Halogenated amine-based antibacterial porous organic polymer-based composite fiber materials, their preparation and application

Abstract

This invention relates to a halogenated amine-based antibacterial porous organic polymer-based composite fiber material, its preparation, and its application. The preparation method uses cellulose-based fibers as the substrate and melamine chloride and polyamine compounds as precursor monomers for the halogenated amine-type porous organic polymer. Through a surface activation-in-situ synthesis reaction, a composite fiber material modified with a high-density secondary amine-based porous organic polymer is obtained. This is followed by a hypohalite rinsing treatment to obtain an antibacterial halogenated amine porous organic polymer composite fiber material (NX-POP@Cell). Compared with existing technologies, the method provided by this invention achieves high-density grafting of antibacterial halogenated amine structures onto cellulose fibers through a simple and efficient preparation method, resulting in a final material exhibiting rapid and efficient contact sterilization performance. It has significant market potential in fields such as water filtration and medical protection.

Description

Technical Field

[0001] This invention relates to the field of polymer materials, and in particular to a halogenated amine-based antibacterial porous organic polymer-based composite fiber material, its preparation, and its application. Background Technology

[0002] Aquatic pathogens contaminating natural lakes and drinking water pose a global public health and safety concern. According to the World Health Organization in 2018, over 2 billion people worldwide face drinking water health issues, and approximately 4.5 billion lack effective and safe drinking water purification systems. Traditional water purification methods primarily involve directly adding disinfectants to water bodies, but the residual disinfectants in the water pose additional challenges to human health and sustainable environmental development. Therefore, ultrafiltration, reverse osmosis, and nanofiltration technologies have been developed and applied in the field of water purification. However, these technologies and the filter materials involved cannot kill aquatic pathogens, and certain safety hazards remain in practical use.

[0003] Based on this, researchers have successfully prepared various new water filtration materials with antibacterial properties by physically blending and chemically cross-linking antibacterial agents with fiber materials. Using fiber materials as carriers for antibacterial agents facilitates macroscopic continuity, ease of operation, and recyclability of the antibacterial agents, while avoiding secondary pollution of water bodies from excessive antibacterial agents. Among these, halogenated amine antibacterial materials have attracted widespread attention in the field of water purification due to their broad-spectrum antibacterial activity, rapid antibacterial action, long-lasting effectiveness, and regenerable function. Halogenated amine antibacterial agents contain NX bonds (X being Cl or Br), which can be obtained by rinsing compounds containing amino, amide, or imide groups with hypohalite salts. The antibacterial properties of halogenated amine compounds originate from the highly oxidizing NX bonds, which can inactivate microorganisms through redox reactions. The regenerability of halogenated amine antibacterial agents is mainly due to the transformation of NX bonds into NH bonds upon contact with microorganisms. After further rinsing, the NH bonds regain X atoms and transform into antibacterial NX bonds. However, the preparation process of existing haloamine antibacterial fiber materials relies on complex surface modification reactions, resulting in low grafting efficiency. This leads to low haloamine density on the surface of the material after rinsing with hypohalates, which severely limits the antibacterial efficiency and application durability of such materials.

[0004] Porous organic polymers are a novel class of organic compounds with three-dimensional networks formed by covalently linked compounds containing multiple functional groups. They possess high specific surface area, microporous and mesoporous characteristics, and abundant active functional groups, and are widely used in separation, adsorption, catalysis, and other fields. The high specific surface area and active sites of porous organic polymers provide the possibility for high-density modification of haloamine structures on fiber surfaces.

[0005] Therefore, in order to achieve efficient filtration and purification of microorganisms in water, the preparation of high-density, high-stability, and renewable antimicrobial halogenated fiber materials is of great significance in ensuring drinking water safety and sustainable environmental development. Summary of the Invention

[0006] The purpose of this invention is to overcome the shortcomings of the prior art and provide a method for preparing a green and sustainable halogen amine porous organic polymer composite fiber material that is simple to prepare, highly efficient, and can rapidly kill bacteria in water.

[0007] The objective of this invention can be achieved through the following technical solutions:

[0008] The first aspect of this invention provides a method for preparing a halogenated amine-based antibacterial porous organic polymer-based composite fiber material, comprising the following steps:

[0009] Using cellulose-based fibers as the substrate and melamine chloride and polyamine compounds as precursor monomers for haloamine-type porous organic polymers, a composite fiber material modified with high-density secondary amine-based porous organic polymers was obtained through a surface activation-in-situ synthesis reaction. After being treated with hypohalite rinsing, a haloamine porous organic polymer composite fiber material (NX-POP@Cell) with antibacterial properties was obtained.

[0010] Furthermore, in the surface activation process, the activator used is selected from one or more of cyanuric chloride, glutaraldehyde, and N,N'-disuccinimidyl carbonate.

[0011] Furthermore, the activator is selected from one or more of the following compounds:

[0012]

[0013] The polyamino compound is selected from one or more of melamine, diphenylamine, p-diaminobiphenyl, ethylenediamine, 2-(aminomethyl)-propanediamine, triaminoethylamine, and polyethyleneimine.

[0014] Furthermore, the polyamino compound is selected from one or more of the following compounds:

[0015]

[0016] Furthermore, the specific steps include:

[0017] S1: Take the hydroxyl activator in dimethylacetamide, add triethylamine as a catalyst, and obtain the activation reaction solution;

[0018] S2: Immerse cellulose-based fibers in the reaction solution and react them under ice-water bath conditions to obtain fiber material A;

[0019] S3: Melamine chloride and polyamino compounds are dissolved separately in anhydrous dimethyl sulfoxide and mixed. Triethylamine is added dropwise to the above mixed solution system as an in-situ synthesis catalyst to obtain solution system A.

[0020] S4: Mix fiber material A with the solution system A and react under nitrogen protection to obtain fiber material B;

[0021] S5: The fiber material B is washed with dimethyl sulfoxide, water, and methanol, and then dried to obtain fiber material C;

[0022] S6: Immerse fiber material C in a hypohalite aqueous solution, rinse at room temperature, wash with water, and dry to obtain a halogen amine porous organic polymer composite fiber material (NX-POP@Cell) with antibacterial properties.

[0023] Further, in S1, the ratio of cyanuric chloride to dimethylacetamide in the activation reaction solution is 0.5–6.0 mmol: 20–100 mL;

[0024] In S1, the ratio of the hydroxyl activator to triethylamine is 0.5–6.0 mmol: 0.5–3.0 mL.

[0025] Furthermore, in S2, the temperature of the ice-water bath is 0–5°C, and the reaction time is 30–180 minutes;

[0026] In S3, the ratio of cyanuric chloride to polyamine compound is 0.5–6.0 mmol: 0.5–6.0 mmol, and the ratio of triethylamine: (cyanuric chloride + polyamine compound) is 0.5–3.0 mL: 0.5–12 mmol; the ratio of (cyanuric chloride + polyamine compound): dimethyl sulfoxide is 0.5–12 mmol: 100 mL.

[0027] In S4, the reaction time is 12–72 hours;

[0028] In S6, the concentration of the hypohalite aqueous solution is 100–500 ppm.

[0029] Furthermore, the cellulose-based fiber is selected from one or more of cotton fiber, hemp fiber, bamboo fiber, viscose fiber, Tencel fiber, and Modal fiber.

[0030] A second aspect of the present invention provides a halogenated amine antibacterial porous organic polymer-based composite fiber material prepared by the method described above.

[0031] A third aspect of the present invention provides an application of the above-mentioned material, wherein the porous organic polymer-based composite fiber material is used as a contact antibacterial water filtration material. The material utilizes the oxidizing halogen amine structure to undergo an oxidation-reduction reaction with the bacteria in contact, thereby destroying the bacteria's proteins, DNA, RNA, and lipids, achieving the effect of killing microorganisms. The halogen amine structure is an N×X bond, wherein X is Cl or Br.

[0032] Compared with the prior art, the present invention has the following technical advantages:

[0033] The method provided by this invention uses a naturally sourced fiber substrate, and the material preparation process is relatively simple, making it suitable for large-scale industrial production. The prepared composite fiber material possesses properties such as high-density haloamine structure, strong oxidizing properties, excellent effective chlorine stability, and functional renewability. Simultaneously, it avoids the potential threat of bactericide release and residues in water bodies, and has broad application value in fields such as environmental water filtration and drinking water purification. Attached Figure Description

[0034] Figure 1 This is a schematic diagram of the preparation and application process of Example 1;

[0035] Figure 2 The reaction equations for the preparation of Examples 1–4 are as follows;

[0036] Figure 3 These are electron microscope (SEM) images of the fiber materials prepared in Example 1 at different monomer concentrations: a) 0.5 mmol, b) 1.5 mmol, c) 3.0 mmol, and d) 6.0 mmol;

[0037] Figure 4 The nitrogen adsorption-desorption curves are for the fiber material prepared in Example 1 at a monomer concentration of 3.0 mmol and the control sample.

[0038] Figure 5 The pore size distribution curves are those of the fiber material prepared in Example 1 at a monomer concentration of 3.0 mmol and the control sample.

[0039] Figure 6 Here are the Fourier transform infrared (FTIR) spectra of the fiber material prepared in Example 1 at a monomer concentration of 3.0 mmol and the control sample:

[0040] Figure 7 Thermogravimetric analysis (TGA) curves of the fiber material prepared in Example 1 at a monomer concentration of 3.0 mmol and the control sample are shown.

[0041] Figure 8 This is the curve showing the relationship between the effective chlorine content and chlorine bleaching time in Example 1;

[0042] Figure 9 This is the curve showing the relationship between the effective chlorine content and the pH of chlorine bleaching in Example 1;

[0043] Figure 10 This is the curve showing the relationship between the effective chlorine content and the chlorine bleaching cycle in Example 1;

[0044] Figure 11 This is the curve showing the relationship between available chlorine content and storage time in Example 1;

[0045] Figure 12 The curve showing the relationship between the killing efficiency of Galanz negative Escherichia coli and contact time, and the image of the bacterial tray, are from Example 1.

[0046] Figure 13 The curve showing the relationship between the killing efficiency of Listeria monocytogenes positive bacteria on Galanz and the contact time, and the image of the bacterial tray are from Example 1.

[0047] Figure 14 This is a schematic diagram of a water filtration device;

[0048] Figure 15 This is the curve showing the relationship between the killing efficiency of Escherichia coli in water and the water flux in Example 1;

[0049] Figure 16 This is the curve showing the relationship between the killing efficiency of Listeria monocytogenes in water and the water flux in Example 1;

[0050] Figure 17 This is the curve showing the relationship between the killing efficiency of E. coli in water and the water filtration flow rate in Example 1;

[0051] Figure 18 This is the curve showing the relationship between the killing efficiency of Listeria monocytogenes in water and the water filtration flow rate in Example 1. Detailed Implementation

[0052] The method provided by this invention uses cellulose-based fibers as the substrate and cyanuric chloride and polyamine compounds as precursor monomers for haloamine-type porous organic polymers. Through a surface activation-in-situ synthesis reaction, a composite fiber material (NH-POP@Cell) modified with high-density secondary amine-based porous organic polymers is obtained. Subsequently, after hypohalite rinsing treatment, a haloamine porous organic polymer composite fiber material (NX-POP@Cell) with antibacterial properties is obtained.

[0053] Specifically, the activator used in the surface activation process of the present invention includes cyanuric chloride, glutaraldehyde, and N,N'-disuccinimidyl carbonate, preferably cyanuric chloride;

[0054] Specifically, the polyamino compounds described in this invention include, but are not limited to, melamine, diphenylamine, p-diaminobiphenyl, ethylenediamine, 2-(aminomethyl)-propanediamine, triaminoethylamine, and polyethyleneimine, with melamine being preferred.

[0055] The structure of the hydroxyl activator described in this invention is shown below:

[0056]

[0057] The structure of the polyamine compound described in this invention is shown below:

[0058]

[0059] The catalyst for the surface activation and in-situ synthesis reaction described in this invention is triethylamine.

[0060] In a preferred embodiment of the present invention, the hydroxyl activator is cyanuric chloride, and the polyamine compound is melamine; the haloamine porous organic polymer fiber material is prepared by a method comprising the following steps:

[0061] (1) Dissolve 0.5–6.0 mmol of cyanuric chloride in dimethylacetamide, and add 1 mL of triethylamine as a catalyst to obtain an activated reaction solution;

[0062] (2) Immerse cotton fibers in the reaction solution and react for 60 minutes in an ice-water bath at 0–5°C;

[0063] (3) Take 3.0 mmol of cyanuric chloride and 3.0 mmol of melamine, dissolve them in 50 mL of anhydrous dimethyl sulfoxide, and add 1 mL of triethylamine to the melamine solution system as a catalyst for in-situ synthesis reaction.

[0064] (4) Mix the activated cellulose-based fibers with the solution system obtained in step (3), purge with nitrogen for 10 minutes, and then react at 50°C for 24 hours under sealed conditions.

[0065] (5) NH-POP@Cell is obtained by washing with dimethyl sulfoxide, water, and methanol, and then drying.

[0066] (6) Immerse the fiber material obtained in step (5) in a 200 ppm sodium hypochlorite solution with a pH of 2–11 and rinse at room temperature for a certain period of time (0–500 minutes).

[0067] (7) Finally, NX-POP@Cell is obtained by washing with a lot of water and drying.

[0068] The antibacterial composite fiber material prepared by this invention has a high specific surface area (50–200 m²). 2 The fiber composite material has a high porosity (g / g) and is structurally stable and insoluble in water and other common organic solvents.

[0069] The antibacterial fiber material prepared by this invention has a high-density haloamine structure, a high available chlorine content (3000–7000 ppm), stable performance, and excellent antibacterial properties, regeneration, and reusability.

[0070] The present invention will now be described in detail with reference to the accompanying drawings and specific embodiments. Any preparation methods, materials, structures, or compositional ratios not explicitly described in this technical solution are considered common technical features disclosed in the prior art.

[0071] The abbreviations used in the following specific implementation have the following indicative meanings: SEM stands for Scanning Electron Microscopy; FTIR stands for Fourier Transform Infrared Spectroscopy; TGA stands for Thermogravimetric Analysis.

[0072] The SEM spectra of the material obtained in Example 1 were measured using a Quattro ESEM; the FTIR spectra of the material were measured using a Nicolet 6700 infrared analyzer; and the TGA curves of the material were measured using a Shimadzu TGA-60 thermogravimetric analyzer.

[0073] Example 1

[0074] Using cotton fiber as the base material, cyanuric chloride as the hydroxyl activator, cyanuric chloride and melamine as monomers of secondary amine porous organic polymers (i.e., haloamine precursors), and sodium hypochlorite as the hypohalate, an antibacterial haloamine porous organic polymer composite fiber material was prepared.

[0075] The specific steps are as follows:

[0076] (1) Dissolve 3.0 mmol of cyanuric chloride in 60 ml of dimethylacetamide, and add 1 mL of triethylamine as a catalyst to obtain an activated reaction solution;

[0077] (2) Immerse the cotton fibers in the reaction solution and react in an ice-water bath at 0–5°C for 60 minutes;

[0078] (3) Take 3.0 mmol of cyanuric chloride and 3.0 mmol of melamine, dissolve them in 50 mL of anhydrous dimethyl sulfoxide and mix them. Add 1 mL of triethylamine to the above mixed solution system as an in-situ reaction catalyst.

[0079] (4) Mix the activated cellulose-based fibers with the solution system obtained in step (3), purge with nitrogen for 10 minutes, and then react at 150°C for 24 hours under closed conditions.

[0080] (5) The cotton fiber modified with the porous organic polymer haloamine precursor is obtained by washing with dimethyl sulfoxide, water, methanol, and drying.

[0081] (6) Immerse the fiber material obtained in step (5) in a 200 ppm sodium hypochlorite solution with pH 2–11 (a series of pH adjustments) and stir at room temperature for a certain period of time (a series of pH adjustments from 0 to 500 minutes).

[0082] (7) The final antibacterial halogen amine porous organic polymer / cotton fiber composite material is obtained by washing with a lot of water and drying.

[0083] Example 2

[0084] Using cotton fiber as the base material, melamine chloride as the hydroxyl activator, melamine chloride and p-phenylenediamine as porous organic polymer monomers, and sodium hypochlorite as hypochlorite, a halogenated amine porous organic polymer antibacterial fiber material was prepared.

[0085] The specific steps are as follows:

[0086] (1) Dissolve 3.0 mmol of cyanuric chloride in 60 ml of dimethylacetamide, and add 1 mL of triethylamine as a catalyst to obtain an activated reaction solution;

[0087] (2) Immerse the cotton fibers in the reaction solution and react in an ice-water bath at 0–5°C for 60 minutes;

[0088] (3) Take 3.0 mmol of cyanuric chloride and 3.0 mmol of p-phenylenediamine, dissolve them in 50 mL of anhydrous dimethyl sulfoxide and mix them. Add 1 mL of triethylamine to the above mixed solution system as an in-situ reaction catalyst.

[0089] (4) Mix the activated cellulose-based fibers with the solution system obtained in step (3), purge with nitrogen for 10 minutes, and then react at 150°C for 24 hours under closed conditions.

[0090] (5) The cotton fiber modified with the porous organic polymer haloamine precursor is obtained by washing with dimethyl sulfoxide, water, methanol, and drying.

[0091] (6) Immerse the fiber material obtained in step (5) in a 200 ppm hypochlorite solution with pH 2–11 (a series of pH adjustments) and stir at room temperature for a certain period of time (a series of pH adjustments from 0 to 500 minutes).

[0092] (7) The final antibacterial halogen amine porous organic polymer / cotton fiber composite material is obtained by washing with a lot of water and drying.

[0093] Example 3

[0094] Using cotton fiber as the base material, melamine chloride as the hydroxyl activator, melamine chloride and ethylenediamine as porous organic polymer monomers, and sodium hypochlorite as hypochlorite, a haloamine porous organic polymer antibacterial fiber material was prepared.

[0095] The specific steps are as follows:

[0096] (1) Dissolve 3.0 mmol of cyanuric chloride in 60 ml of dimethylacetamide, and add 1 mL of triethylamine as a catalyst to obtain an activated reaction solution;

[0097] (2) Immerse the cotton fibers in the reaction solution and react in an ice-water bath at 0–5°C for 60 minutes;

[0098] (3) Take 3.0 mmol of cyanuric chloride and 6.0 mmol of ethylenediamine, dissolve them in 50 mL of anhydrous dimethyl sulfoxide and mix them. Add 1 mL of triethylamine to the above mixed solution system as an in-situ reaction catalyst.

[0099] (4) Mix the activated cellulose-based fibers with the solution system obtained in step (3), purge with nitrogen for 10 minutes, and then react at 110°C for 24 hours under closed conditions.

[0100] (5) The cotton fiber modified with the porous organic polymer haloamine precursor is obtained by washing with dimethyl sulfoxide, water, methanol, and drying.

[0101] (6) Immerse the fiber material obtained in step (5) in a 200 ppm hypochlorite solution with pH 2–11 (a series of pH adjustments) and stir at room temperature for a certain period of time (a series of pH adjustments from 0 to 500 minutes).

[0102] (7) The final antibacterial halogen amine porous organic polymer / cotton fiber composite material is obtained by washing with a lot of water and drying.

[0103] Example 4

[0104] Using cotton fiber as the base material, cyanuric chloride as the hydroxyl activator, cyanuric chloride and triaminoethylamine as porous organic polymer monomers, and sodium hypochlorite as hypochlorite, a haloamine porous organic polymer antibacterial fiber material was prepared.

[0105] The specific steps are as follows:

[0106] (1) Dissolve 3.0 mmol of cyanuric chloride in 60 ml of dimethylacetamide, and add 1 mL of triethylamine as a catalyst to obtain an activated reaction solution;

[0107] (2) Immerse the cotton fibers in the reaction solution and react in an ice-water bath at 0–5°C for 60 minutes;

[0108] (3) Take 3.0 mmol of cyanuric chloride and 6.0 mmol of triaminoethylamine, dissolve them in 50 mL of anhydrous dimethyl sulfoxide and mix them. Add 1 mL of triethylamine to the above mixed solution system as an in-situ reaction catalyst.

[0109] (4) Mix the activated cellulose-based fibers with the solution system obtained in step (3), purge with nitrogen for 10 minutes, and then react at 150°C for 24 hours under closed conditions.

[0110] (5) The cotton fiber modified with the porous organic polymer haloamine precursor is obtained by washing with dimethyl sulfoxide, water, methanol, and drying.

[0111] (6) Immerse the fiber material obtained in step (5) in a 200 ppm hypochlorite solution with pH 2–11 (a series of pH adjustments) and stir at room temperature for a certain period of time (a series of pH adjustments from 0 to 500 minutes).

[0112] (7) The final antibacterial halogen amine porous organic polymer / cotton fiber composite material is obtained by washing with a lot of water and drying.

[0113] Characterization data and analysis

[0114] Figure 1 This diagram illustrates the preparation and application process of the halogenated amine porous organic polymer / cotton fiber composite material (NX-POPx@Cell, where x represents the monomer concentration of NH-POP) as shown in Example 1. Cotton fiber is used as the cellulose-based fiber substrate, and cyanuric chloride is used as the hydroxyl activator. This provides covalent reaction sites for the subsequent modification of the fiber with the secondary amine-based porous organic polymer halogenated amine precursor constructed using melamine and cyanuric chloride monomers, which helps improve the functional stability of the final material in long-term and cyclic applications. Subsequently, the fiber material is rinsed with sodium hypochlorite to generate halogenated amine structures (i.e., N-Cl); upon contact with bacteria, a redox reaction occurs, achieving the purpose of killing bacteria. The used fiber material can be recycled by chlorination in an aqueous sodium hypochlorite solution to regenerate its antibacterial properties.

[0115] Figure 2 The diagram shows the chemical reaction process in Examples 1-4. Using cotton fiber as the base material and cyanuric chloride as the hydroxyl activator, cyanuric chloride and four polyamine compounds were used to construct monomers to prepare antibacterial fiber materials with different pore structures and haloamine precursor densities. Subsequently, the materials were washed with sodium hypochlorite aqueous solution to obtain antibacterial fiber composite materials with high-density haloamine structures.

[0116] To investigate the optimal conditions for modifying and grafting the haloamine-type porous organic polymer onto cotton fibers in Example 1, we screened the concentrations of the building monomers of the haloamine precursor. For example... Figure 3As shown, when the concentrations of melamine and cyanuric chloride increased from 0.5 mmol to 6.0 mmol, the surface roughness of the fibers significantly improved, indicating that more haloamine precursors were grafted onto the cotton fiber surface. Based on the weight changes before and after in-situ synthesis of haloamine precursors on cotton fibers, the grafting rates of the fiber composites prepared at monomer concentrations of 0.5, 1.5, 3.0, and 6.0 mmol were characterized as 8%, 13%, 23%, and 26%, respectively.

[0117] Figure 4 and Figure 5 The nitrogen adsorption-desorption curves and pore size distribution curves of fiber composites prepared under different monomer concentrations are shown. With the increase of the grafting rate of the haloamine precursor (i.e., the secondary amine porous organic polymer), the specific surface area and porosity of the cotton fibers significantly increase. For example, compared to ordinary cotton fibers, the specific surface area of ​​NH-POP3@Cell increases from 1.69 μm. 2 g -1 Increased to 97.52m 2 g -1 The pore volume ranges from 0.004 cm³. 3 g -1 Increased to 0.662cm 3 g -1 The significant increase in specific surface area and pore volume enabled high-density modification of the haloamine structure on the fiber surface and the stable presence of antibacterial available chlorine.

[0118] Taking into account factors such as the grafting rate of NH-POP on the composite fiber material, raw material utilization rate, and strength, a monomer concentration of 3.0 mmol is preferred for preparing antibacterial halogen amine fiber composite materials.

[0119] Figure 6 The FTIR spectrum of NH-POPx@Cell is shown. It is clearly visible in the figure that after NH-POP modification, the spectrum at 1548 cm⁻¹... -1 1474cm -1 1354cm -1 A new absorption peak appears at 813 cm⁻¹, indicating the stretching vibration of the unsaturated carbon-nitrogen bonds in the triazine ring; additionally, at 813 cm⁻¹... -1 The new peak appearing is the respiratory vibration peak of the triazine group. These results demonstrate that NH-POP was successfully grafted onto the surface of cotton fibers.

[0120] Figure 7The TGA curves of NH-POPx@Cell are shown. With increasing temperature, the sample exhibits some mass loss up to 100℃, mainly due to the presence of free water or residual solvent in NH-POPx@Cell. Cotton fiber decomposes at around 300℃, while the decomposition temperature of NH-POP powder is 430℃. This results in the decomposition temperature of NH-POPx@Cell falling between that of cotton fiber and POP powder (350℃). Furthermore, only one distinct degradation peak appears in the TGA curves, further demonstrating that NH-POP and cotton fiber are connected by covalent bonds rather than through physical mixing.

[0121] Sodium hypochlorite was used as the representative hypohalite to chlorinate NH-POPx@Cell, thereby imparting antibacterial properties and yielding NCl-POPx@Cell. The available chlorine content on NCl-POPx@Cell is a key factor determining the material's bactericidal performance. Therefore, we screened the chlorination process time and pH. Figure 8 As shown, with the extension of chlorine bleaching time, the available chlorine content on NCl-POP3@Cell increases linearly within 0–60 minutes, and then reaches saturation. Its available chlorine saturation level can reach 5500–5800 ppm, with 60 minutes being the optimal time for the chlorine bleaching reaction.

[0122] Figure 9 The available chlorine content curves of NCl-POP3@Cell after 60 minutes of chlorine bleaching and water washing under different pH conditions are shown. The optimal pH for the chlorine bleaching reaction is 4.0, corresponding to an available chlorine content of 6638 ppm in the material.

[0123] Figure 10 The regenerability of available chlorine in NCl-POP3@Cell was demonstrated. Specifically, NCl-POP3@Cell was subjected to chlorine bleaching using a 200 ppm sodium hypochlorite solution, followed by available chlorine quenching using a 0.1 M sodium thiosulfate solution. Figure 9 As shown, NCl-POP3@Cell maintains a stable and high concentration of available chlorine throughout five chlorine bleaching-quenching cycles, ensuring its efficient, long-lasting, and regenerable antibacterial performance in water filtration applications.

[0124] Figure 11The available chlorine stability of NCl-POP3@Cell under ambient temperature and light-protected conditions was demonstrated. During 20 days of storage, the available chlorine content on NCl-POP3@Cell remained stably at a high level (6250–7000 ppm), ensuring the durability of the material's antibacterial properties and its storage resistance. The excellent storage stability of NCl-POP3@Cell can be mainly attributed to the following two aspects: (1) The haloamine structure in NH-POP is a secondary amine structure, which has stronger available chlorine stability compared to amides and imides; (2) The microporous structure of NH-POP can, to a certain extent, regulate the gradual release of available chlorine, thereby improving its storage stability.

[0125] The antibacterial properties of NCl-POP3@Cell were first evaluated through a contact sterilization experiment, using *Escherichia coli* and *Listeria* as representative bacteria of Galanz negative and positive bacteria, respectively. Specifically, 10 μL of a 10 μL solution was used. 6 -10 7 CFU / mL of bacterial suspension was dropped onto the surface of 20 mg NCl-POP3@Cell and completely wetted. After standing for 0–10 minutes, the NCl-POP3@Cells with bacterial suspension were washed with 1 mL of PBS buffer by shaking. The washing solution was serially diluted and inoculated into agar plates and incubated at 37°C for 24 hours. The antimicrobial properties of the material in relation to contact time were obtained by calculating the number of bacteria on the agar plates.

[0126] like Figure 12 and 13 As shown, using chlorinated cotton fibers and unchlorinated NH-POP3@Cell as control groups, NCl-POP3@Cell showed a 99.9999% killing efficiency against Escherichia coli and Listeria within a 1-minute contact time. However, the control group, lacking halogen amine precursors or N-Cl structures, showed no significant killing effect against Escherichia coli and Listeria.

[0127] use Figure 14 The dynamic water filtration device shown is Figure 15 and 16 The relationship between the bactericidal efficiency of NCl-POP3@Cell after chlorination and the water filtration volume is shown. Chlorinated cotton fibers and NH-POP3@Cell were used as control groups. The NCl-POP3@Cell was tested during dynamic water filtration (water flow rate controlled at 250 mL / h). -1 It exhibits excellent bactericidal properties. Specifically, its effectiveness in killing Escherichia coli is particularly high at a water flux of 325 L / m³. -2 It can still maintain a 99.9999% kill efficiency; while for Listeria, even at water fluxes exceeding 100 L / m³, it can still achieve a kill efficiency of 99.9999%; -2Afterwards, the sterilization efficiency gradually decreased to 99%.

[0128] like Figure 17 and 18 As shown, the water filtration rate had no significant effect on the bactericidal efficiency of NCl-POP3@Cell after chlorination. The flow rate was between 159 and 2229 L / m. -2 h -1 When the range of variation was within a certain range, the material's killing efficiency against Escherichia coli and Listeria remained stable at 99.9999%. In contrast, ordinary cotton fibers after chlorine bleaching had no filtering or killing effect on bacteria in water.

[0129] The above description of the embodiments is provided to enable those skilled in the art to understand and use the invention. It will be apparent to those skilled in the art that various modifications can be made to these embodiments, and the general principles described herein can be applied to other embodiments without inventive effort. Therefore, the present invention is not limited to the above embodiments, and any improvements and modifications made by those skilled in the art based on the disclosure of the present invention without departing from the scope of the invention should be within the protection scope of the present invention.

Claims

1. An application of a halogenated amine-based antibacterial porous organic polymer-based composite fiber material, characterized in that, Porous organic polymer-based composite fiber material is used as a dynamic contact antibacterial water filtration material. The material utilizes the oxidizing halogen amine structure to undergo an oxidation-reduction reaction with the bacteria in contact, thereby destroying the proteins, DNA, RNA, and lipids of the bacteria and achieving the efficiency of killing microorganisms. The halogen amine structure is an N×N bond, where X is Cl. The specific surface area of ​​haloamine porous organic polymer composite fiber materials is 50-200 m². 2 / g; At the dynamic water filtration flow rate of At that time, the bactericidal efficiency of the haloamine porous organic polymer composite fiber material against Escherichia coli and Listeria in water was 99.9999%. The preparation method of porous organic polymer-based composite fiber materials includes the following steps: S1: Take the activator in dimethylacetamide, add triethylamine as a catalyst, and obtain the activation reaction solution; the activator is selected from one or more of cyanuric chloride, glutaraldehyde, and N,N'-disuccinimidyl carbonate; the ratio of the activator to the dimethylacetamide is 3.0 mmol: 20-100 ml; the ratio of the activator to the triethylamine is 3.0 mmol: 0.5-3.0 mL; S2: Using cellulose-based fibers as the substrate, the cellulose-based fibers are immersed in the activation reaction solution and reacted under ice-water bath conditions to obtain fiber material A; S3: Using cyanuric chloride and polyamine compounds as precursor monomers for haloamine-type porous organic polymers, cyanuric chloride and polyamine compounds are dissolved in anhydrous dimethyl sulfoxide and mixed. Triethylamine is added dropwise to the above mixed solution system as an in-situ synthesis catalyst to obtain solution system A. The ratio of cyanuric chloride to the polyamine compound is 3.0 mmol: 3.0 mmol, and the ratio of triethylamine: (cyanuric chloride + polyamine compound) is 0.5-3.0 mL: 6.0 mmol; the ratio of (cyanuric chloride + polyamine compound): dimethyl sulfoxide is 6.0 mmol: 100 mL. S4: Mix fiber material A with the solution system A and react under nitrogen protection to obtain fiber material B; S5: The fiber material B is washed with dimethyl sulfoxide, water, and methanol, and then dried to obtain fiber material C; S6: Immerse fiber material C in hypohalite aqueous solution, rinse at room temperature, wash with water, and dry to obtain halogen amine porous organic polymer composite fiber material with antibacterial properties; The concentration of the hypohalite aqueous solution is 100-500 ppm; the pH value is 4.0; and the rinsing time is 60 min. The available chlorine content in haloamine porous organic polymer composite fiber materials is 3000-7000 ppm.

2. The application of the halogenated amine-based antibacterial porous organic polymer-based composite fiber material according to claim 1, characterized in that, The activator is selected from one or more of the following compounds: ； The polyamino compound is selected from one or more of melamine, diphenylamine, p-diaminobiphenyl, ethylenediamine, 2-(aminomethyl)-propanediamine, triaminoethylamine, and polyethyleneimine.

3. The application of the halogenated amine-based antibacterial porous organic polymer-based composite fiber material according to claim 1, characterized in that, In S2, the temperature of the ice-water bath is 0-5℃, and the reaction time is 30-180 minutes; in S4, the reaction time is 12-72 hours.

4. The application of the halogenated amine-based antibacterial porous organic polymer-based composite fiber material according to claim 1, characterized in that, Cellulose-based fibers are selected from one or more of cotton fibers, hemp fibers, bamboo fibers, viscose fibers, Tencel fibers, and Modal fibers.

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