Triazine halamine antibacterial agent and method for preparing liquid ammonia mercerizing antibacterial fabric

Abstract

The invention provides a preparation method of a triazine halamine antibacterial agent and a precursor thereof, and also provides a preparation method of a liquid ammonia mercerized antibacterial fabric. The preparation method of the liquid ammonia mercerizing antibacterial fabric comprises the following steps: soaking a fabric in anhydrous liquid ammonia under a tension-free condition, drying and cleaning; dissolving a halamine antibacterial precursor and a metal salt catalyst in water to prepare an antibacterial finishing solution, and dipping the liquid ammonia mercerized fabric in the antibacterial finishing solution; adding a solid alkali agent into the antibacterial finishing liquid, continuously dipping the liquid ammonia mercerized fabric, washing with water, and drying; soaking the fabric in a sodium hypochlorite solution for reaction, taking out and drying to obtain the liquid ammonia mercerizing antibacterial fabric. The liquid ammonia is adopted for pretreatment of the fabric, the excellent mercerizing effect is given to the fabric, meanwhile, the grafting rate of the halamine antibacterial agent is remarkably increased, the antibacterial agent can be more firmly finished on the fabric at the low temperature, the reaction process is simple, the production speed is high, efficiency is high, no toxicity and no pollution are achieved, and the processing requirements of ecological textiles are met.

Description

Technical Field

[0001] The invention relates to the technical field of antibacterial finishing of textiles, in particular to a triazine halamine antibacterial agent and a method for preparing liquid ammonia mercerized antibacterial fabric. Background Art

[0002] As people's concerns about bacterial infection and cross-contamination increase, the demand for antibacterial textiles is also increasing. People can come into contact with various microorganisms through textiles. Textiles are a good medium for the growth and reproduction of microorganisms such as bacteria and fungi. During use, fabrics will have more contact with human skin, hair, etc., providing conditions for the spread of viruses and bacteria, thereby endangering human health. Textiles, especially hemp fibers, have natural antibacterial and antifungal properties, which can inhibit the growth of some bacteria and fungi, but the antibacterial effect is limited and cannot meet higher requirements. Therefore, it is of great significance to develop textiles with good antibacterial and antifungal properties.

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

[0004] Halamine antimicrobial agents are a new type of green and pollution-free organic antimicrobial agent with cheap raw materials, simple synthesis methods, easy storage, high sterilization efficiency, broad-spectrum antibacterial, renewable antibacterial, no toxic byproducts, safe and environmentally friendly, etc. Halamine antimicrobial agents contain one or more NX (X represents C1, Br, I) covalent bonds, which inhibit or destroy the metabolism of microorganisms by releasing halogen atoms with strong oxidizing properties to achieve the purpose of sterilization. In the sterilization process, the NX bond is reduced to an NH bond, and can be converted back to an NX bond structure through halogenation with sodium hypochlorite solution to regain sterilization ability.

[0005] However, the existing halamine antibacterial agents have the problems of complex preparation process, high cost of synthetic raw materials, long reaction time, high reaction energy consumption, insufficient antibacterial effect, etc. Chinese Patent Publication No. CN 111635427 A relates to an antibacterial silane coupling agent and its preparation method, which is prepared by reacting 3-hydroxypropyl-5,5-dimethylhydantoin and sodium p-aminobenzenesulfonate with cyanuric chloride to generate a monochloro-s-triazine halamine antibacterial agent, and then dissolving γ-aminopropyltriethoxysilane and p-toluenesulfonic acid in toluene to prepare an antibacterial silane coupling agent. The chlorinated textiles have certain antibacterial properties, but the preparation process is relatively complicated and the reaction time is long. Chinese patent publication number CN 111979767 A relates to a method for preparing halamine antibacterial cotton fabric using ultraviolet grafting technology. The cotton fabric treated with BPTCD and ADMH is subjected to pad baking treatment and then irradiated under ultraviolet light. After chlorination, the fabric has certain antibacterial properties and ultraviolet protection properties. However, the conventional pad baking process has high reaction energy consumption, and the high temperature treatment has a great influence on the physical and mechanical properties of the cotton fabric.

[0006] Cellulosic fiber materials with high crystallinity and high orientation, such as hemp fiber, face problems such as difficult grafting and poor finishing effects during antibacterial finishing. Summary of the invention

[0007]

Technical issues

[0008] Existing halamine antimicrobial agents have problems such as complex preparation process, high cost of synthetic raw materials, long reaction time, high reaction energy consumption, insufficient antimicrobial effect, etc. Conventional pad baking antimicrobial finishing process has high reaction energy consumption, and high temperature treatment has a great impact on the physical and mechanical properties of fabrics.

[0009]

Technical solution

[0010] In view of the above problems existing in the prior art, the present invention provides a triazine halamine antibacterial agent and a method for preparing liquid ammonia mercerized antibacterial fabric. The antibacterial agent of the present invention has a simple reaction process, fast production speed, high efficiency, is non-toxic and pollution-free, and meets the processing requirements of ecological textiles. The fabric is firstly subjected to liquid ammonia mercerization pretreatment to reduce the crystallinity and orientation of the fabric, so as to improve the antibacterial finishing effect of the halamine antibacterial agent.

[0011] The first object of the present invention is to provide a precursor I of a triazine halamine antibacterial agent, characterized in that the structural formula is as follows:

[0012]

[0013] Wherein, X is a halogen.

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

[0015] The second object of the present invention is to provide a method for preparing the above-mentioned precursor I, comprising the steps of:

[0016] (1) adding an aqueous sodium p-aminobenzenesulfonate solution dropwise to a cyanuric halide solution for reaction, and maintaining the pH value of the reaction solution during the reaction process;

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

[0018] (3) filtering the reaction solution prepared in step (2), washing and drying to obtain the halamine antibacterial precursor I.

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

[0020] In one embodiment of the present invention, in step (1), the cyanuric halide 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 to 20 g / 100 mL.

[0022] In one embodiment of the present invention, in step (1), the solvent of the cyanuric halide solution is one of acetone, ethanol and dioxane; and the concentration of the cyanuric halide solution is 1 to 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 5.0-7.0.

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

[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, and the concentration is 0.1-1 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 to 20 g / 100 mL. In one embodiment of the present invention, in step (2), the reaction temperature is 35 to 60° C. and the reaction time is 2 to 5 h.

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

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

[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, and the concentration is 0.1-1 kg / L.

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

[0032] In one embodiment of the present invention, in step (3), the washing is washing with 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), the drying is performed at 45°C.

[0034] The third object of the present invention is the triazine halamine antibacterial agent II prepared from the above-mentioned precursor I, and the general structural formula is as follows:

[0035]

[0036] Wherein, R1 is halogen or -H, R2 is halogen or -H, R1 and R2 are not -H at the same time; and X is 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] The fourth object of the present invention is to provide the use of the precursor I or the triazine halamine antibacterial agent II in the antibacterial finishing of textiles.

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

[0040] The fifth object of the present invention is to provide a method for preparing a liquid ammonia mercerized antibacterial fabric containing the above-mentioned triazine halamine antibacterial agent II, comprising the steps of:

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

[0042] (2) dissolving the precursor I and the metal salt catalyst in water to prepare an antibacterial finishing liquid, and immersing the liquid ammonia mercerized fabric in the antibacterial finishing liquid;

[0043] (3) adding a solid alkali agent to the antibacterial finishing liquid, continuing to immerse the mercerized fabric in liquid ammonia, taking out the fabric, washing it, and drying it;

[0044] (4) The fabric obtained in step (3) is immersed in a sodium hypochlorite solution for reaction, taken out and dried, so as to obtain a 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, and cupro-ammonia 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 to 80° C., and the drying time is 10 to 15 minutes.

[0048] In one embodiment of the present invention, in step (1), washing is washing 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 halamine antibacterial precursor (I) in the antibacterial finishing liquid is 1 to 10 g / L, and the concentration of the metal salt catalyst is 50 to 200 g / L.

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

[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 liquid is 1 to 5 g / L.

[0055] In one embodiment of the present invention, in step (3), the immersion temperature is 60 to 80° C., and the immersion time is 1 to 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 the sodium hypochlorite solution is 0.01-1 wt %.

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

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

[0060] The sixth object of the present invention is to provide liquid ammonia mercerized antibacterial fabric prepared by the above preparation method.

[0061] Beneficial effects:

[0062] In the preparation of the halamine antibacterial precursor (II), sodium p-aminobenzenesulfonate is first used to replace a halogen atom on the cyanuric halide, which solves the problem that the hydroxyl group in 1-hydroxymethyl-5,5-dimethylhydantoin is inactive at low temperatures and is not easy to react.

[0063] The introduction of sodium p-aminobenzenesulfonate into the halamine antibacterial precursor (II) improves the water solubility of the halamine antibacterial precursor, and adds an amino group, which increases the number of chlorinated amino groups in a single molecule, thereby enhancing the antibacterial activity of the prepared triazine halamine antibacterial agent (I), and making the prepared antibacterial fabric have excellent antibacterial and bactericidal functions.

[0064] The preparation method of the halamine antibacterial precursor (II) is simple to operate, does not produce toxic by-products, and the synthetic raw materials are simple, easy to obtain and low in price.

[0065] The fabric is pre-treated and modified, and then mercerized with liquid ammonia under tension-free conditions, which gives the fabric an excellent mercerizing effect while effectively reducing the crystallinity of the cellulose fibers, significantly increasing the grafting rate of the halamine antibacterial agent and allowing the antibacterial agent to be more firmly attached to the fabric.

[0066] The liquid ammonia mercerizing antibacterial fabric finishing method of the present invention can make the halamine antibacterial precursor (II) react with the hydroxyl groups on the fabric fiber molecules at a relatively low temperature (60-80°C) to undergo a nucleophilic substitution reaction, thereby forming a covalent bond with the hydroxyl groups and grafting the hydroxyl groups on the fabric fiber molecules. The reaction process is simple, the production speed is fast, the efficiency is high, the halogenated amine precursor (II) is non-toxic and pollution-free, and the processing requirements of ecological textiles are met.

[0067] The maximum chlorine content of the liquid ammonia mercerized antibacterial fabric can reach 0.35%, the sterilization rate of Staphylococcus aureus can reach 100% within 10 minutes, and the sterilization rate of Escherichia coli O157:H7 can reach 100% within 1 minute. BRIEF DESCRIPTION OF THE DRAWINGS

[0068] Figure 1The synthetic route and chlorination reaction equation of the triazine halamine antibacterial precursor prepared in Example 1 of the present invention.

[0069] Figure 2 This is the H NMR spectrum of the triazine halamine antibacterial precursor prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0070] Test method:

[0071] Mercerizing effect test: The mercerizing effect of fabrics is expressed by barium value. Put the mercerized and unmercerized linen fabrics into an oven at 110℃ for 2h and put them into a dryer to balance to room temperature. Prepare 2g of mercerized and unmercerized linen fabrics, cut them into pieces less than 5mm×5mm, put them into 150ml stoppered conical flasks, add 30mL, 0.25mol / L barium hydroxide solution, immerse them for 2h and shake them continuously. Take two other 150ml stoppered conical flasks, add 30ml barium hydroxide solution, leave it for 2h, and do a blank experiment. Take 10ml of the immersion solution from each conical flask, add 2-3 drops of phenolphthalein indicator, and titrate with 0.1mol / L hydrochloric acid standard solution. Perform two parallel experiments for each sample, and calculate the barium value according to the following formula. A barium value between 100 and 105 indicates no mercerization; 105-150 indicates incomplete mercerization; and above 150 indicates sufficient mercerization.

[0072]

[0073] Wherein: V0 represents the volume of the standard hydrochloric acid solution consumed in the blank test (mL); V1 represents the volume of the standard hydrochloric acid solution consumed by the mercerized flax impregnation liquid (mL); V2 represents the volume of the standard hydrochloric acid solution consumed by the unmercerized flax impregnation liquid (mL).

[0074] Nuclear magnetic resonance testing: The triazine halamine antibacterial precursor prepared in Example 1 was tested using a Bruker AVANCE NEO 400 MHz.

[0075] Active chlorine content test: The chlorine content in linen fabric is determined by iodine / thiosulfate titration. The concentration of the sodium thiosulfate solution used is 0.001N, and the calculation formula is as follows:

[0076]

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

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

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

[0080] Preparation Example 1

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

[0082] (1) 3.65 g of cyanuric chloride was dissolved in 50 mL of acetone to prepare a cyanuric chloride acetone solution, 3.83 g of sodium p-aminobenzenesulfonate was dissolved in 20 mL of water to prepare a sodium p-aminobenzenesulfonate aqueous solution, the sodium p-aminobenzenesulfonate aqueous solution was added dropwise to the cyanuric chloride acetone solution, the mixture was mixed in a 250 mL three-necked flask, and the mixture was reacted at 0° C. for 3 h. During the reaction, a sodium carbonate aqueous solution with a concentration of 0.1 kg / L was used to maintain the pH value of the reaction solution at 5.0 to 6.0;

[0083] (2) 3.1 g of 1-hydroxymethyl-5,5-dimethylhydantoin was dissolved in 20 mL of water, and the reaction solution prepared in step (1) was added thereto. The reaction was carried out at 40° C. for 3 h. During the reaction, a 0.1 kg / L sodium carbonate aqueous solution was used to maintain the pH value of the reaction solution at 6.0 to 7.0.

[0084] (3) The reaction solution prepared in step (2) was filtered, washed with acetone and ice water, and dried at 45° C. to obtain a halamine antibacterial precursor, whose H NMR spectrum is as follows: 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 halamine antibacterial precursor 2-chloro-4-(sodium benzenesulfonate-4-amino)-6-(5,5-dimethylhydantoin-1-methoxy)-1,3,5-triazine:

[0087] (1) 3.65 g of cyanuric chloride was dissolved in 50 mL of dioxane to prepare a cyanuric chloride solution, 3.83 g of sodium p-aminobenzenesulfonate was dissolved in 20 mL of water to prepare a sodium p-aminobenzenesulfonate aqueous solution, the sodium p-aminobenzenesulfonate aqueous solution was added dropwise to the cyanuric chloride solution, the mixture was mixed in a 250 mL three-necked flask, and the mixture was reacted at 5° C. for 4 h. During the reaction, a sodium bicarbonate solution with a concentration of 0.1 kg / L was used to maintain the pH value of the reaction solution at 5.0 to 6.0;

[0088] (2) dissolving 3.1 g of 1-hydroxymethyl-5,5-dimethylhydantoin in 20 mL of water, adding the reaction solution prepared in step (1), and reacting at 60° C. for 5 h. During the reaction, a 0.1 kg / L sodium bicarbonate solution was used to maintain the pH value of the reaction solution at 6.0 to 7.0;

[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 by ethanol.

[0092] Application Example 1

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

[0094] (1) impregnating a linen fabric with anhydrous liquid ammonia at -40°C for 3 minutes under tension-free conditions, drying it in an oven at 60°C for 10 minutes, washing away residual liquid ammonia in tap water to make the pH of the fabric neutral, and drying it at 45°C to obtain a liquid ammonia mercerized fabric;

[0095] (2) 0.05 g of the halamine antibacterial precursor 2-chloro-4-(sodium benzenesulfonate-4-amino)-6-(5,5-dimethylhydantoin-1-methoxy)-1,3,5-triazine prepared in Preparation Example 1 and 1 g of sodium sulfate were dissolved in 20 ml of water to prepare an antibacterial finishing liquid, and 0.5 g of liquid ammonia mercerized fabric was immersed in the antibacterial finishing liquid at room temperature for 0.5 h;

[0096] (3) Raise the temperature of the antibacterial finishing liquid to 60°C, add 0.1 g of sodium hydroxide, and continue to immerse the liquid ammonia mercerized fabric for 2 hours. Take out the fabric, soap and wash it with water, and dry it at 45°C;

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

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

[0099] Application Example 2

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

[0101] (1) impregnating a linen fabric with anhydrous liquid ammonia at -33°C for 2 minutes under tension-free conditions, drying it in an oven at 80°C for 15 minutes, washing away residual liquid ammonia in tap water to make the pH of the fabric neutral, and drying it at 45°C to obtain a liquid ammonia mercerized fabric;

[0102] (2) 0.1 g of the halamine antibacterial precursor 2-chloro-4-(sodium benzenesulfonate-4-amino)-6-(5,5-dimethylhydantoin-1-methoxy)-1,3,5-triazine prepared in Preparation Example 1 and 2 g of sodium sulfate were dissolved in 20 ml of water to prepare an antibacterial finishing liquid, and 0.5 g of liquid ammonia mercerized fabric was immersed in the antibacterial finishing liquid at room temperature for 1 h;

[0103] (3) Raise the temperature of the antibacterial finishing liquid to 80°C, add 0.02 g of sodium hydroxide, and continue to immerse the liquid ammonia mercerized fabric for 4 hours. Take out the fabric, soap and 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 0.05 wt % and reacted at 35° C. for 3 h. After being taken out, the fabric is dried in an oven at 45° C. to obtain a liquid ammonia mercerized antibacterial linen fabric.

[0105] The active chlorine content of 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 linen fabric, the preparation method comprises the following steps:

[0108] (1) impregnating a linen fabric with anhydrous liquid ammonia at -37°C for 1 min under tension-free conditions, drying it in an oven at 70°C for 12 min, washing away residual liquid ammonia in tap water to make the pH of the fabric neutral, and obtaining a liquid ammonia mercerized fabric;

[0109] (2) 0.2 g of the halamine antibacterial precursor 2-chloro-4-(sodium benzenesulfonate-4-amino)-6-(5,5-dimethylhydantoin-1-methoxy)-1,3,5-triazine prepared in Preparation Example 1 and 4 g of sodium sulfate were dissolved in 20 ml of water to prepare an antibacterial finishing liquid, and 0.5 g of liquid ammonia mercerized fabric was immersed in the antibacterial finishing liquid at room temperature for 10 min;

[0110] (3) Raise the temperature of the antibacterial finishing liquid to 70°C, add 0.1 g of sodium carbonate, and continue to immerse the liquid ammonia mercerized fabric for 5 hours. Take out the fabric, soap and wash it with water, and dry it at 45°C;

[0111] (4) The fabric obtained in step (3) is immersed in a 0.01 wt% sodium hypochlorite solution at 20°C for reaction for 0.5 h, and then taken out and dried in an oven at 45°C to obtain a liquid ammonia mercerized antibacterial linen fabric.

[0112] The active chlorine content of 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 not performed.

[0115] Application Comparative Example 2

[0116] An unmercerized antibacterial linen fabric, which is different from Application Example 2 in that step (1) is not performed.

[0117] Application Comparative Example 3

[0118] A non-chlorinated tension-free alkali mercerized antibacterial linen fabric, which differs from Application Example 2 in that step (4) is not performed and step (1) is replaced by alkali mercerization: the linen fabric is immersed in a 240 g / L sodium hydroxide solution for 150 s at room temperature 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 becomes 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 mercerization: the linen fabric is immersed in a 240 g / L sodium hydroxide solution for 150 s at room temperature and 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 becomes neutral.

[0121] Application Comparative Example 5

[0122] A non-chlorinated tension-free liquid ammonia mercerized antibacterial linen fabric, which is different from Application Example 2 in that step (4) is not performed.

[0123] Application Comparative Example 6

[0124] A tension-free alkali mercerized linen fabric, the preparation method of which comprises the steps of:

[0125] At room temperature, the linen fabric was 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 became neutral.

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

[0127] Table 1 Antibacterial performance test of comparative examples 1 and 2 against Staphylococcus aureus and Escherichia coli O157:H7

[0128]

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

[0130] Table 2 Antibacterial performance test of comparative examples 3 and 4 against Staphylococcus aureus and Escherichia coli O157:H7

[0131]

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

[0133] Table 3 Antibacterial performance test of comparative example 5 and example 2 on Staphylococcus aureus and Escherichia coli O157:H7

[0134]

[0135]

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

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

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

[0139] It can be seen from Tables 1, 2 and 3 that chlorination can significantly improve the antibacterial properties of antibacterial linen fabrics.

[0140] It can be seen from the antibacterial properties of application comparative examples 3 and 5 that for non-chlorinated antibacterial linen fabrics, tension-free liquid ammonia mercerization treatment has better antibacterial properties than tension-free alkali mercerization treatment. The reason is that liquid ammonia mercerization is beneficial to reducing the crystallinity and orientation of linen fabrics and increasing the grafting rate of precursor I of linen fabrics.

[0141] The embodiments provided above are not intended to limit the scope of the present invention, and the steps described are not intended to limit the execution order thereof. Those skilled in the art may make obvious improvements to the present invention in combination with existing common knowledge, which also fall within the scope of protection defined by the claims of the present invention.

Claims

1. A precursor I of a triazine halamine antibacterial agent, characterized in that: The structural formula is as follows: Wherein, X is a halogen.

2. The method for preparing the precursor I according to claim 1, characterized in that the steps include: (1) adding an aqueous sodium p-aminobenzenesulfonate solution dropwise to a cyanuric halide solution for reaction, and maintaining the pH value of the reaction solution during the reaction process; (2) adding an aqueous solution of 1-hydroxymethyl-5,5-dimethylhydantoin to the reaction solution prepared in step (1) for reaction, and maintaining the pH value of the reaction solution during the reaction process; (3) filtering the reaction solution prepared in step (2), washing and drying to obtain the halamine antibacterial precursor I.

3. The preparation method according to claim 2, characterized in that: The molar ratio of cyanuric halide, sodium p-aminobenzenesulfonate and 1-hydroxymethyl-5,5-dimethylhydantoin is 1:1:1; In step (1), The cyanuric halide is one or more of cyanuric chloride and cyanuric fluoride; The concentration of the sodium p-aminobenzenesulfonate aqueous solution is 1 to 20 g / 100 mL; The solvent of the cyanuric halide solution is one of acetone, ethanol and dioxane; the concentration of the cyanuric halide solution is 1 to 20 g / 100 mL; The reaction temperature is 0-5°C and the reaction time is 2-6h; The pH value of the reaction solution is maintained at 5.0-7.0; the pH value of the reaction solution is maintained with an acid-binding agent aqueous solution; the acid-binding agent is one or more of sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, and calcium hydroxide; the concentration of the acid-binding agent aqueous solution is 0.1-1 kg / L; In step (2), The concentration of the 1-hydroxymethyl-5,5-dimethylhydantoin aqueous solution is 1 to 20 g / 100 mL; The reaction temperature is 35-60°C and the reaction time is 2-5h; The pH value of the reaction solution is maintained at 5.0-7.0; the pH value of the reaction solution is maintained by using an acid-binding agent aqueous solution; the acid-binding agent is one or more of sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium hydroxide, and calcium hydroxide; and the concentration of the acid-binding agent aqueous solution is 0.1-1 kg / L.

4. The triazine halamine antibacterial agent II prepared from the precursor I according to claim 1, characterized in that: The general structure is as follows: Wherein, R1 is halogen or -H, R2 is halogen or -H, R1 and R2 are not -H at the same time; and X is halogen.

5. Use of the precursor I according to claim 1 or the triazine halamine antibacterial agent II according to claim 4 in antibacterial finishing of textiles.

6. A method for preparing liquid ammonia mercerized antibacterial fabric containing the triazine halamine antibacterial agent II according to claim 4, characterized in that: Includes steps: (1) The fabric is impregnated with anhydrous liquid ammonia under tension-free conditions, dried, cleaned, and dried to obtain a liquid ammonia mercerized fabric; (2) dissolving the precursor I and the metal salt catalyst in water to prepare an antibacterial finishing liquid, and immersing the liquid ammonia mercerized fabric in the antibacterial finishing liquid; (3) adding a solid alkali agent to the antibacterial finishing liquid, continuing to immerse the mercerized fabric in liquid ammonia, taking out the fabric, washing it, and drying it; (4) The fabric obtained in step (3) is immersed in a sodium hypochlorite solution for reaction, taken out and dried, so as to obtain a 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, and cuprammonia fiber; the temperature of anhydrous liquid ammonia impregnation is -40 to -33°C, and the impregnation time is 1 to 3 minutes; the temperature of drying is 60 to 80°C, and the drying time is 10 to 15 minutes; and the washing is 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 the precursor I of the antibacterial finishing liquid is 1 to 10 g / L, and the concentration of the metal salt catalyst is 50 to 200 g / L; the immersion temperature is 20 to 30° C., and the immersion time is 10 to 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 solid alkali agent concentration of the antibacterial finishing liquid is 1 to 5 g / L; the immersion temperature is 60 to 80° C., and the immersion time is 1 to 5 hours; in step (4), the concentration of the sodium hypochlorite solution is 0.01 to 1 wt %; the reaction temperature is 20 to 40° C., and the reaction time is 0.5 to 4 hours.

10. Liquid ammonia mercerized antibacterial fabric prepared by the preparation method according to any one of claims 6 to 9.

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