / quaternary ammonium salt structure, and surface-modified cotton fabric with chloro-haloamine / quaternary ammonium salt structure were ground and pressed into tablets, and placed in an infrared spectrometer for testing to obtain an infrared spectrogram as shown in Figure 2 shown. From the infrared spectrogram of Figure 2 , it can be found that the absorption bands of Si-O-Si, Si-OH, and Si-O change at 1275 cm -1 , 792 cm -1 , and 758 cm -1 respectively, proving the introduction of CPTMO onto the cotton cloth. Under alkaline conditions, VAC was grafted onto the cotton cloth through a nucleophilic substitution reaction with chlorine atoms on CTPMO. The characteristic peaks of the VAC-modified cotton fabric near 1741 cm -1 and 1591 cm -1 are the stretching vibration of the imide C=O bond and the bending vibration of the triazine ring N-H bond, indicating the successful grafting of VAC. In the VAC / DMAEMA copolymer-modified cotton fabric, due to the introduction of a large number of ester groups onto the cotton fiber surface through polymerization reaction, a stronger signal of the ester carbonyl group was observed at 1721 cm Figure 2 in -1 . Then, the surface of the cotton cloth was quaternized, and the dimethylamino group on DMAEMA was replaced by a long-chain quaternary ammonium salt through hexadecyl bromide. It can be seen from Figure 2 that there are significant signals of the C-H stretching vibration in the corresponding bands at 2856 cm -1 and 2927 cm -1 , indicating the formation of quaternary ammonium salt on the surface of the cotton fabric. Finally, the cotton cloth was chlorinated to convert the N-H structure on the cyanuric acid ring into an N-Cl structure, and it was found that the imide N-H stretching vibration peak at 3300 - 3500 cm -1 weakened significantly, indicating the formation of the haloamine structure.

[0057] (2) X-ray photoelectron spectroscopy test: The pure cotton cloth obtained in Comparative Example 1 and the CPTMO-modified cotton fabric, VAC-modified cotton fabric, VAC / DMAEMA copolymer-modified cotton fabric, surface-modified cotton fabric with haloamine / quaternary ammonium salt structure, and surface-modified cotton fabric with chloro-haloamine / quaternary ammonium salt structure were ground and pressed into tablets, and placed in an XPS spectrometer for X-ray photoelectron spectroscopy test. The X-ray photoelectron spectroscopy test results are as shown in Figure 3 shown. The main elements on the surface of the pure cotton sample are carbon and oxygen, both of which belong to the inherent groups of the cotton cloth. After being modified with CTPMO, new peaks appear at the binding energies of 102 eV, 153 eV, and 199 eV, corresponding to Si 2p, Si 2s , Cl 2p , further confirmed that CTPMO was grafted onto the cotton fabric surface through hydrolysis curing. After nucleophilic substitution of VAC, a new N 1s peak appeared at a binding energy of 398.3 eV. Since VAC existed in the form of Na salt on the cotton fabric surface at this time, an Auger peak attributed to Na element appeared at 513.2 eV. At the same time, the Cl element peak disappeared, proving the occurrence of the nucleophilic substitution reaction of halogenated hydrocarbons. After further copolymerization of VAC and DMAEMA, the N 1s peak was further enhanced, indicating the occurrence of surface polymerization. The cotton fabric was quaternized. New peaks attributed to Br 3p , Br 3d appeared at 69 eV and 181.5 eV. At the same time, the peak at Br 3d was deconvoluted, and the peaks at 67.5 eV and 68.5 eV indicated the presence of Br - ions, confirming the formation of quaternary ammonium salt functional groups. The quaternary ammonium salt / hydroxyhalamine modified cotton fabric was further chlorinated, and the peak originally attributed to Br - disappeared, while new peaks appeared at Cl 2p (199 eV) and Cl 2s (269 eV).

[0058] (3) Contact angle measurement: The static contact angle changes of the pure cotton fabric obtained in Comparative Example 1, the CPTMO modified cotton fabric, the VAC modified cotton fabric, the VAC / DMAEMA copolymer modified cotton fabric, the surface modified cotton fabric with hydroxyhalamine / quaternary ammonium salt structure, and the surface modified cotton fabric with chlorinated hydroxyhalamine / quaternary ammonium salt structure were measured. The test results are as Figure 4As shown, the contact angle of the pure cotton cloth in the comparative example is 75.6°. Its contact angle is relatively small and the water droplet is quickly absorbed by the cotton cloth and disappears on the surface. This is because there are a large number of hydroxyl groups on the surface of the cotton cloth, resulting in strong hydrophilicity of the pure cotton cloth. With the addition of the silane coupling agent CPTMO, the hydrophobicity of the cotton cloth increases significantly, and the contact angle value is 118.7°. This is because the hydrophobic siloxane groups form a coating on the surface of the cotton cloth, covering the hydrophilic hydroxyl groups, carboxyl groups, etc., thus causing a large change in the hydrophilicity and hydrophobicity of the cotton cloth. With the introduction of VAC, the contact angle is 122°. Its contact angle value increases slightly. Because the VAC structure is relatively symmetrical and has strong hydrophobicity, it further increases the contact angle. When VAC and DMAEMA are copolymerized on the material surface, the contact angle decreases slightly. This is because a large number of hydrophilic dimethylamine functional groups are introduced. However, after quaternization modification, with the introduction of hexadecyl functional groups, the contact angle rises again to 123.4°. The long-chain alkyl groups can assist the material to have better hydrophobic performance. The hydrophobicity of its surface does not decrease due to the formation of a large number of hydrophilic quaternary ammonium salt functional groups, but instead increases slightly. With the progress of chlorination, the contact angle does not change much, indicating that the chlorination oxidation process does not damage the material structure and the hydrophobic performance of the material remains good. The modification process endows the material with self-cleaning properties.

[0059] (4) Antibacterial property test: The pure cotton cloth obtained in Comparative Example 1 and the surface-modified cotton fabric with haloamine / quaternary ammonium salt structure and the surface-modified cotton fabric with chlorinated haloamine / quaternary ammonium salt structure obtained in Example 1 were used to test the antibacterial properties of the pure cotton cloth and the chlorinated modification by the plate counting method. The antibacterial property test diagram is as Figure 5 shown. The pure cotton cloth shows a relatively low antibacterial effect. There are still a large number of bacteria after 60 minutes of contact. There are still a small number of bacteria on the non-chlorinated quaternary ammonium salt / haloamine modified fabric after 30 minutes, and the bacteria can be completely killed after 60 minutes; the chlorinated quaternary ammonium salt / haloamine modified fabric has good antibacterial effects on Escherichia coli and Staphylococcus aureus. No viable bacteria were detected after 10 minutes of contact; and an inhibition zone experiment was carried out with Escherichia coli and Staphylococcus aureus. As Figure 5 can be observed in the figure, there is an obvious inhibition zone, indicating that the chlorinated quaternary ammonium salt / haloamine copolymer-modified cotton cloth can release chlorine oxide into the surrounding environment to inactivate bacteria and play a role in bacteriostasis. There is no obvious inhibition zone for the modified fabric and the non-chlorinated quaternary ammonium salt / haloamine modified cotton cloth, indicating that the haloamine functional group has a strong synergistic antibacterial effect on the quaternary ammonium salt.

[0060] (5) Anti-ultraviolet test: The pure cotton fabric obtained in Comparative Example 1, the CPTMO-modified cotton fabric obtained in Example 1, the surface-modified cotton fabric with a haloamine / quaternary ammonium salt structure, and the surface-modified cotton fabric with a chlorinated haloamine / quaternary ammonium salt structure were cut into 1 cm x 1 cm sizes and placed in a UV-visible spectrophotometer for testing the UV transmittance curve. Among them, the CPTMO-modified cotton fabric showed a significantly enhanced ability to absorb ultraviolet rays and a lower UV transmittance. With the occurrence of the copolymerization reaction, the UPF value of the anti-ultraviolet index continued to rise, indicating that its chlorination would cause the UPF value to decline somewhat, but it was still higher than 50, further indicating that the fabric had good anti-ultraviolet performance.

[0061] (6) Wound infection test: The pure cotton fabric obtained in Comparative Example 1 and the surface-modified cotton fabric with a chlorinated haloamine / quaternary ammonium salt structure in Example 1 were respectively dropped with Staphylococcus aureus under similar wounds (8 mm in diameter) for the wound infection test, and the recording period was at the beginning, the first day, the second day, the fourth day, the eighth day, and the twelfth day. The wound infection test is as Figure 7 shown. It can be seen from the figure that the surface-modified cotton fabric with a modified chlorinated haloamine / quaternary ammonium salt structure had a significantly better healing rate within 12 days than the ordinary pure cotton fabric, further indicating that the surface-modified cotton fabric with a modified chlorinated haloamine / quaternary ammonium salt structure had a stronger ability to recover and regenerate.

[0062] The present invention provides the preparation and application of a haloamine / quaternary ammonium salt copolymer-modified antibacterial material containing cyanuric acid. The haloamine / quaternary ammonium salt copolymer-modified antibacterial material containing cyanuric acid synthesizes potassium 1-allyl-s-triazine-2,4,6-trione through nucleophilic substitution, grafts it onto a natural fiber pretreated with 3-chloropropyltrimethoxysilane, copolymerizes the modified fiber with dimethylethyl methacrylate through a continuous step, reacts with an alkyl bromide in ethanol, and then undergoes substitution in a disinfectant solution to obtain a chlorinated haloamine / quaternary ammonium salt copolymer-modified material. The haloamine / quaternary ammonium salt copolymer-modified antibacterial material containing cyanuric acid prepared by the present invention can quickly and efficiently kill Escherichia coli and Staphylococcus aureus, and at the same time has good recovery and regeneration ability, anti-ultraviolet irradiation ability, and self-cleaning ability.

[0063] The above are only the preferred embodiments of the present invention and are not used to limit the present invention. For those skilled in the art, the present invention can have various changes and modifications. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A halogenamine / quaternary ammonium salt copolymer modified antibacterial material containing cyanuric acid, characterized in that, The structural formula of the haloamine / quaternary ammonium salt copolymer is as follows: Wherein, R is a straight-chain alkane with 12-18 carbon atoms, and X is chlorine or bromine.

2. Preparation method of a cyanuric acid-containing halogenamine / quaternary ammonium salt copolymer-modified antibacterial material, characterized in that: It includes the following steps: S1. Immerse the fiber fabric in a weakly alkaline solution, perform ultrasonic cleaning, washing and drying to obtain the cleaned fiber fabric; take an appropriate amount of ethanol / aqueous solution of 3-chloropropyltrimethoxysilane and perform oscillating stirring to obtain a mixed solution; immerse the cleaned fiber fabric in the mixed solution, cure at a high temperature for several hours, and then perform washing and drying to obtain CPTMO-modified fiber; S2. Weigh an appropriate amount of cyanuric acid, stir it in an alkaline aqueous solution, and then slowly drop allyl bromide to obtain a 1-allyl-s-triazine-2,4,6-trione salt solution. Place the CPTMO-modified fiber fabric prepared in step S1 in the 1-allyl-s-triazine-2,4,6-trione salt solution, and then add a small amount of potassium iodide and tetrabutylammonium iodide to obtain VAC-modified fiber; S3. Weigh an appropriate amount of dimethylethyl methacrylate and potassium persulfate, add them to the VAC-modified fiber fabric obtained in step S2, carry out temperature-raising polymerization, and then perform multiple washings to obtain VAC / DMAEMA copolymer-modified fiber; S4. Immerse the VAC / DMAEMA copolymer-modified fiber prepared in step S3 in an ethanol solution and a haloalkane for reflux immersion to obtain a QACs-modified fiber fabric; immerse the QACs-modified fiber fabric in a disinfectant solution and place it at room temperature for 1 hour to obtain a surface-modified fiber with a chloro-haloamine / quaternary ammonium salt structure.

3. The preparation method of a cyanuric acid-containing haloamine / quaternary ammonium salt copolymer-modified antibacterial material according to claim 2, characterized in that, In step S1, the mass ratio of the ethanol / aqueous solution of 3-chloropropyltrimethoxysilane is 3-5:50:50, and the pH range of the ethanol / aqueous solution of 3-chloropropyltrimethoxysilane is 4-6.

4. The preparation method of a cyanuric acid-containing haloamine / quaternary ammonium salt copolymer modified antibacterial material according to claim 2, characterized in that: In step S1, the soaking time is 30-120 s, the high-temperature curing time is 5-30 min, and the temperature range is 60-95 °C.

5. The preparation method of a cyanuric acid-containing haloamine / quaternary ammonium salt copolymer modified antibacterial material according to claim 2, characterized in that, In step S2, the alkaline aqueous solution is one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

6. The preparation method of a cyanuric acid-containing haloamine / quaternary ammonium salt copolymer modified antibacterial material according to claim 5, characterized in that, The mass fraction of the alkali in the alkaline aqueous solution is 10-15%, and the molar ratio of the alkaline aqueous solution to cyanuric acid is 2.5-3.5:

1.

7. The preparation method of a cyanuric acid-containing haloamine / quaternary ammonium salt copolymer-modified antibacterial material according to claim 2, characterized in that: In step S2, the mass ratio of potassium iodide to tetrabutylammonium iodide is 0.05-0.15 g:100 mL.

8. The preparation method of a cyanuric acid-containing haloamine / quaternary ammonium salt copolymer-modified antibacterial material according to claim 2, characterized in that: In step S4, the haloalkane is one or more of monobromo- and monochloro-substituted straight-chain alkanes with C 12 -C 18 , and the molar ratio of the haloalkane to DMAEMA is 1 - 1.1:

1.

9. The preparation method of a cyanuric acid-containing haloamine / quaternary ammonium salt copolymer-modified antibacterial material according to claim 2, characterized in that: In step S4, the disinfectant is sodium hypochlorite or household sodium hypochlorite disinfectant with a mass concentration of 0.1-3% and a pH value of 4-7.

5.

10. A protective article, characterized in that: It includes the cyanuric acid-containing haloamine / quaternary ammonium salt copolymer-modified antibacterial material according to claim 1.

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