Halogenated copolymer antibacterial cotton fabric based on LbL self-assembly and preparation method

Abstract

This invention provides an antibacterial cotton fabric based on LbL self-assembly of haloamine copolymers and its preparation method. The antibacterial cotton fabric utilizes LbL self-assembly technology to alternately coat anionic haloamine copolymer PASPA and cationic haloamine copolymer PADAC onto cotton fabric, forming a self-assembled antibacterial coating. This process prepares two antibacterial agent precursors. After alternating impregnation, rinsing, drying, and chlorination treatment, the antibacterial cotton fabric is obtained. This antibacterial cotton fabric exhibits high antibacterial efficiency, good breathability and mechanical properties, excellent self-cleaning ability, and washability. Furthermore, the preparation process is environmentally friendly and gentle. The number of assembled layers can be adjusted to suit different applications, facilitating industrial production.

Description

Technical Field

[0001] This invention relates to the field of antibacterial finishing technology for textiles, specifically to an antibacterial cotton fabric based on LbL self-assembly of halogen amine copolymers and its preparation method. Background Technology

[0002] Cotton fibers are widely used in textiles and medical devices due to their natural biodegradability, excellent moisture absorption, breathability, and wearing comfort. However, the porous structure and hydrophilicity of cotton fabrics make them a carrier for microbial attachment and reproduction under certain temperature and humidity conditions. This can lead to fabric mildew, decreased mechanical properties, and even cross-infection, posing a serious threat to human health.

[0003] To address the antibacterial issue in cotton fabrics, current technologies primarily rely on applying antibacterial finishing agents to the fiber surface. Common antibacterial agents include metal ions, quaternary ammonium salts, and biguanides. However, biguanide antibacterial agents exhibit weak bonding with cotton fabrics, resulting in poor wash resistance and durability of the antibacterial coating, making it difficult to meet the requirement for long-lasting antibacterial effects. Furthermore, some metal ion antibacterial agents present biotoxicity issues, limiting their application in skin-contact textiles.

[0004] Halogenated amine compounds are widely used in the field of antibacterial materials due to their excellent bactericidal efficiency, broad-spectrum antibacterial properties, long-term stability, and unique renewability. Their mechanism of action lies in the strong oxidizing power of the NX bond (where X is a halogen, usually Cl or Br) in their structure, which damages the cell membrane of microorganisms or interferes with metabolic enzyme systems. Furthermore, after their antibacterial activity is depleted, they can be regenerated through chlorine bleaching, allowing for repeated use. Existing methods for preparing halogenated amine antibacterial cotton fabrics mainly include high-temperature crosslinking, chemical grafting, and blending modification. However, these methods have the following problems:

[0005] 1. It has a significant impact on the properties of the fabric itself. High-temperature cross-linking or chemical grafting reactions have strict conditions, which can easily lead to a decrease in the strength of cotton fibers; while traditional coating finishing forms a thick coating on the fiber surface, which blocks the gaps between fibers, resulting in a decrease in the breathability of the fabric and a stiffer hand feel.

[0006] 2. The preparation process has shortcomings. The antibacterial agent obtained by blending modification has weak bonding force with fabric and poor water resistance; the chemical grafting method requires the use of organic solvents, which is not environmentally friendly; small molecule haloamine compounds have poor water solubility and are easy to fall off, making it difficult to achieve long-lasting antibacterial effect.

[0007] 3. Limited structural control capabilities. Existing single-layer coating processes struggle to achieve precise control over coating thickness and composition, limiting the amount of antibacterial agent that can be loaded and hindering multifunctional applications.

[0008] Layer-by-layer (LbL) self-assembly is an advanced method for constructing ultrathin films based on the alternating deposition of polyelectrolytes with opposite charges. This technology offers significant advantages such as ease of operation, mild film-forming conditions, precise nanoscale control over film thickness and composition, and wide applicability to various substrates. However, detailed reports on the use of LbL technology to precisely assemble oppositely charged haloamine polymer precursors onto cotton fabric surfaces to prepare antibacterial coatings with high antibacterial activity and excellent durability have not yet been published. Therefore, developing a novel haloamine polymer with a simple synthesis process, readily available raw materials, stable performance, and effective integration with biodegradable materials, and combining it with electrostatic self-assembly technology to construct an efficient and environmentally friendly method for preparing antibacterial materials, has significant practical implications and application value. Summary of the Invention

[0009] To address the aforementioned technical problems, this invention provides an antibacterial cotton fabric based on LbL self-assembly of a halogenated amine copolymer. Potassium 3-sulfopropyl acrylate, acryloyloxyethyltrimethylammonium chloride, and an acetylenic halogenated amine antibacterial agent are selected as synthetic raw materials to prepare anionic and cationic halogenated amine antibacterial agents. These agents are then coated onto cotton fabric using LbL deposition technology to form a thin film. This imparts antibacterial properties to the cotton fabric while also providing regenerable antibacterial properties, making it convenient to use. This invention significantly enhances the self-cleaning function of cotton fabrics while imparting antibacterial properties. Simple rinsing is sufficient to effortlessly remove dust from the fabric without wetting it. This innovation eliminates the need for complex washing and drying processes while retaining functional characteristics, including its antibacterial properties.

[0010] To achieve the above technical objectives, the present invention provides an antibacterial cotton fabric based on LbL self-assembly of halogenated amine copolymers. The antibacterial cotton fabric is formed by alternating anionic halogenated amine copolymer antibacterial agent PASPA and cationic halogenated amine copolymer antibacterial agent PADAC on the cotton fabric through LbL self-assembly technology to form an antibacterial coating.

[0011] The anionic haloamine copolymer antibacterial agent PASPA has the structural formula shown in formula (I):

[0012] General Formula I

[0013] Where R is selected from fluorine, chlorine or bromine; m:n=1:(1-19).

[0014] The cationic halogenated amine copolymer antibacterial agent PADAC has the structural formula shown in formula (II):

[0015] General Formula II

[0016] Where R is selected from fluorine, chlorine, or bromine; p:q = 1:(1-19)

[0017] In some embodiments of the present invention, the cationic haloamine copolymer antibacterial agent PADAC has a weight-average molecular weight of 3000-3600.

[0018] In some embodiments of the present invention, the weight average molecular weight of the anionic halogenated amine copolymer antibacterial agent PASPA and the cationic halogenated amine copolymer antibacterial agent PADAC is 3100-3700.

[0019] In some embodiments of the present invention, the molecular weight distribution index of the anionic halogenated amine copolymer antibacterial agent PASPA and the cationic halogenated amine copolymer antibacterial agent PADAC does not exceed 1.05.

[0020] In some technical solutions of the present invention, the antibacterial cotton fabric comprises anionic halogenated amine copolymer antibacterial agent PASPA and cationic halogenated amine copolymer antibacterial agent PADAC, which are alternately treated by LbL self-assembly 1-15 times. Specifically, the antibacterial cotton fabric is treated with one layer of anionic halogenated amine copolymer antibacterial agent PASPA and one layer of cationic halogenated amine copolymer antibacterial agent PADAC by LbL self-assembly as a group, and this treatment is repeated 1-15 times.

[0021] This invention also provides a method for preparing antibacterial cotton fabric based on LbL self-assembly of haloamine copolymers, specifically including the following steps:

[0022] Step 1: Prepare anionic halogenated amine copolymer antibacterial agent precursor PASPA and cationic halogenated amine copolymer antibacterial agent precursor PADAC;

[0023] Step 2: Dissolve PASPA and PADAC in deionized water to prepare PASPA and PADAC solutions. Place the raw cotton fabric in the PADAC solution for 4-6 minutes, then remove it, rinse it with deionized water for 55-65 seconds, and then put it in a forced-air drying oven to dry. Then immerse the fabric in the PASPA solution for 4-6 minutes, remove it, rinse it, and dry it to complete the assembly of layer 1.

[0024] Step 3: Repeat step 2 until the ideal requirements are met and the finishing process is finished. After 15 minutes, rinse with deionized water and dry for later use. The fabric sample of the n-layer composite membrane is labeled Cotton-(PADAC / PASPA)n.

[0025] Step 4: Prepare a chlorination solution using sodium hypochlorite solution, immerse the fabric obtained in Step 3 in the chlorination solution, control the bath ratio and continuously stir the reaction. After chlorination treatment, the fabric is marked as Cotton-(PADAC / PASPA)n-Cl.

[0026] In some technical solutions of the present invention, the anionic halogenated amine copolymer antibacterial agent precursor PASPA and the cationic halogenated amine copolymer antibacterial agent precursor PADAC in step 1 include at least the preparation of the halogenated amine monomer APDMH, which mainly includes the following steps:

[0027] Step 1.1: 5,5-Dimethylhydantoin was refluxed with NaOH in distilled water, and then 1-chloro-3-hydroxypropane was added to react and give the product 3-(3'-hydroxypropyl)-5,5-dimethylhydantoin;

[0028] Step 1.2: Dissolve the product 3-(3'-hydroxypropyl)-5,5-dimethylhydantoin from Step 1.1 in tetrahydrofuran and stir well, then cool to 0°C;

[0029] Step 1.3: Add acryloyl chloride dropwise to the solution in Step 1.2, stir for 1 hour, raise to room temperature and continue stirring until the reaction is terminated, and then wash to obtain the haloamine monomer APDMH.

[0030] In some technical solutions of the present invention, the concentration of 5,5-dimethylhydantoin in distilled water in step 1.1 is 1.5-2.3 mol / L; the amount of NaOH and 5,5-dimethylhydantoin is added.

[0031] In some technical solutions of the present invention, the reflux time in step 1.1 is 13-20 min.

[0032] In some technical solutions of the present invention, the molar ratio of 1-chloro-3-hydroxypropane to 5,5-dimethylhydantoin in step 1.1 is (1-1.05):1.

[0033] In some technical solutions of the present invention, the molar ratio of 3-(3'-hydroxypropyl)-5,5-dimethylhydantoin to triethylamine in step 1.2 is 1:1.

[0034] In some technical solutions of the present invention, the volume of the product of step 1.1 in step 1.2 in tetrahydrofuran is 80-120 ml.

[0035] In some technical solutions of the present invention, the molar ratio of acryloyl chloride to 3-(3'-hydroxypropyl)-5,5-dimethylhydantoin in step 1.3 is (1-1.05):1.

[0036] In some technical solutions of the present invention, the preparation of the anionic halogenated amine copolymer antibacterial agent PASPA in step 1 further includes the following steps: dissolving the product APDMH from step 1.3 and potassium 3-sulfopropyl acrylate SPA in deionized water and stirring, adding initiator 1, reacting at 70-80℃ for 4-6 hours under nitrogen protection, and after the reaction is completed, distilling under reduced pressure, filtering and purifying, and drying to obtain the anionic halogenated amine copolymer antibacterial agent PASPA.

[0037] In some preferred embodiments of the present invention, the molar ratio of the two monomers, the halogenated amine monomer APDMH and the potassium 3-sulfopropyl acrylate SPA, is 5:95-50:50.

[0038] In some preferred embodiments of the present invention, the total concentration of the two monomers, APDMH (a halogenated amine monomer) and SPA (potassium 3-sulfopropyl acrylate), in water is 0.5-0.65 mol / L.

[0039] In some preferred embodiments of the present invention, the initiator is selected from at least one of persulfate, water-soluble azo, and redox initiator systems. Further, the initiator is selected from persulfate, specifically from potassium persulfate, sodium persulfate, and ammonium persulfate.

[0040] In some technical solutions of the present invention, the preparation of the cationic halogenated amine copolymer antibacterial agent PADAC in step 1 further includes the following steps: dissolving the product APDMH from step 1.3 and acryloyloxyethyltrimethylammonium chloride DAC in deionized water and stirring, adding initiator 2, reacting at 70-80℃ for 4-6 hours under nitrogen protection, and after the reaction is completed, distilling under reduced pressure, filtering and purifying, and drying to obtain the cationic halogenated amine copolymer antibacterial agent PADAC.

[0041] In some preferred embodiments of the present invention, the molar ratio of the two monomers, APDMH (a halogenated amine monomer) and acryloyloxyethyltrimethylammonium chloride (DAC), is 5:95-50:50.

[0042] In some preferred embodiments of the present invention, the total concentration of the two monomers, APDMH (a halogenated amine monomer) and acryloyloxyethyltrimethylammonium chloride (DAC), in water is 0.5-0.65 mol / L.

[0043] In some preferred embodiments of the present invention, the initiator 2 is selected from at least one of persulfate, water-soluble azo, and redox initiator systems. Further, the initiator 2 is selected from persulfate, specifically from potassium persulfate, sodium persulfate, and ammonium persulfate.

[0044] In some technical solutions of the present invention, the mass concentration of the PASPA solution in step 2 is 2%-10%.

[0045] In some technical solutions of the present invention, the mass concentration of the PADAC solution in step 2 is 2%-10%.

[0046] In some technical solutions of the present invention, the ratio of the volume of PASPA solution to the mass of the original cotton fabric in step 2 is (25-35):1.

[0047] In some technical solutions of the present invention, the ratio of the volume of PADAC solution to the mass of the original cotton fabric in step 2 is (25-35):1.

[0048] In some technical solutions of this invention, the number of layers of the composite membrane Cotton-(PADAC / PASPA)n in step 3 is 1-15. The antibacterial effect of the fabric gradually increases with the increase of the number of self-assembled layers, but the increasing trend of the effect gradually slows down after the number of layers reaches 10, and the effect does not change significantly after exceeding 15 layers.

[0049] In some technical solutions of the present invention, the bath ratio in step 4 is 1:(20-80).

[0050] In some technical solutions of the present invention, the reaction time in step 4 is 0.5-3h.

[0051] Compared with the prior art, the present invention has the following beneficial effects:

[0052] 1. The antibacterial cotton fabric provided by this invention has an anionic and cationic halogenated amine copolymer antibacterial agent on its surface, which is copolymerized from anionic and cationic acetylenyl monomers and acetylenyl-containing halogenated amine monomers. It possesses both water solubility and high molecular stability. Compared to traditional small-molecule antibacterial agents, its antibacterial components are less prone to migration, significantly improving safety and stability. The electrostatic interaction between anions and cations can form a stable antibacterial coating on the cotton fabric surface. After chlorination, this copolymer can form a powerful bactericidal N-Cl bond. The treated cotton fabric exhibits excellent antibacterial properties and high antibacterial efficiency. After 1 minute of contact, it can inactivate Staphylococcus aureus and Escherichia coli, and kill all bacteria within 10 minutes. Within 30 minutes, the bacterial reduction compared to pure cotton fabric increased by 6.46 log and 5.94 log, respectively. This invention imparts antibacterial properties to cotton fabrics while also ensuring the fabric's breathability, flexibility, and mechanical properties.

[0053] 2. The antibacterial cotton fabric provided by this invention utilizes LbL deposition technology to coat the cotton fabric with anionic and cationic haloamine copolymer antibacterial agents PASPA and PADAC, forming an antibacterial coating. This significantly enhances the self-cleaning function of the cotton fabric; simple rinsing is sufficient to effortlessly remove dust without wetting the fabric. After multiple sterilization, washing, UV treatment, and storage cycles, the chlorine content can be rapidly restored to over 85% of its original level through re-chlorination. This innovation eliminates the need for complex washing and drying processes while retaining functional properties, including its antibacterial properties.

[0054] 3. LbL self-assembly technology allows for precise nanoscale control of the thickness and composition of antibacterial coatings by adjusting the number of assembled layers. This enables the adjustment of the composite film layer count to create cotton fabrics with varying antibacterial strengths, tailored to different application scenarios such as medical, home textiles, and public spaces. The technology offers high flexibility and wide applicability. Furthermore, the preparation process for antibacterial cotton fabrics is environmentally friendly, with mild reaction conditions that do not damage the inherent structure and properties of cotton fibers. It is compatible with the material properties of cotton fabrics and the production processes of the textile industry, facilitating industrial-scale application. Attached Figure Description

[0055] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the description of the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0056] Figure 1 This is a synthetic route diagram of the anionic and cationic haloamine copolymer antibacterial agent in the embodiments of the present invention;

[0057] Figure 2 Infrared characterization images of the anionic and cationic halogen amine copolymer antibacterial agent and the antibacterial renewable cotton fabric in the embodiments of the present invention;

[0058] Figure 3 These are scanning electron microscope (SEM) and atomic force microscope (AFM) images of the anionic and cationic halogen amine copolymer antibacterial agents in the embodiments of the present invention.

[0059] Figure 4 This is a schematic diagram of the layer-by-layer self-assembly, bacterial killing, and re-chlorination process in an embodiment of the present invention;

[0060] Figure 5 The graphs show the antibacterial performance test results for Example 13 and Comparative Example 1.

[0061] Figure 6 The graphs show the hydrophobicity and self-cleaning performance test results of Examples 11-15 and Comparative Example 1. Detailed Implementation

[0062] The technical solutions of this invention will be clearly and completely described below with reference to the embodiments thereof. These described embodiments are only some, not all, of the embodiments of this invention. All other embodiments obtained by those skilled in the art based on the embodiments of this invention without creative effort are within the scope of protection of this invention.

[0063] I. Synthesis of anionic halogenated amine copolymer antibacterial agent PASPA and cationic halogenated amine copolymer antibacterial agent PADAC

[0064] 1. Preparation of the haloamine monomer APDMH: 0.2 mol of 5,5-dimethylhydantoin and 0.2 mol of NaOH were mixed in 100 mL of distilled water and refluxed for 15 min to obtain the sodium salt of 5,5-dimethylhydantoin. 0.2 mol of 1-chloro-3-hydroxypropane was added to the above solution, and the mixture was stirred at 100 °C for 10 h. After the reaction was complete, the mixture was filtered. The solid product was dissolved in acetone, filtered, and rotary evaporated. 0.05 mol of 3-(3'-hydroxypropyl)-5,5-dimethylhydantoin and 0.05 mol of triethylamine were added to 100 mL of tetrahydrofuran (THF), and stirred for 10 min to obtain a homogeneous solution. After cooling to 0 °C, 0.05 mol of acryloyl chloride was added dropwise to the solution and stirred for 1 h, then stirred at room temperature for 20 h. The product was collected by filtration and washed with THF and acetone.

[0065] 2. Synthesis of the anionic haloamine copolymer antibacterial agent PASPA: APDMH and potassium 3-sulfopropyl acrylate (SPA) (different proportions for different examples are shown in Table 1) were dissolved in 80 mL of deionized water and stirred until homogeneous in a 250 mL three-necked flask. The mixture was sonicated for 10 min to obtain a homogeneous solution. 0.05 g of potassium persulfate was dissolved in 20 mL of deionized water. Then, the mixture was heated to 75 °C while the potassium persulfate solution was added dropwise to the mixture. The entire process was carried out under N2 protection for 5 h. The resulting product was vacuum rotary evaporated and dried in a vacuum drying oven at 60 °C for 12 h.

[0066] Table 1: Addition ratio of the two monomers in Examples 1-5

[0067] Example 1 Example 2 Example 3 Example 4 Example 5 APDMH / mol 0.0015 0.003 0.005 0.006 0.008 SPA / mol 0.0285 0.017 0.020 0.014 0.008 The ratio of the amounts of substance 5:95 15:85 20:80 30:70 50:50

[0068] 3. Synthesis of the cationic halogenated amine copolymer antibacterial agent PADAC: APDMH and acryloyloxyethyltrimethylammonium chloride (DAC) (different proportions for different examples are shown in Table 2) were dissolved in 80 mL of deionized water and stirred until homogeneous in a 250 mL three-necked flask. The mixture was sonicated for 10 min to obtain a homogeneous solution. 0.05 g of potassium persulfate was dissolved in 20 mL of deionized water. Then, the mixture was heated to 75 °C while the potassium persulfate solution was added dropwise to the mixture. The entire process was carried out under N2 protection for 5 h. The resulting product was vacuum rotary evaporated and dried in a vacuum drying oven at 60 °C for 12 h.

[0069] Table 2: Addition ratio of the two monomers in Examples 5-9

[0070]

[0071] II. Preparation of antibacterial cotton fabrics based on LbL self-assembly of haloamine copolymers

[0072] PASPA and PADAC solutions were prepared by dissolving PASPA and PADAC in deionized water. These solutions were then coated onto cotton fabric using LbL deposition technology to form a thin film. First, the impregnated cotton fabric was placed in a 2% PADAC solution (liquid ratio 30:1) for 5 minutes. After 5 minutes, it was removed, rinsed with running deionized water for 60 seconds, and then dried in a forced-air oven. Next, the fabric was impregnated in a 2% PASPA solution (liquid ratio 30:1) for 5 minutes, rinsed, and dried to complete one layer assembly. The above steps were repeated. The preparation configurations for each example and comparative example are shown in Table 3. After 15 minutes, the fabric was rinsed with deionized water, dried, and set aside. The fabric sample with n layers of composite film was labeled Cotton-(PADAC / PASPA)n. A chlorination solution was prepared using sodium hypochlorite solution. The assembled fabric Cotton-(PADAC / PASPA)n was then impregnated in this solution with continuous stirring.

[0073] Table 3: Preparation of cotton fabrics in the examples and comparative examples

[0074]

[0075] III. Testing Experiments

[0076] 1. Antibacterial Performance Test: Following the modified AATCC 100-2014 test method, antibacterial experiments were conducted on chlorinated samples against Staphylococcus aureus and Escherichia coli O157:H7. 25 μL of bacterial suspension was added to the center of a 2.54 cm × 2.54 cm square membrane. Another membrane was then pressed over the suspension to ensure full contact. After contact times of 1, 10, and 30 min, the sample was transferred to a centrifuge tube containing sterile Na2S2O3 solution and left to stand for 2 min to quench any residual chlorine oxide. The quenched solution was then serially diluted and dropped into TSA plates. Incubation was performed at 37°C for 24 h, and the colony count on the plate was recorded.

[0077] The formula for calculating the bacterial logarithmic decrease value is as follows:

[0078] Bacterial logarithmic decrease value = LogN0 - LogN1

[0079] In the formula, N0 is the initial number of bacteria, and N1 is the number of bacteria remaining after a certain period of time.

[0080] 2. Washing Resistance Test: The washing resistance of chlorinated cotton fabrics was tested according to AATCC 61-2001 standard. The procedure was as follows: The test sample was cut into several small samples of 2.54cm × 5.08cm and placed in four steel bottles containing 150mL of 0.15% soap solution. To ensure the smooth conduct of the experiment, at least three test samples were placed in each steel bottle. Fifty standard steel balls were placed in each steel bottle, which was then sealed and fixed in the slot of the wash fastness tester. The washing test parameters were set as follows: washing temperature 49℃, rotation speed 42rpm. After 1, 2, 5, 10, and 25 cycles of washing (each 45 minutes is equivalent to 5 cycles), one steel bottle was removed sequentially, the cotton fabric sample was taken out and rinsed with plenty of deionized water. After drying, some samples were directly titrated for chlorine content to analyze the stability of the N-Cl bond; the other samples were re-chlorinated.

[0081] 3. UV Stability Test: The UV stability of chlorinated coated cotton fabrics was studied according to ASTM D4587 standard. The chlorinated modified cotton fabrics were placed in a UV aging chamber with a wavelength range of 315-400 nm and a temperature of 60℃. The fabrics were irradiated with UV light for 1 h, 2 h, 4 h, 8 h, 12 h, and 24 h, and then removed. A portion of the samples was tested for chlorine content, while another portion was chlorinated again and tested. The obtained data were compared and analyzed to evaluate the UV stability of the chlorinated coated cotton fabrics.

[0082] 4. Storage stability test: The chlorinated cotton fabric was stored at room temperature away from light for 30 days. A small sample was taken out every 5 days, and the chlorine content of the sample was titrated. After 30 days of storage, the fabric was rechlorinated, and the storage stability was analyzed.

[0083] 5. Water contact angle test: Measured using a DSA00 contact angle meter (KRUSS, Germany). The needle tip diameter was 0.5 mm, and the water droplet volume was 5 μL. Each sample was tested 5 times, and the average value was calculated.

[0084] 6. Self-cleaning performance test: Four common liquids (water, milk, tea, and cola) were dropped onto pure cotton samples and chlorinated cotton fabrics to study the wetting transition of the cotton fabrics. One study used ground-level yellow chalk powder as an alternative to household airborne dust and common solid contaminants to evaluate the self-cleaning effect of treated cotton fabrics. The experiment involved applying chalk powder to the surfaces of untreated and chlorinated cotton fabrics, followed by applying water droplets to remove solid dirt. The self-cleaning performance of the two types of fabrics was observed.

[0085] IV. Test Results Explanation

[0086] 1. Antibacterial performance test results are as follows: Figure 5 As shown, for chlorinated Cotton-(PADAC / PASPA)5-Cl cotton fabric, the reduction in the amount of both bacteria gradually increased with the extension of the contact time with bacteria, indicating that Cotton-(PADAC / PASPA)5-Cl fabric has a good bactericidal effect and can kill all inoculated Escherichia coli O157:H7 and Staphylococcus aureus within 10 minutes.

[0087] Table 4 Antibacterial performance test data

[0088]

[0089] 2. Resistance to washing, UV radiation, and storage.

[0090] Table 5. Test data for water resistance, UV resistance, and storage stability.

[0091]

[0092] The table above shows the wash stability, UV resistance stability, and storage stability of antimicrobial fabrics after chlorination. After 25 washes, 30 days of storage, and 24 hours of light exposure, the chlorine content of the antimicrobial fabrics decreased; however, rechlorination could increase the chlorine content again. Figure 6 A detailed analysis revealed that chlorinated Cotton-(PADAC / PASPA) could further increase its chlorine content after multiple washes, different irradiation times, and long-term storage, indicating that the antibacterial fabric has good regenerative properties.

[0093] 3. The water contact angle test results are shown in Table 6: As the number of LbL self-assembled layers increases, the contact angle of the fabric gradually increases, indicating that the addition of PADAC / PASPA improves the hydrophobicity of the fabric. The contact angle of the chlorinated cotton fabric increases significantly, and the hydrophobic performance is further enhanced, thus giving it excellent self-cleaning function.

[0094] Table 6: Water Contact Angle Test Data

[0095]

[0096] 4. Self-cleaning performance test results are as follows: Figure 4 As shown, four common liquids—water, milk, tea, and cola—as well as chalk powder were dropped or placed on the surfaces of raw pure cotton fabric and chlorinated cotton-coated fabric, respectively. The results showed that the chlorinated cotton-coated fabric effectively blocked the penetration and wetting of the liquids and easily removed chalk powder adhering to its surface, demonstrating excellent self-cleaning properties.

[0097] Finally, it should be noted that although the present invention has been described in detail above with general descriptions and specific embodiments, the above embodiments are only used to illustrate the technical solutions of the present invention, and not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, those skilled in the art should understand that modifications can still be made to the technical solutions described in the foregoing embodiments, or equivalent substitutions can be made to some or all of the technical features; and these modifications or substitutions do not cause the essence of the corresponding technical solutions to deviate from the scope of the technical solutions of the embodiments of the present invention.

Claims

1. A haloamine copolymer antibacterial cotton fabric based on LbL self-assembly, characterized in that, The antibacterial cotton fabric is formed by LbL self-assembly, which alternately processes anionic halogenated amine copolymer antibacterial agent PASPA and cationic halogenated amine copolymer antibacterial agent PADAC onto the cotton fabric to form an antibacterial coating. The anionic haloamine copolymer antibacterial agent PASPA has the structural formula shown in formula (I): General Formula I Where R is selected from fluorine, chlorine or bromine; m:n=1:(1-19). The cationic halogenated amine copolymer antibacterial agent PADAC has the structural formula shown in formula (II): General Formula II Where R is selected from fluorine, chlorine or bromine; p:q=1:(1-19).

2. The antibacterial cotton fabric based on LbL self-assembly of haloamine copolymers according to claim 1, characterized in that, The cationic halogenated amine copolymer antibacterial agent PADAC has a weight-average molecular weight of 3000-3600; the anionic halogenated amine copolymer antibacterial agent PASPA has a weight-average molecular weight of 3100-3700; and the molecular weight distribution index of the anionic halogenated amine copolymer antibacterial agent PASPA and the cationic halogenated amine copolymer antibacterial agent PADAC does not exceed 1.

05.

3. The antibacterial cotton fabric based on LbL self-assembly of haloamine copolymers according to claim 1, characterized in that, The antibacterial cotton fabric comprises anionic halogenated amine copolymer antibacterial agent PASPA and cationic halogenated amine copolymer antibacterial agent PADAC, which are alternately treated with LbL self-assembly in 1-15 groups.

4. A method for preparing antibacterial cotton fabric based on LbL self-assembly of haloamine copolymers, characterized in that, Specifically, the following steps are included: Step 1: Prepare anionic halogenated amine copolymer antibacterial agent precursor PASPA and cationic halogenated amine copolymer antibacterial agent precursor PADAC; Step 2: Dissolve PASPA and PADAC in deionized water to prepare PASPA and PADAC solutions. Place the raw cotton fabric in the PADAC solution for 4-6 minutes, then remove it, rinse it with deionized water for 55-65 seconds, and then put it in a forced-air drying oven to dry. Then immerse the fabric in the PASPA solution for 4-6 minutes, remove it, rinse it, and dry it to complete the assembly of layer 1. Step 3: Repeat step 2 until the ideal requirements are met and the finishing process is finished. After 15 minutes, rinse with deionized water and dry for later use. The fabric sample of the n-layer composite membrane is labeled Cotton-(PADAC / PASPA)n. Step 4: Prepare a chlorination solution using sodium hypochlorite solution, immerse the fabric obtained in Step 3 in the chlorination solution, control the bath ratio and continuously stir the reaction. After chlorination treatment, the fabric is marked as Cotton-(PADAC / PASPA)n-Cl.

5. The method for preparing antibacterial cotton fabric based on LbL self-assembly of haloamine copolymers according to claim 3, characterized in that, The anionic halogenated amine copolymer antibacterial agent precursor PASPA and the cationic halogenated amine copolymer antibacterial agent precursor PADAC mentioned in step 1 include at least the preparation of the halogenated amine monomer APDMH, which mainly includes the following steps: Step 1.1: 5,5-Dimethylhydantoin was refluxed with NaOH in distilled water, and then 1-chloro-3-hydroxypropane was added to react and give the product 3-(3'-hydroxypropyl)-5,5-dimethylhydantoin; Step 1.2: Dissolve the product 3-(3'-hydroxypropyl)-5,5-dimethylhydantoin from Step 1.1 in tetrahydrofuran and stir well, then cool to 0°C; Step 1.3: Add acryloyl chloride dropwise to the solution in Step 1.2, stir for 1 hour, raise to room temperature and continue stirring until the reaction is terminated, and then wash to obtain the haloamine monomer APDMH.

6. The method for preparing antibacterial cotton fabric based on LbL self-assembly of haloamine copolymers according to claim 4, characterized in that, The preparation of the anionic halogenated amine copolymer antibacterial agent PASPA in step 1 further includes the following steps: dissolving the product APDMH from step 1.3 and potassium 3-sulfopropyl acrylate SPA in deionized water and stirring, adding initiator 1, reacting at 70-80℃ for 4-6 hours under nitrogen protection, after the reaction is completed, distilling under reduced pressure, filtering and purifying, and drying to obtain the anionic halogenated amine copolymer antibacterial agent PASPA; the molar ratio of the two monomers APDMH and potassium 3-sulfopropyl acrylate SPA is 5:95-50:50; the total concentration of the two monomers APDMH and potassium 3-sulfopropyl acrylate SPA in water is 0.5-0.65 mol / L; the initiator 1 is selected from at least one of persulfate, water-soluble azo, and redox initiator systems.

7. The method for preparing antibacterial cotton fabric based on LbL self-assembly of haloamine copolymers according to claim 4, characterized in that, The preparation of the cationic halogenated amine copolymer antibacterial agent PADAC in step 1 further includes the following steps: dissolving the product APDMH from step 1.3 and acryloyloxyethyltrimethylammonium chloride DAC in deionized water and stirring, adding initiator 2, reacting at 70-80℃ for 4-6 hours under nitrogen protection, after the reaction is completed, distilling under reduced pressure, filtering and purifying, and drying to obtain the cationic halogenated amine copolymer antibacterial agent PADAC; the molar ratio of the two monomers APDMH and acryloyloxyethyltrimethylammonium chloride DAC is 5:95-50:50; the total concentration of the two monomers APDMH and acryloyloxyethyltrimethylammonium chloride DAC in water is 0.5-0.65 mol / L; the initiator 2 is selected from at least one of persulfate, water-soluble azo, and redox initiator systems.

8. The method for preparing antibacterial cotton fabric based on LbL self-assembly of haloamine copolymers according to claim 3, characterized in that, The mass concentration of the PASPA solution in step 2 is 2%-10%; the mass concentration of the PADAC solution in step 2 is 2%-10%; the ratio of the volume of the PASPA solution to the mass of the original cotton fabric in step 2 is (25-35):1; the ratio of the volume of the PADAC solution to the mass of the original cotton fabric in step 2 is (25-35):

1.

9. The method for preparing antibacterial cotton fabric based on LbL self-assembly of haloamine copolymers according to claim 3, characterized in that, The number of layers in the composite membrane Cotton-(PADAC / PASPA)n described in step 3 is 1-15.

10. The method for preparing antibacterial cotton fabric based on LbL self-assembly of haloamine copolymers according to claim 3, characterized in that, The bath ratio in step 4 is 1:(20-80); the reaction time is 0.5-3h.

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