Triazine-based halamine antimicrobial agents and methods of preparing liquid ammonia silk screened antimicrobial fabrics

Abstract

The application provides a preparation method of a triazine halamine antibacterial agent and a precursor thereof, and further provides a preparation method of liquid ammonia mercerized antibacterial fabric. The preparation method of the liquid ammonia mercerized antibacterial fabric comprises the following steps: impregnating the fabric with anhydrous liquid ammonia under tensionless condition, drying and cleaning; dissolving the halamine antibacterial precursor and a metal salt catalyst in water to prepare an antibacterial finishing liquid, and impregnating the liquid ammonia mercerized fabric in the antibacterial finishing liquid; adding a solid alkali agent into the antibacterial finishing liquid, continuously impregnating the liquid ammonia mercerized fabric, washing and drying; and reacting the fabric in a sodium hypochlorite solution, taking out and drying to obtain the liquid ammonia mercerized antibacterial fabric. The liquid ammonia is used for pretreatment of the fabric, which can significantly improve the grafting rate of the halamine antibacterial agent while giving the fabric excellent mercerizing effect, so that the antibacterial agent can be more firmly finished on the fabric at a lower temperature, the reaction process is simple, the production speed is fast, the efficiency is high, and the process is non-toxic and non-polluting, which meets the processing requirements of ecological textiles.

Description

Technical Field

[0001] This invention relates to the field of antibacterial finishing technology for textiles, and particularly to triazine-based halogenated amine antibacterial agents and methods for preparing liquid ammonia mercerized antibacterial fabrics. Background Technology

[0002] With increasing public concern about bacterial infections and cross-contamination, the demand for antibacterial textiles is also rising. People can come into contact with various microorganisms through textiles, which serve as excellent mediums for the growth and reproduction of bacteria and fungi. During use, fabrics come into frequent contact with human skin and hair, providing conditions for the spread of viruses and bacteria, thus endangering human health. Linen fibers, in particular, possess natural antibacterial and bacteriostatic properties, inhibiting the growth of some bacteria and fungi; however, their antibacterial effect is limited and cannot meet higher requirements. Therefore, developing textiles with good antibacterial and bacteriostatic properties is of great significance.

[0003] Currently, commonly used antibacterial agents can be mainly divided into the following categories: organic antibacterial agents, inorganic antibacterial agents, and natural antibacterial agents. However, most antibacterial agents have their drawbacks. Natural antibacterial agents are difficult to extract and have weak antibacterial ability; inorganic antibacterial agents have poor stability and high cost; and most organic antibacterial agents have toxic side effects, are harmful to the human body, and may also lead to microbial resistance.

[0004] Halogenated amine antibacterial agents are a novel, green, and pollution-free organic antibacterial agent, characterized by inexpensive raw materials, simple synthesis methods, easy storage, high bactericidal efficiency, broad-spectrum antibacterial activity, regenerable antibacterial properties, no toxic byproducts, and safety and environmental friendliness. Halogenated amine antibacterial agents contain one or more NX (X represents C1, Br, I) covalent bonds. They achieve bactericidal effects by releasing halogen atoms with strong oxidizing properties to inhibit or disrupt the metabolism of microorganisms. During the bactericidal process, the NX bonds are reduced to NH bonds, and can be halogenated again with sodium hypochlorite solution to regain the NX bond structure and bactericidal ability.

[0005] However, existing halogenated amine antibacterial agents suffer from problems such as complex preparation processes, high raw material costs, long reaction times, high energy consumption, and insufficient antibacterial effects. Chinese Patent Publication No. CN 111635427 A discloses an antibacterial silane coupling agent and its preparation method. The method involves reacting 3-hydroxypropyl-5,5-dimethylhydantoin and sodium p-aminobenzenesulfonate with cyanuric chloride to generate a monochlorotriazine halogenated amine antibacterial agent. Then, γ-aminopropyltriethoxysilane and p-toluenesulfonic acid are dissolved in toluene to obtain the antibacterial silane coupling agent. The chlorinated textiles exhibit certain antibacterial properties, but the preparation process is complex and the reaction time is long. Chinese Patent Publication No. CN 111979767 A relates to a method for preparing halogenated amine antibacterial cotton fabric using ultraviolet light grafting technology. The method involves padding and baking cotton fabric treated with BPTCD and ADMH, followed by irradiation under ultraviolet light. After chlorination, the fabric exhibits certain antibacterial and ultraviolet protection properties. However, the conventional padding and baking process has high energy consumption, and the high-temperature treatment has a significant impact on the physical and mechanical properties of the cotton fabric.

[0006] Cellulose fiber materials with high crystallinity and high orientation, such as hemp fiber, face problems such as grafting difficulties and poor finishing effects during the antibacterial finishing process. Summary of the Invention

[0007] [Technical Issues]

[0008] Existing halogenated amine antibacterial agents suffer from problems such as complex preparation processes, high raw material costs, long reaction times, high energy consumption, and insufficient antibacterial effects. Conventional pad-baking antibacterial finishing processes have high energy consumption, and the high-temperature treatment has a significant impact on the physical and mechanical properties of fabrics.

[0009] [Technical Solution]

[0010] To address the aforementioned problems in existing technologies, this invention provides a triazine-based halogenated amine antibacterial agent and a method for preparing liquid ammonia mercerized antibacterial fabrics. The antibacterial agent of this invention features a simple reaction process, rapid production speed, high efficiency, and is non-toxic and pollution-free, meeting the processing requirements of eco-textiles. The fabric is first subjected to liquid ammonia mercerizing pretreatment to reduce its crystallinity and orientation, thereby improving the antibacterial finishing effect of the halogenated amine antibacterial agent.

[0011] The first objective of this invention is to provide a precursor I of a triazine-based halogenated amine antibacterial agent, characterized by the following structural formula:

[0012]

[0013] Where X is a halogen.

[0014] The halogen is -F, -Cl, -Br or -I.

[0015] A second objective of this invention is to provide a method for preparing the precursor I described above, comprising the following steps:

[0016] (1) Add sodium p-aminobenzenesulfonate aqueous solution dropwise to cyanuric trihalomethane solution and react, maintaining the pH value of the reaction solution during the reaction process;

[0017] (2) Add 1-hydroxymethyl-5,5-dimethylhydantoin aqueous solution to the reaction solution prepared in step (1) and react, maintaining the pH value of the reaction solution during the reaction process;

[0018] (3) Filter the reaction solution prepared in step (2), wash and dry it to obtain halogen amine antibacterial precursor I.

[0019] In one embodiment of the present invention, the molar ratio of cyanuric trihalomethane, sodium p-aminobenzenesulfonate, and 1-hydroxymethyl-5,5-dimethylhydantoin is 1:1:1.

[0020] In one embodiment of the present invention, in step (1), cyanuric trihalomethane is one or more of cyanuric chloride and cyanuric fluoride.

[0021] In one embodiment of the present invention, in step (1), the concentration of the sodium p-aminobenzenesulfonate aqueous solution is 1-20 g / 100 mL.

[0022] In one embodiment of the present invention, in step (1), the solvent of the cyanuric trihalomethane solution is one of acetone, ethanol, or dioxane; the concentration of the cyanuric trihalomethane solution is 1-20 g / 100 mL.

[0023] In one embodiment of the present invention, in step (1), the reaction temperature is 0 to 5°C and the reaction time is 2 to 6 hours.

[0024] In one embodiment of the present invention, in step (1), the pH value of the reaction solution is maintained at 5.0 to 7.0.

[0025] In one embodiment of the present invention, in step (1), the pH value of the reaction solution is maintained by an aqueous solution of an acid-binding agent.

[0026] In one embodiment of the present invention, in step (1), the acid-binding agent is one or more of sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, and calcium hydroxide, with a concentration of 0.1 to 1 kg / L.

[0027] In one embodiment of the present invention, in step (2), the concentration of the 1-hydroxymethyl-5,5-dimethylhydantoin aqueous solution is 1–20 g / 100 mL. In one embodiment of the present invention, in step (2), the reaction temperature is 35–60 °C, and the reaction time is 2–5 h.

[0028] In one embodiment of the present invention, in step (2), the pH value of the reaction solution is maintained at 5.0 to 7.0.

[0029] In one embodiment of the present invention, in step (2), the pH value of the reaction solution is maintained by an aqueous solution of an acid-binding agent.

[0030] In one embodiment of the present invention, in step (2), the acid-binding agent is one or more of sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, and calcium hydroxide, with a concentration of 0.1 to 1 kg / L.

[0031] In one embodiment of the present invention, in step (3), filtration is performed by vacuum filtration.

[0032] In one embodiment of the present invention, in step (3), the cleaning is performed using an organic solvent and ice water; the organic solvent is one or more of acetone, ethanol, and dioxane.

[0033] In one embodiment of the present invention, in step (3), drying is performed at 45°C.

[0034] The third objective of this invention is to prepare a triazine-based halogenated amine antibacterial agent II from the aforementioned precursor I, with the following general structural formula:

[0035]

[0036] Wherein, R1 is a halogen or -H, R2 is a halogen or -H, and R1 and R2 are not both -H; X is a halogen.

[0037] In one embodiment of the present invention, R1 is Cl or Br, R2 is Cl or Br, and X is Cl or Br.

[0038] A fourth objective of this invention is to provide the application of precursor I or triazine halogen amine antimicrobial agent II in antimicrobial finishing of textiles.

[0039] In one embodiment of the present invention, the application in antimicrobial finishing of textiles includes the preparation of antimicrobial finishing agents and the preparation of antimicrobial textiles.

[0040] The fifth objective of this invention is to provide a method for preparing a liquid ammonia mercerized antibacterial fabric containing the above-mentioned triazine halogen amine antibacterial agent II, comprising the following steps:

[0041] (1) The fabric is impregnated with anhydrous liquid ammonia under tension-free conditions, dried, washed, and baked to obtain liquid ammonia mercerized fabric.

[0042] (2) Dissolve precursor I and metal salt catalyst in water to prepare antibacterial finishing solution, and immerse liquid ammonia mercerized fabric in antibacterial finishing solution;

[0043] (3) Add solid alkali to the antibacterial finishing solution, continue to soak the liquid ammonia mercerized fabric, take out the fabric, wash and dry it;

[0044] (4) The fabric obtained in step (3) is immersed in sodium hypochlorite solution for reaction, taken out and dried to obtain liquid ammonia mercerized antibacterial fabric.

[0045] In one embodiment of the present invention, in step (1), the fabric is one of cotton, linen, bamboo, modal, Tencel, viscose, or cupro fiber.

[0046] In one embodiment of the present invention, in step (1), the temperature of the anhydrous liquid ammonia impregnation is -40 to -33°C, and the impregnation time is 1 to 3 minutes.

[0047] In one embodiment of the present invention, in step (1), the drying temperature is 60-80°C and the drying time is 10-15 min.

[0048] In one embodiment of the present invention, in step (1), the washing is to wash the fabric with water to make the pH of the fabric neutral.

[0049] In one embodiment of the present invention, in step (1), the drying temperature is 40-55°C.

[0050] In one embodiment of the present invention, in step (2), the metal salt catalyst is selected from one or more of sodium sulfate, calcium sulfate, magnesium sulfate, zinc sulfate, sodium chloride, magnesium chloride, and calcium chloride.

[0051] In one embodiment of the present invention, in step (2), the concentration of the halogenated amine antibacterial precursor (I) in the antibacterial finishing solution is 1-10 g / L, and the concentration of the metal salt catalyst is 50-200 g / L.

[0052] In one embodiment of the present invention, in step (2), the immersion temperature is 20-30°C and the immersion time is 10-40 min.

[0053] In one embodiment of the present invention, in step (3), the solid alkali agent is selected from one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, and sodium bicarbonate.

[0054] In one embodiment of the present invention, in step (3), the concentration of the solid alkali agent in the antibacterial finishing solution is 1-5 g / L.

[0055] In one embodiment of the present invention, in step (3), the immersion temperature is 60-80°C and the immersion time is 1-5 hours.

[0056] In one embodiment of the present invention, in step (3), the drying temperature is 40-55°C.

[0057] In one embodiment of the present invention, in step (4), the concentration of sodium hypochlorite solution is 0.01 to 1 wt%.

[0058] In one embodiment of the present invention, in step (4), the reaction temperature is 20-40°C and the reaction time is 0.5-4h.

[0059] In one embodiment of the present invention, in step (4), the drying temperature is 40-55°C.

[0060] The sixth objective of this invention is to provide a liquid ammonia-silky antibacterial fabric prepared by the above-described preparation method.

[0061] Beneficial effects:

[0062] In the preparation of the halogen amine antibacterial precursor (II), sodium p-aminobenzenesulfonate was used to replace one halogen atom on cyanuric trihalomethane, which solved the problem that the hydroxyl group in 1-hydroxymethyl-5,5-dimethylhydantoin is not reactive at low temperature and does not easily react.

[0063] Introducing sodium p-aminobenzenesulfonate into the halogen amine antibacterial precursor (II) improves the water solubility of the halogen amine antibacterial precursor and adds an extra amino group, which increases the number of chlorinated amino groups per molecule, thereby enhancing the antibacterial activity of the prepared triazine halogen amine antibacterial agent (I) and giving the prepared antibacterial fabric excellent antibacterial and bactericidal functions.

[0064] The preparation method of halogen amine antibacterial precursor (II) is simple, does not produce toxic byproducts, and uses readily available and inexpensive raw materials.

[0065] The fabric is pretreated and modified, and then mercerized with liquid ammonia under tension-free conditions. This gives the fabric an excellent mercerizing effect while effectively reducing the crystallinity of cellulose fibers and significantly improving the grafting rate of halogen amine antibacterial agents, so that the antibacterial agents can be more firmly attached to the fabric.

[0066] The liquid ammonia mercerizing antibacterial fabric finishing method of the present invention enables the halogen amine antibacterial precursor (II) to undergo a nucleophilic substitution reaction with the hydroxyl groups on the fabric fiber molecules at a relatively low temperature (60-80℃), forming covalent bonds and grafting onto the fabric. The reaction process is simple, the production speed is fast, the efficiency is high, and it is non-toxic and pollution-free, meeting the processing requirements of ecological textiles.

[0067] The liquid ammonia mercerized antibacterial fabric produced can have a maximum chlorine content of 0.35%, and achieves a 100% sterilization rate against Staphylococcus aureus within 10 minutes and a 100% sterilization rate against Escherichia coli O157:H7 within 1 minute. Attached Figure Description

[0068] Figure 1The synthetic route and chlorination reaction equation for the preparation of the triazine haloamine antibacterial precursor in Example 1 of this invention are provided.

[0069] Figure 2 The 1H NMR spectrum of the triazine haloamine antibacterial precursor prepared in Example 1 of this invention. Detailed Implementation

[0070] Test method:

[0071] Mercerizing Effect Test: The mercerizing effect of fabrics is represented by the barium value. Mercerized and unmercerized linen fabrics were dried in an oven at 110℃ for 2 hours, then equilibrated to room temperature in a desiccator. 2g of each of the mercerized and unmercerized linen fabrics were cut into pieces smaller than 5mm × 5mm and placed separately into 150ml stoppered conical flasks. 30mL of 0.25mol / L barium hydroxide solution was added, and the flasks were immersed for 2 hours with continuous shaking. Two additional 150ml stoppered conical flasks were prepared, each containing 30ml of barium hydroxide solution, and left to stand for 2 hours as blank experiments. 10ml of the immersion solution was taken from each conical flask, 2–3 drops of phenolphthalein indicator were added, and titrated with 0.1mol / L hydrochloric acid standard solution. Each sample was tested in duplicate, and the barium value was calculated using the following formula. A barium value between 100 and 105 indicates no mercerizing; 105–150 indicates incomplete mercerizing; and above 150 indicates sufficient mercerizing.

[0072]

[0073] In the formula: V0 represents the volume (mL) of standard hydrochloric acid solution consumed in the blank test; V1 represents the volume (mL) of standard hydrochloric acid solution consumed in the mercerized linen impregnation solution; V2 represents the volume (mL) of standard hydrochloric acid solution consumed in the unmercerized linen impregnation solution.

[0074] Nuclear magnetic resonance (NMR) test: The triazine haloamine antibacterial precursor prepared in Example 1 was tested using a Bruker AVANCE NEO 400MHz.

[0075] Active chlorine content test: The chlorine content in linen fabrics was determined using the iodometric titration / thiosulfate method. The concentration of the sodium thiosulfate solution used was 0.001N, and the calculation formula is as follows:

[0076]

[0077] In the formula, [Cl + ]% represents the active chlorine content of the fabric (%), N represents the concentration of the titrant (N), V represents the volume of the titrant (L), and W represents the mass of the sample used for titration (g).

[0078] Antimicrobial performance test: The test was conducted according to the revised AATCC 100-2004 antimicrobial performance test standard, and the inoculated bacteria were Staphylococcus aureus and Escherichia coli O157:H7.

[0079] All raw materials used in the examples and comparative examples are commercially available products, and all instruments and equipment used are conventional equipment in the art. Staphylococcus aureus and Escherichia coli O157:H7 were purchased from the American Type Culture Collection (ATCC).

[0080] Preparation Example 1

[0081] Preparation of the halogenated antibacterial precursor 2-chloro-4-(sodium benzenesulfonate-4-amino)-6-(5,5-dimethylhydantoin-1-methoxy)-1,3,5-triazine:

[0082] (1) Dissolve 3.65g of cyanuric chloride in 50mL of acetone to prepare cyanuric chloride acetone solution, dissolve 3.83g of sodium p-aminobenzenesulfonate in 20mL of water to prepare sodium p-aminobenzenesulfonate aqueous solution, add the sodium p-aminobenzenesulfonate aqueous solution dropwise to the cyanuric chloride acetone solution, mix in a 250mL three-necked flask, and react at 0℃ for 3h. During the reaction, maintain the pH of the reaction solution at 5.0~6.0 with sodium carbonate aqueous solution at a concentration of 0.1kg / L.

[0083] (2) Dissolve 3.1g of 1-hydroxymethyl-5,5-dimethylhydantoin in 20mL of water, add the reaction solution prepared in step (1), and react at 40℃ for 3h. During the reaction, maintain the pH of the reaction solution at 6.0~7.0 with a sodium carbonate aqueous solution of 0.1kg / L.

[0084] (3) The reaction solution prepared in step (2) was filtered, washed with acetone and ice water, and dried at 45°C to obtain the halogenated antibacterial precursor, the 1H NMR spectrum of which is shown below. Figure 2 As shown, it is 2-chloro-4-(sodium benzenesulfonate-4-amino)-6-(5,5-dimethylhydantoin-1-methoxy)-1,3,5-triazine.

[0085] Preparation Example 2

[0086] Preparation of the halogenated antibacterial precursor 2-chloro-4-(sodium benzenesulfonate-4-amino)-6-(5,5-dimethylhydantoin-1-methoxy)-1,3,5-triazine:

[0087] (1) Dissolve 3.65g of cyanuric chloride in 50mL of dioxane to prepare a cyanuric chloride solution. Dissolve 3.83g of sodium p-aminobenzenesulfonate in 20mL of water to prepare an aqueous solution of sodium p-aminobenzenesulfonate. Add the aqueous solution of sodium p-aminobenzenesulfonate dropwise to the cyanuric chloride solution and mix them in a 250mL three-necked flask. React at 5℃ for 4h. During the reaction, maintain the pH of the reaction solution at 5.0-6.0 with a sodium bicarbonate solution of 0.1kg / L.

[0088] (2) Dissolve 3.1g of 1-hydroxymethyl-5,5-dimethylhydantoin in 20mL of water, add the reaction solution prepared in step (1), and react at 60℃ for 5h. During the reaction, maintain the pH of the reaction solution at 6.0~7.0 with sodium bicarbonate solution of 0.1kg / L.

[0089] (3) The reaction solution prepared in step (2) was filtered, washed with dioxane and ice water, and dried at 45°C to obtain 2-chloro-4-(sodium benzenesulfonate-4-amino)-6-(5,5-dimethylhydantoin-1-methoxy)-1,3,5-triazine.

[0090] Preparation Example 3

[0091] The difference from Preparation Example 1 is that acetone is replaced with ethanol.

[0092] Application Example 1

[0093] A liquid ammonia mercerized antibacterial flax fabric, the preparation method includes the following steps:

[0094] (1) The linen fabric was immersed in anhydrous liquid ammonia at -40℃ for 3 minutes under tension-free conditions, dried in an oven at 60℃ for 10 minutes, and the residual liquid ammonia was washed away in tap water to make the fabric pH neutral. The fabric was then dried at 45℃ to obtain liquid ammonia mercerized fabric.

[0095] (2) Dissolve 0.05g of the halogen amine antibacterial precursor 2-chloro-4-(sodium benzenesulfonate-4-amino)-6-(5,5-dimethylhydantoin-1-methoxy)-1,3,5-triazine prepared in Example 1 and 1g of sodium sulfate in 20ml of water to prepare an antibacterial finishing solution. Immerse 0.5g of mercerized fabric in the antibacterial finishing solution at room temperature for 0.5h.

[0096] (3) Heat the antibacterial finishing solution to 60°C, add 0.1g sodium hydroxide, continue to soak the mercerized fabric in the solution for 2 hours, take out the fabric, soap it, wash it with water, and dry it at 45°C.

[0097] (4) The fabric obtained in step (3) is immersed in a sodium hypochlorite solution with a concentration of 0.1wt% and reacted at 30°C for 1 hour. After being taken out, it is dried in an oven at 45°C to obtain liquid ammonia mercerized antibacterial flax fabric.

[0098] The active chlorine content of the liquid ammonia mercerized antibacterial linen fabric was measured to be 0.21%.

[0099] Application Example 2

[0100] A liquid ammonia mercerized antibacterial flax fabric, the preparation method includes the following steps:

[0101] (1) The linen fabric was immersed in anhydrous liquid ammonia at -33℃ for 2 minutes under tension-free conditions, dried in an oven at 80℃ for 15 minutes, and the residual liquid ammonia was washed away in tap water to make the fabric pH neutral. The fabric was then dried at 45℃ to obtain liquid ammonia mercerized fabric.

[0102] (2) Dissolve 0.1g of the halogen amine antibacterial precursor 2-chloro-4-(sodium benzenesulfonate-4-amino)-6-(5,5-dimethylhydantoin-1-methoxy)-1,3,5-triazine prepared in Example 1 and 2g of sodium sulfate in 20ml of water to prepare an antibacterial finishing solution. Immerse 0.5g of mercerized fabric in the antibacterial finishing solution at room temperature for 1h.

[0103] (3) Heat the antibacterial finishing solution to 80°C, add 0.02g sodium hydroxide, continue to soak the mercerized fabric in the solution for 4 hours, take out the fabric, soap it, wash it with water, and dry it at 45°C.

[0104] (4) The fabric obtained in step (3) is immersed in a sodium hypochlorite solution with a concentration of 0.05wt% and reacted at 35°C for 3 hours. After being taken out, it is dried in an oven at 45°C to obtain liquid ammonia mercerized antibacterial flax fabric.

[0105] The active chlorine content of the liquid ammonia mercerized antibacterial linen fabric was measured to be 0.35%, and the barium value was 239.75.

[0106] Application Example 3

[0107] A liquid ammonia mercerized antibacterial flax fabric, the preparation method includes the following steps:

[0108] (1) The linen fabric was immersed in anhydrous liquid ammonia at -37℃ for 1 min under tension-free conditions, dried in an oven at 70℃ for 12 min, and the residual liquid ammonia was washed away in tap water to make the pH of the fabric neutral, thus obtaining liquid ammonia mercerized fabric.

[0109] (2) Dissolve 0.2g of the halogen amine antibacterial precursor 2-chloro-4-(sodium benzenesulfonate-4-amino)-6-(5,5-dimethylhydantoin-1-methoxy)-1,3,5-triazine prepared in Example 1 and 4g of sodium sulfate in 20ml of water to prepare an antibacterial finishing solution. Immerse 0.5g of liquid ammonia mercerized fabric in the antibacterial finishing solution at room temperature for 10min.

[0110] (3) Heat the antibacterial finishing solution to 70°C, add 0.1g sodium carbonate, continue to soak the ammonia mercerized fabric for 5 hours, take out the fabric, soap, wash with water, and dry at 45°C.

[0111] (4) The fabric obtained in step (3) is immersed in a sodium hypochlorite solution with a concentration of 0.01wt% and reacted at 20°C for 0.5h. After being taken out, it is dried in an oven at 45°C to obtain liquid ammonia mercerized antibacterial flax fabric.

[0112] The active chlorine content of the liquid ammonia mercerized antibacterial linen fabric was measured to be 0.14%.

[0113] Application Comparative Example 1

[0114] An unmercerized, unchlorinated antibacterial linen fabric, which differs from Application Example 2 in that steps (1) and (4) are omitted.

[0115] Application Comparative Example 2

[0116] An unmercerized antibacterial linen fabric, which differs from Application Example 2 in that step (1) is omitted.

[0117] Application Comparative Example 3

[0118] A non-chlorinated, tension-free, alkaline mercerized antibacterial linen fabric, differing from Application Example 2 in that step (4) is omitted, and step (1) is replaced with alkaline mercerizing: at room temperature, under tension-free conditions, the linen fabric is immersed in a 240 g / L sodium hydroxide solution for 150 s, washed with 65°C hot water for 5 min, rinsed with tap water, then washed with 1 g / L acetic acid at room temperature for 5 min, and finally rinsed with tap water until the fabric is neutral.

[0119] Application Comparative Example 4

[0120] A tension-free alkali mercerized antibacterial linen fabric, which differs from application example 2 in that step (1) is replaced with alkali mercerizing: at room temperature, the linen fabric is immersed in a 240 g / L sodium hydroxide solution for 150 s under tension-free conditions, washed with 65°C hot water for 5 min, rinsed with tap water, then washed with 1 g / L acetic acid at room temperature for 5 min, and finally rinsed with tap water until the fabric is neutral.

[0121] Application Comparative Example 5

[0122] An unchlorinated, tension-free liquid ammonia mercerized antibacterial linen fabric, which differs from Application Example 2 in that step (4) is omitted.

[0123] Application Comparative Example 6

[0124] A tension-free alkali-mercerized linen fabric, the preparation method includes the following steps:

[0125] At room temperature, under tension-free conditions, the linen fabric was immersed in a 240 g / L sodium hydroxide solution for 150 s, washed with 65°C hot water for 5 min, rinsed with tap water, then washed with 1 g / L acetic acid at room temperature for 5 min, and finally rinsed with tap water until the fabric was neutral.

[0126] The barium value of the tension-free alkali-mercerized linen fabric produced is 185.70.

[0127] Table 1. Antibacterial performance tests of Comparative Examples 1 and 2 against Staphylococcus aureus and Escherichia coli O157:H7.

[0128]

[0129] Note: The inoculation concentration for Staphylococcus aureus is 5.00 × 10⁻⁶. 6 CFU / sample; the inoculation concentration for E. coli O157:H7 was 4.00 × 10⁻⁶. 6 cfu / sample.

[0130] Table 2 shows the antibacterial performance tests of Comparative Examples 3 and 4 against Staphylococcus aureus and Escherichia coli O157:H7.

[0131]

[0132] Note: The inoculation concentration for Staphylococcus aureus is 5.00 × 10⁻⁶. 6 CFU / sample; the inoculation concentration for E. coli O157:H7 was 4.00 × 10⁻⁶. 6 cfu / sample.

[0133] Table 3 shows the antibacterial performance tests of Comparative Example 5 and Application Example 2 against Staphylococcus aureus and Escherichia coli O157:H7.

[0134]

[0135]

[0136] Note: The inoculation concentration for Staphylococcus aureus is 5.00 × 10⁻⁶. 6 CFU / sample; the inoculation concentration for E. coli O157:H7 was 4.00 × 10⁻⁶. 6 cfu / sample.

[0137] The test data in Table 3 show that the antibacterial flax fabric prepared by Example 2 of the present invention has good antibacterial properties and high antibacterial efficiency. The bactericidal rate against Staphylococcus aureus and Escherichia coli O157:H7 can reach 100% within 10 min and 1 min, respectively.

[0138] The barium value of the tension-free alkali mercerized linen fabric in Comparative Example 6 was only 185.70, while the barium value in Example 2 was 239.75, indicating that the mercerizing effect of liquid ammonia is better under tension-free conditions.

[0139] As shown in Tables 1, 2 and 3, chlorination can significantly improve the antibacterial properties of antibacterial flax fabrics.

[0140] The antibacterial properties observed in Comparative Examples 3 and 5 indicate that for unchlorinated antibacterial flax fabrics, tension-free liquid ammonia mercerizing treatment provides better antibacterial performance than tension-free alkali mercerizing treatment. This is because liquid ammonia mercerizing helps reduce the crystallinity and orientation of the flax fabric, thereby increasing the grafting rate of precursor I.

[0141] The embodiments provided above are not intended to limit the scope of the invention, nor are the described steps intended to limit the order of execution. Any obvious modifications made to the invention by those skilled in the art based on existing common knowledge also fall within the scope of protection defined by the claims.

Claims

1. A precursor I of a triazine-based halogenated amine antibacterial agent, characterized in that, The structure is as follows: Where X is a halogen.

2. The method for preparing precursor I according to claim 1, characterized in that, step include: (1) Add sodium p-aminobenzenesulfonate aqueous solution dropwise to cyanuric trihalomethane solution and react, maintaining the pH of the reaction solution at 5.0~7.0 during the reaction process; (2) Add 1-hydroxymethyl-5,5-dimethylhydantoin aqueous solution to the reaction solution prepared in step (1) and react. Maintain the pH of the reaction solution at 5.0~7.0 during the reaction process. (3) Filter the reaction solution prepared in step (2), wash and dry it to obtain halogen amine antibacterial precursor I.

3. The preparation method according to claim 2, characterized in that, The molar ratio of cyanuric trihalomethane, sodium p-aminobenzenesulfonate, and 1-hydroxymethyl-5,5-dimethylhydantoin is 1:1:

1. In step (1), cyanuric trihalomethane is one or more of cyanuric chloride and cyanuric fluoride; The concentration of sodium p-aminobenzenesulfonate aqueous solution is 1~20 g / 100 mL; The solvent for the cyanuric trihalomethane solution is one of acetone, ethanol, or dioxane; the concentration of the cyanuric trihalomethane solution is 1~20 g / 100 mL. The reaction temperature is 0~5℃, and the reaction time is 2~6 h; The pH of the reaction solution is maintained by an aqueous solution of an acid-binding agent; the acid-binding agent is one or more of sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, and calcium hydroxide; the concentration of the aqueous solution of the acid-binding agent is 0.1~1 kg / L; In step (2), The concentration of the aqueous solution of 1-hydroxymethyl-5,5-dimethylhydantoin is 1~20 g / 100 mL; The reaction temperature is 35~60℃, and the reaction time is 2~5 h; The pH of the reaction solution is maintained by an aqueous solution of an acid-binding agent; the acid-binding agent is one or more of sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, and calcium hydroxide; the concentration of the aqueous solution of the acid-binding agent is 0.1~1 kg / L.

4. The triazine haloamine antibacterial agent II prepared from precursor I according to claim 1, characterized in that, The general structural formula is as follows: Wherein, R1 is a halogen or -H, R2 is a halogen or -H, and R1 and R2 are not both -H; X is a halogen.

5. The application of the precursor I of claim 1 or the triazine halogen amine antibacterial agent II of claim 4 in antibacterial finishing of textiles.

6. A method for preparing a liquid ammonia-silky antibacterial fabric containing the triazine halogen amine antibacterial agent II as described in claim 4, characterized in that, Including the following steps: (1) The fabric is impregnated with anhydrous liquid ammonia under tension-free conditions, dried, washed, and baked to obtain liquid ammonia mercerized fabric; (2) Dissolve precursor I and metal salt catalyst in water to prepare antibacterial finishing solution, and immerse liquid ammonia mercerized fabric in antibacterial finishing solution. (3) Add solid alkali to the antibacterial finishing solution, continue to soak the liquid ammonia mercerized fabric, take out the fabric, wash and dry it; (4) The fabric obtained in step (3) is immersed in sodium hypochlorite solution for reaction, taken out and dried to obtain liquid ammonia mercerized antibacterial fabric.

7. The preparation method according to claim 6, characterized in that, In step (1), the fabric is one of cotton, linen, bamboo, modal, Tencel, viscose, or cupro fiber; the temperature for immersion in anhydrous liquid ammonia is -40 to -33°C, and the immersion time is 1 to 3 minutes; the drying temperature is 60 to 80°C, and the drying time is 10 to 15 minutes; the washing is done by washing with water to make the pH of the fabric neutral.

8. The preparation method according to claim 6, characterized in that, In step (2), the metal salt catalyst is selected from one or more of sodium sulfate, calcium sulfate, magnesium sulfate, zinc sulfate, sodium chloride, magnesium chloride, and calcium chloride; the concentration of precursor I of the antibacterial finishing solution is 1~10 g / L, the concentration of the metal salt catalyst is 50~200 g / L; the impregnation temperature is 20~30℃, and the impregnation time is 10~40 min.

9. The preparation method according to claim 6, characterized in that, In step (3), the solid alkali agent is selected from one or more of sodium hydroxide, potassium hydroxide, calcium hydroxide, sodium carbonate, and sodium bicarbonate; the concentration of the solid alkali agent in the antibacterial finishing solution is 1~5 g / L; the impregnation temperature is 60~80℃ and the impregnation time is 1~5 h; in step (4), the concentration of sodium hypochlorite solution is 0.01~1wt%; the reaction temperature is 20~40℃ and the reaction time is 0.5~4 h.

10. Liquid ammonia silicified antibacterial fabric prepared by any one of the preparation methods of claims 6 to 9.

Images