Multi-quaternary ammonium salt textile antibacterial agent with anti-wrinkle function and preparation method thereof

Abstract

The present application belongs to the field of textile finishing, and particularly relates to a kind of multi-quaternary ammonium salt textile antibacterial agent with wrinkle resistance function and a preparation method thereof.Cyanuric chloride is reacted with anhydrous piperazine to obtain 2,4,6-tripiperazinyl-s-triazine, then 2,4,6-tripiperazinyl-s-triazine is reacted with chlorobenzene to synthesize 2,4,6-tris(4-benzylpiperazine-1-yl)-1,3,5-triazine, then the quaternary ammonium salt is prepared by reacting with halogenated alkane, finally hydrochloric acid is added to form a salt, and the multi-quaternary ammonium salt textile antibacterial agent with wrinkle resistance function is prepared.The antibacterial agent contains nine nitrogen atoms, multiple quaternary ammonium salts, multiple tertiary amine hydrochlorides, and groups that can couple with fibers, so the molecular bonding with fibers has high firmness, the overall cation density is high, thereby enhancing the antibacterial activity and antibacterial durability.Meanwhile, the molecule has a large skeletal structure extending in the s-triazine direction with triazine ring as the center, which not only imparts excellent antibacterial properties to the fabric, but also improves its wrinkle resistance and dimensional stability.

Description

Technical Field

[0001] This invention belongs to the field of textile finishing, specifically relating to a class of multi-quaternary ammonium salt antibacterial agents for textiles with anti-wrinkle function and their preparation method. Background Technology

[0002] Textiles are prone to the growth of bacteria, fungi, and other microorganisms during use, which not only affects the lifespan of the fabric but may also cause problems such as odors, skin allergies, and even infections. With the improvement of people's living standards and increased health awareness, the demand for antibacterial textiles in daily life, healthcare, and sportswear is growing.

[0003] Commonly used antibacterial agents for textiles on the market mainly include inorganic antibacterial agents, such as silver ion and zinc ion antibacterial agents; organic antibacterial agents, such as quaternary ammonium salts and triclosan; and natural antibacterial agents, such as chitosan.

[0004] Silver-based inorganic antibacterial agents are relatively expensive, as silver is a rare and valuable raw material that is easily reduced, leading to discoloration. They also have poor inhibitory effects on fungi and molds, and a relatively narrow antibacterial spectrum. Furthermore, they cannot kill bacteria as quickly as organic antibacterial agents, thus limiting their applicability. Triclosan may interfere with the human endocrine system, particularly affecting the normal function of estrogen and thyroid hormones, posing potential safety concerns. The antibacterial stability of natural antibacterial agents is not guaranteed.

[0005] Quaternary ammonium salts exert their bactericidal effect by disrupting the cell membrane structure of microorganisms, causing leakage of cell contents. Due to their broad-spectrum antibacterial properties, low toxicity, and good chemical stability, quaternary ammonium compounds have become a research hotspot in the field of antibacterial textiles.

[0006] Currently, most quaternary ammonium salt structures are in the form of mono-quaternary ammonium or bis-quaternary ammonium. Their binding with fibers mainly relies on electrostatic adsorption or weak bond bonding. They are easily detached under external forces such as washing, friction, and water immersion, making it difficult to maintain a long-term stable antibacterial effect. In addition, the bactericidal mechanism of monocationic structures is relatively simple, with limited inhibitory and bactericidal effects on certain bacterial species, resulting in insufficient antibacterial range.

[0007] To improve the adhesion and durability of quaternary ammonium salts on textiles, researchers have proposed strategies to fix them onto fibers using covalent bonds. For example, patent CN109577000A describes a method involving graft polymerization of textiles in a solution containing tertiary amine vinyl monomers, followed by quaternization with haloalkanes to obtain antibacterial fibers with a surface-fixed quaternary ammonium salt structure. However, this method requires a reaction on the fiber, is a heterogeneous reaction, and is difficult to operate. Patent CN1792158A reports an organosilicon quaternary ammonium salt antibacterial agent prepared from dimethyloctadecylamine and chloropropyltriethoxysilane, which improves the durability and performance of the antibacterial agent to some extent. Of course, organosilicones also have disadvantages such as high price and hydrolysis.

[0008] Furthermore, currently used antibacterial agents have limited functionality and do not simultaneously impart additional functions such as wrinkle resistance and shape retention to fabrics. CN 115262212 A reports a method for wrinkle-resistant and antibacterial finishing of cotton fabrics based on organosilicon resin. However, this method uses expensive raw materials, requires ultraviolet irradiation for both the synthesis and application of the antibacterial agent, and the process is difficult to operate. The photo-initiating alkali agent used is a substance with a special structure and is also expensive. Therefore, the industrial application of this method faces certain difficulties. Thus, developing a wash-resistant, wrinkle-resistant, and highly efficient antibacterial agent has significant research value and industrial significance. Summary of the Invention

[0009] To address the shortcomings of existing quaternary ammonium salt-based antibacterial agents for textiles, such as insufficient antibacterial durability, weak fiber bonding, and limited functionality, this invention provides an antibacterial agent with a skeleton containing multiple nitrogen compounds, multiple quaternary ammonium salts, and multiple hydrochloric acid salts, centered on a triazine ring and extending symmetrically in three directions. This enhances the wash resistance, long-lasting antibacterial effect, and wrinkle resistance of antibacterial finishing agents on textiles. This type of antibacterial agent has the following structure:

[0010]

[0011] Where R1, R2, and R3 are alkyl groups of haloalkanes; n represents the number of amino groups in the molecule that form hydrochloride salts, with a value of 1 to 3.

[0012] This invention also provides a method for preparing quaternary ammonium salt antibacterial agents for textiles, specifically including the following steps:

[0013] (1) Anhydrous piperazine reacts with cyanuric chloride under the action of an acid-binding agent to give 2,4,6-tripiperazine-triazine.

[0014]

[0015] To prevent the piperazine ring from having two triazine rings attached to it as much as possible, anhydrous piperazine needs to be in excess, and the molar ratio of anhydrous piperazine to cyanuric chloride is 3.5:1 to 6:1; preferably, the molar ratio is 4.5:1 to 5.5:1; in addition, even if a small amount of piperazine ring has two triazine rings attached to it, thus forming a compound with two triazine ring centers connected by piperazine, it does not need to be removed.

[0016] The solvent for the reaction can be one or a mixture of several of 1,4-dioxane, benzene, toluene, and xylene. Using 1,4-dioxane as a reaction solvent facilitates the complete dissolution and uniform mixing of the reactants, thereby improving the controllability of the reaction, reducing the occurrence of side reactions, and resulting in products with better structural stability and reproducibility. Therefore, 1,4-dioxane is preferred.

[0017] The reaction involves dissolving piperazine in a solvent and then adding cyanuric chloride dropwise. To ensure that the three chlorine atoms in the cyanuric chloride are completely substituted and to avoid precipitation due to mono- or di-substitution, the temperature is increased to 90℃~95℃.

[0018] Acid-binding agents include: triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. Sodium carbonate has moderate alkalinity and is unlikely to undergo competitive substitution reactions with cyanuric chloride, which is beneficial for controlling the stepwise substitution process of piperazine on cyanuric chloride. Compared with strong bases such as sodium hydroxide and potassium hydroxide, sodium carbonate has a milder alkalinity, which can effectively neutralize the acidic substances generated during the reaction, while avoiding hydrolysis or side reactions caused by excessive alkalinity. Therefore, sodium carbonate is preferred.

[0019] The product obtained from the reaction can be quickly washed with an alkaline aqueous solution to remove the adsorbed acid.

[0020] (2) Under the action of the acid-binding agent, 2,4,6-tripiperazinyltriazine reacts with benzyl chloride to generate 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine.

[0021]

[0022] The reaction needs to be carried out in the presence of an acid-binding agent, and DMF can be used as a solvent.

[0023] Theoretically, the molar ratio of benzyl chloride to 2,4,6-tripiperazinyltriazine is 3:1. In order to react the tripiperazinyltriazine as completely as possible and to increase the reaction rate, the molar ratio of benzyl chloride to 2,4,6-tripiperazinyltriazine is 3.2:1 to 6:1, preferably 4:1 to 5:1.

[0024] The acid-binding agents include: triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate. Since sodium carbonate has moderate alkalinity and does not participate in the reaction, it is beneficial to improve the selectivity of the tertiary amination reaction and reduce the occurrence of side reactions, so sodium carbonate is preferred.

[0025] The reaction temperature is 100-150℃, preferably 120-130℃, and the reaction time is 8-10h.

[0026] (3) 2,4,6-tris(4-benzylpiperazine-1-yl)-1,3,5-triazine reacts with haloalkanes to prepare quaternary ammonium salt compounds.

[0027] The 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine molecule contains nine nitrogen atoms of tertiary amine groups. To determine which nitrogen atoms could form quaternary ammonium salts, the experiment first investigated the reaction of 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine with benzyl chloride in excess. NMR results showed that, under the experimental conditions, only three quaternary ammonium salts could be formed. From a steric hindrance perspective, it is likely that the nitrogen atoms attached to the benzyl groups formed the quaternary ammonium salts. Therefore, the quaternary ammonium salts prepared in this step are considered to have formed three quaternary ammonium salts.

[0028] The halogenated alkane used includes benzyl chloride, epichlorohydrin, chloroacetamide, and 2-chloroethanol, with benzyl chloride preferably used in combination with other halogenated compounds.

[0029] The reaction solvent can be DMF, DMSO, THF, 1,4-dioxane and mixtures thereof, or alcohols such as ethanol, propanol, and butanol. Because DMF has high polarity and strong dissolving power, it is preferred for dissolving the raw material 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine.

[0030] Depending on the type and characteristics of the selected haloalkane, when the chloroalkane has high reactivity, such as epichlorohydrin, it can react at a lower temperature. Therefore, the preferred reaction temperature is 60℃~100℃.

[0031] The molar ratio of the haloalkane to the tertiary amine can be 3:1 to 6:1, preferably 3.2:1 to 5:1. When multiple haloalkanes are used for quaternization, the total molar amount relative to the tertiary amine can be controlled within the range of 3.2:1 to 5:1. Each haloalkane can be added in equimolar or unequal molar amounts, thereby achieving controllable introduction of the quantity and type of quaternary ammonium salt in the molecule.

[0032] The quaternary ammonium salt obtained in this step also has antibacterial and anti-wrinkle effects.

[0033] The quaternary ammonium salt obtained in this step has a bactericidal effect, but the type is limited. In order to improve the overall bactericidal effect, the tertiary amine group in the quaternary ammonium salt obtained in this step can be further salted. The hydrochloride salt of organic amines also has a bactericidal effect.

[0034] (4) The quaternary ammonium salt compound obtained in step (3) undergoes a salt formation reaction with hydrochloric acid, resulting in a molecule containing not only quaternary ammonium salt groups but also tertiary amine hydrochloride groups. Both groups have bactericidal functions and are complementary. A multi-quaternary ammonium salt antibacterial agent for textiles with anti-wrinkle function is obtained.

[0035] In step (4), the number of tertiary amine molecules in the quaternary ammonium salt compound that react with hydrochloric acid to form salts affects the overall molecular cation density and water solubility. However, excessive hydrochloric acid salts can cause the system to become too acidic, affecting the stability of the finishing solution or the fabric's hand feel. In step (4), the number of tertiary amine molecules in the quaternary ammonium salt compound that react with hydrochloric acid to form salts should be controlled between 1 and 3.

[0036] The amount of hydrochloric acid used depends on the amount of hydrochloride salt to be generated, and the overall error is controlled within ±10%.

[0037] The quaternary ammonium salt compound obtained in step (3) is soluble in an alcohol / water mixed solvent, such as an ethanol / water mixed solvent, a methanol / water mixed solvent, or an isopropanol / water mixed solvent. After adding hydrochloric acid, it forms a salt. Then, the water is removed, and the product precipitates out as a solid powder or a viscous substance. The preferred solvent is an ethanol / water mixed solvent.

[0038] The reaction temperature can be 0 to 40°C, preferably 0 to 10°C for adding hydrochloric acid, and the reaction is completed at 20 to 30°C.

[0039] Beneficial effects: The molecular characteristics of this antibacterial agent include nine nitrogen atoms, multiple quaternary ammonium salts, multiple tertiary amine hydrochlorides, and groups that can couple with fibers. Therefore, the molecule has a high degree of bonding with the fiber and a high overall cationic density, thereby enhancing antibacterial activity and durability. Simultaneously, the molecule possesses a large skeletal structure centered on a triazine ring extending in a trigonal direction, which not only imparts excellent antibacterial properties to the fabric but also improves its wrinkle resistance and dimensional stability, achieving a dual effect of antibacterial and wrinkle resistance. Attached Figure Description

[0040] Figure 1 The 1H NMR spectrum of 2,4,6-tripiperazine-based triazine prepared in Example 1.

[0041] Figure 2 The 1H NMR spectrum of 2,4,6-tris(4-benzylpiperazine-1-yl)-1,3,5-triazine prepared in Example 1.

[0042] Figure 3 The image shows the 1H NMR spectrum of the quaternary ammonium salt prepared in Example 5. Detailed Implementation

[0043] The following specific embodiments provide illustrative examples and further explanation of this application. However, these embodiments are given only as examples and are not considered as all the technical solutions of the present invention, nor are they a limitation on the overall technical solution of the present invention. Any simple changes or substitutions to the same or similar technical features are within the protection scope of the present invention.

[0044] Example 1

[0045] Anhydrous piperazine (0.175 mol, 15.14 g) was dissolved in 100 mL of 1,4-dioxane and added to a 500 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser. Sodium carbonate (0.15 mol, 15.9 g) was then added. Stirring was started, and a solution of 9.22 g (0.05 mol) cyanuric chloride dissolved in 50 mL of 1,4-dioxane was slowly added dropwise to the flask, maintaining the temperature at approximately 90 °C. The addition was completed in 47 minutes. Stirring continued, and a white solid gradually precipitated. After 9 hours of reaction, the amount of white solid no longer increased. The reaction was stopped, and the resulting solid-liquid mixture was filtered. The filter cake was washed with sodium carbonate aqueous solution, followed by three washes with 50 mL of water each time, maintaining a near-neutral pH. Vacuum drying at 80℃ for 4 hours yielded 15.68 g of the product 2,4,6-tripiperazine-triazine, with a yield of 94.14% (1H NMR spectrum attached). Figure 1 (As shown).

[0046] Repeat the above steps to obtain 15.70g of the product 2,4,6-tripiperazine-triazine.

[0047] Weigh out 0.05 mol (16.67 g) of 2,4,6-tripiperazinyltriazine and 0.085 mol (9 g) of sodium carbonate, and add them to a 500 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser. Add 150 mL of DMF as solvent, start stirring, and maintain the temperature at 100 °C. Add benzyl chloride (0.16 mol, 20.25 mL) dropwise over 40 min. After continued stirring, a white solid precipitates, and the liquid gradually turns red. The reaction takes 10 h. After the reaction is complete, filter to remove the solid. Add 200 mL of water to the filtrate to precipitate the solid. Filter the solid-liquid mixture, and wash the filter cake three times with 20 mL of water each time. Dry under vacuum at 80 °C for 4 h to obtain 27.85 g of 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine, with a yield of 92.31% (1H NMR spectrum attached). Figure 2 (As shown).

[0048] Example 2

[0049] Anhydrous piperazine (0.20 mol, 17.23 g) was dissolved in 120 mL of 1,4-dioxane and added to a 500 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser. Sodium carbonate (0.15 mol, 15.9 g) was then added. Stirring was started, and a solution of 9.22 g (0.05 mol) cyanuric chloride dissolved in 50 mL of 1,4-dioxane was slowly added dropwise to the flask at approximately 92 °C over 45 min. Stirring continued, and a white solid gradually precipitated. After 9 h of reaction, the amount of white solid no longer increased. The reaction was stopped, and the resulting solid-liquid mixture was filtered. The filter cake was washed with sodium carbonate aqueous solution, followed by three washes with 50 mL of water each time, maintaining a near-neutral pH. The mixture was then vacuum dried at 80 °C for 4 h to obtain 16.36 g of the product 2,4,6-tripiperazine-based triazine, with a yield of 98.14%.

[0050] Repeat the above steps to obtain 15.41g of the product 2,4,6-tripiperazine-triazine.

[0051] 0.05 mol (16.67 g) of 2,4,6-tripiperazinyltriazine and 0.085 mol (9 g) of sodium carbonate were weighed and added to a 500 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser. 170 mL of DMF was added as solvent, stirring was started, and the temperature was controlled at 110 °C. 0.20 mol (23 mL) of benzyl chloride was added dropwise over 45 min. With continued stirring, a white solid precipitated, and the liquid gradually turned red. The reaction proceeded for 9 h. After the reaction was complete, the solid was removed by filtration. 220 mL of water was added to the filtrate to precipitate the solid. The solid-liquid mixture was filtered, and the filter cake was washed three times with 20 mL of water each time. The mixture was dried under vacuum at 80 °C for 4 h to obtain 28.15 g of 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine, with a yield of 93.24%.

[0052] Example 3

[0053] Anhydrous piperazine (0.25 mol, 21.53 g) was dissolved in 140 mL of 1,4-dioxane and added to a 500 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser. Sodium carbonate (0.15 mol, 15.9 g) was then added. Stirring was started, and a solution of 9.22 g (0.05 mol) cyanuric chloride dissolved in 50 mL of 1,4-dioxane was slowly added dropwise to the flask at approximately 93 °C over 48 min. Stirring continued, and a white solid gradually precipitated. After 8 h of reaction, the white solid content stopped increasing. The reaction was stopped, and the resulting solid-liquid mixture was filtered. The filter cake was washed with sodium carbonate aqueous solution, followed by three washes with 50 mL of water each time, maintaining a near-neutral pH. The mixture was then vacuum dried at 80 °C for 4 h to obtain 16.60 g of the product 2,4,6-tripiperazine-based triazine, with a yield of 99.61%.

[0054] Repeat the above steps to obtain 16.62g of the product 2,4,6-tripiperazine-triazine.

[0055] 0.05 mol (16.67 g) of 2,4,6-tripiperazinyltriazine and 0.085 mol (9 g) of sodium carbonate were weighed and added to a 500 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser. 190 mL of DMF was added as solvent, stirring was started, and the temperature was controlled at 120 °C. 0.25 mol (28.77 mL) of benzyl chloride was added dropwise over 48 min. With continued stirring, a white solid precipitated, and the liquid gradually turned red. The reaction proceeded for 9 h. After the reaction was complete, the solid was removed by filtration. 240 mL of water was added to the filtrate to precipitate the solid. The solid-liquid mixture was filtered, and the filter cake was washed three times with 20 mL of water each time. The mixture was dried under vacuum at 80 °C for 4 h to obtain 28.12 g of 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine, with a yield of 93.17%.

[0056] Example 4

[0057] Anhydrous piperazine (0.30 mol, 25.84 g) was dissolved in 160 mL of 1,4-dioxane and added to a 500 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser. Sodium carbonate (0.15 mol, 15.9 g) was then added. Stirring was started, and a solution of 9.22 g (0.05 mol) cyanuric chloride dissolved in 50 mL of 1,4-dioxane was slowly added dropwise to the flask at approximately 95 °C over 50 minutes. Stirring continued, and a white solid gradually precipitated. After 8 hours of reaction, the amount of white solid no longer increased. The reaction was stopped, and the resulting solid-liquid mixture was filtered. The filter cake was washed with sodium carbonate aqueous solution, followed by three washes with 50 mL of water each time, maintaining a near-neutral pH. The mixture was then vacuum dried at 80 °C for 4 hours to obtain 16.59 g of the product 2,4,6-tripiperazine-based triazine, with a yield of 99.58%.

[0058] Repeat the above steps to obtain 16.61g of the product 2,4,6-tripiperazine-triazine.

[0059] 0.05 mol (16.67 g) of 2,4,6-tripiperazinyltriazine and 0.085 mol (9 g) of sodium carbonate were weighed and added to a 500 mL four-necked flask equipped with a stirrer, thermometer, dropping funnel, and reflux condenser. 210 mL of DMF was added as solvent, stirring was started, and the temperature was controlled at 130 °C. 0.30 mol (37.97 mL) of benzyl chloride was added dropwise over 50 min. With continued stirring, a white solid precipitated, and the liquid gradually turned red. The reaction proceeded for 8 h. After the reaction was complete, the solid was removed by filtration. 260 mL of water was added to the filtrate to precipitate the solid. The solid-liquid mixture was filtered, and the filter cake was washed three times with 20 mL of water each time. The mixture was dried under vacuum at 80 °C for 4 h to obtain 28.07 g of 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine, with a yield of 93.16%.

[0060] Example 5

[0061] 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine (0.01 mol, 6.04 g) prepared in Example 1 was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 80 mL of DMF was added as a solvent, and the mixture was heated to 40 °C to dissolve it. Stirring continued, and the temperature was raised to 100 °C. Benzyl chloride (0.03 mol, 3.45 mL) was added dropwise over 8 minutes. The reaction was carried out at 100 °C. After 6 hours of addition, a solid gradually precipitated. Once the solid content stopped increasing, the resulting solid-liquid mixture was filtered. The filter cake was washed five times with 50 mL of ethanol each time to remove excess DMF. The filter cake was then vacuum dried at 80 °C for 5 hours. 8.08 g of the product was obtained, with a yield of 92.42%, and designated as antibacterial agent A.

[0062] Example 6

[0063] 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine (0.01 mol, 6.04 g) prepared in Example 1 was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 80 mL of DMF was added as a solvent, and the mixture was heated to 40 °C to dissolve it. Stirring continued, and the temperature was raised to 100 °C. Benzyl chloride (0.04 mol, 4.60 mL) was added dropwise over 10 min. The reaction was continued at 100 °C. After 6 h of addition, a solid gradually precipitated. Once the solid content stopped increasing, the resulting solid-liquid mixture was filtered. The filter cake was washed five times with 50 mL of ethanol each time to remove excess DMF. The filter cake was then vacuum dried at 80 °C for 5 h. 8.33 g of the product was obtained, with a yield of 95.19%, designated as antibacterial agent A.

[0064] Example 7

[0065] 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine (0.01 mol, 6.04 g) prepared in Example 1 was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 80 mL of DMF was added as a solvent, and the mixture was heated to 40 °C to dissolve it. Stirring continued, and the temperature was raised to 100 °C. Benzyl chloride (0.05 mol, 5.75 mL) was added dropwise over 10 min. The reaction was carried out at 100 °C. After 6 h of addition, a solid gradually precipitated. Once the solid content stopped increasing, the resulting solid-liquid mixture was filtered. The filter cake was washed five times with 50 mL of ethanol each time to remove excess DMF. The filter cake was then vacuum dried at 80 °C for 5 h. Product 8.47 was obtained, with a yield of 96.74%, and designated as antibacterial agent A.

[0066] Example 8

[0067] 0.01 mol of antibacterial agent A (8.00 g) prepared in Example 5 and antibacterial agent A (0.76 g) prepared in Example 6 were added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 80 mL of anhydrous ethanol and 10 mL of deionized water were added as solvents, and the mixture was stirred at room temperature to dissolve. Concentrated hydrochloric acid (0.01 mol, 0.85 mL) was added dropwise under ice bath conditions at approximately 5°C. After the addition was complete, the temperature was raised to room temperature, and stirring continued for 5 hours. After the reaction was complete, some ethanol was removed by rotary evaporation, yielding a viscous substance. This substance was dried under vacuum at 60°C for 4 hours to obtain 8.34 g of product, with a yield of 91.44%, designated as antibacterial agent A1.

[0068] Example 9

[0069] 0.01 mol of antibacterial agent A (7.00 g) prepared in Example 6 and antibacterial agent A (1.76 g) prepared in Example 7 were added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 90 mL of anhydrous ethanol and 15 mL of deionized water were added as solvents, and the mixture was stirred at room temperature to dissolve. Concentrated hydrochloric acid (0.02 mol, 1.70 mL) was added dropwise under an ice bath at approximately 6°C. After the addition was complete, the temperature was raised to room temperature, and stirring continued for 5 hours. After the reaction was complete, some ethanol was removed by rotary evaporation, yielding a viscous substance. This substance was dried under vacuum at 60°C for 4 hours to obtain 8.57 g of product, with a yield of 90.18%, designated as antibacterial agent A2.

[0070] Example 10

[0071] Antibacterial agent A (0.01 mol, 8.76 g), prepared using the same method as in Example 6, was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 90 mL of anhydrous ethanol and 20 mL of deionized water were added as solvents, and the mixture was stirred at room temperature to dissolve. Concentrated hydrochloric acid (0.03 mol, 2.55 mL) was added dropwise under an ice bath at approximately 7°C. After the addition was complete, the temperature was raised to room temperature, and stirring continued for 6 hours. After the reaction was complete, some ethanol was removed by rotary evaporation, yielding a viscous substance. This substance was dried under vacuum at 60°C for 4 hours to obtain 9.19 g of product, with a yield of 93.27%, designated as antibacterial agent A3.

[0072] Example 11

[0073] 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine (0.01 mol, 6.04 g) prepared in Example 1 was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 80 mL of DMF was added as a solvent, and the mixture was heated to 40 °C to dissolve it. Stirring continued, and the temperature was raised to 90 °C. Benzyl chloride (0.02 mol, 2.30 mL) was added dropwise over 5 minutes. The reaction was continued at 90 °C for 8 hours. The reaction solution was then cooled to 60 °C, and epichlorohydrin (0.013 mol, 1.02 mL) was added. The reaction continued at 60 °C for another 8 hours, after which a solid gradually precipitated. Once the solid content stopped increasing, the resulting solid-liquid mixture was filtered. The filter cake was washed three times with 20 mL of a 1:1 (v / v) ethanol / ether mixture to remove excess DMF. The filter cake was then vacuum dried at 80 °C for 5 hours. 8.12g of product was obtained, with a yield of 96.57%, and it was designated as antibacterial agent B.

[0074] Example 12

[0075] Antibacterial agent B (0.01 mol, 8.41 g), prepared using the same method as in Example 11, was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 80 mL of anhydrous ethanol and 10 mL of deionized water were added as solvents, and the mixture was stirred at room temperature to dissolve. Concentrated hydrochloric acid (0.01 mol, 0.85 mL) was added dropwise under an ice bath at approximately 5°C. After the addition was complete, the temperature was raised to room temperature, and stirring continued for 4 hours. After the reaction was complete, some ethanol was removed by rotary evaporation, yielding a viscous substance. This substance was dried under vacuum at 60°C for 4 hours to obtain 7.80 g of product, with a yield of 88.71%, designated as antibacterial agent B1.

[0076] Example 13

[0077] Antibacterial agent B (0.01 mol, 8.41 g), prepared using the same method as in Example 11, was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 85 mL of anhydrous ethanol and 15 mL of deionized water were added as solvents, and the mixture was stirred at room temperature to dissolve. Concentrated hydrochloric acid (0.02 mol, 1.70 mL) was added dropwise under an ice bath at approximately 6°C. After the addition was complete, the temperature was raised to room temperature, and stirring continued for 4 hours. After the reaction was complete, some ethanol was removed by rotary evaporation, yielding a viscous substance. This substance was then vacuum dried at 60°C for 4 hours to obtain 8.24 g of the product, with a yield of 89.96%, designated as antibacterial agent B2.

[0078] Example 14

[0079] Antibacterial agent B (0.01 mol, 8.41 g), prepared using the same method as in Example 11, was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 90 mL of anhydrous ethanol and 20 mL of deionized water were added as solvents, and the mixture was stirred at room temperature to dissolve. Concentrated hydrochloric acid (0.03 mol, 2.55 mL) was added dropwise under an ice bath at approximately 4°C. After the addition was complete, the temperature was raised to room temperature, and stirring continued for 5 hours. After the reaction was complete, some ethanol was removed by rotary evaporation, yielding a viscous substance. This substance was then vacuum dried at 60°C for 4 hours to obtain 8.60 g of the product, with a yield of 90.27%, designated as antibacterial agent B3.

[0080] Example 15

[0081] 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine (0.01 mol, 6.04 g), prepared using the same method as in Example 1, was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 80 mL of DMF was added as a solvent, and the mixture was heated to 40 °C to dissolve. Stirring continued, and the temperature was raised to 80 °C. Benzyl chloride (0.01 mol, 1.15 mL) was added dropwise over 5 minutes. The reaction was continued at 80 °C for 10 hours. The reaction solution was then cooled to 50 °C, and epichlorohydrin (0.026 mol, 2.04 mL) was added. The reaction was continued at 60 °C for 9 hours, after which a solid gradually precipitated. Once the solid content stopped increasing, the resulting solid-liquid mixture was filtered. The filter cake was washed three times with 30 mL of a 1:1 (v / v) ethanol / ether mixture to remove excess DMF. The filter cake was then vacuum-dried at 80 °C for 5 hours. 7.40g of product was obtained, with a yield of 91.54%, and it was designated as antibacterial agent C.

[0082] Example 16

[0083] Antibacterial agent C (0.01 mol, 8.09 g), prepared using the same method as in Example 15, was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 80 mL of anhydrous ethanol and 10 mL of deionized water were added as solvents, and the mixture was stirred at room temperature to dissolve. Concentrated hydrochloric acid (0.01 mol, 0.85 mL) was added dropwise under an ice bath at approximately 8°C. After the addition was complete, the temperature was raised to room temperature, and stirring continued for 4 hours. After the reaction was complete, some ethanol was removed by rotary evaporation, yielding a viscous substance. This substance was dried under vacuum at 60°C for 4 hours to obtain 7.35 g of product, with a yield of 86.92%, designated as antibacterial agent C1.

[0084] Example 17

[0085] Antibacterial agent C (0.01 mol, 8.09 g), prepared using the same method as in Example 15, was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 85 mL of anhydrous ethanol and 15 mL of deionized water were added as solvents, and the mixture was stirred at room temperature to dissolve. Concentrated hydrochloric acid (0.02 mol, 1.70 mL) was added dropwise under an ice bath at approximately 6°C. After the addition was complete, the temperature was raised to room temperature, and stirring continued for 5 hours. After the reaction was complete, some ethanol was removed by rotary evaporation, yielding a viscous substance. This substance was then vacuum dried at 60°C for 5 hours to obtain 7.80 g of product, with a yield of 88.43%, designated as antibacterial agent C2.

[0086] Example 18

[0087] Antibacterial agent C (0.01 mol, 8.09 g), prepared using the same method as in Example 15, was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 90 mL of anhydrous ethanol and 20 mL of deionized water were added as solvents, and the mixture was stirred at room temperature to dissolve. Concentrated hydrochloric acid (0.03 mol, 2.55 mL) was added dropwise under an ice bath at approximately 4°C. After the addition was complete, the temperature was raised to room temperature, and stirring continued for 5 hours. After the reaction was complete, some ethanol was removed by rotary evaporation, yielding a viscous substance. This substance was dried under vacuum at 60°C for 5 hours to obtain 8.37 g of product, with a yield of 91.17%, designated as antibacterial agent C3.

[0088] Example 19

[0089] 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine (0.01 mol, 6.04 g), prepared using the same method as in Example 1, was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 80 mL of DMF was added as a solvent, and the mixture was heated to 50 °C to dissolve it. Stirring continued, and the temperature was raised to 70 °C. Epichlorohydrin (0.04 mol, 3.14 mL) was added dropwise over 10 min. After reacting at 70 °C for 8 h, a solid gradually precipitated. Once the solid content decreased, the resulting solid-liquid mixture was filtered. The filter cake was washed five times with 30 mL of a 1:1 (v / v) ethanol / ether mixture to remove excess DMF. The filter cake was then vacuum-dried at 80 °C for 5 h. 7.22 g of the product was obtained, with a yield of 93.27%, designated as antibacterial agent D.

[0090] Example 20

[0091] Antibacterial agent D (0.01 mol, 7.75 g), prepared using the same method as in Example 19, was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 80 mL of anhydrous ethanol and 10 mL of deionized water were added as solvents, and the mixture was stirred at room temperature to dissolve. Concentrated hydrochloric acid (0.01 mol, 0.85 mL) was added dropwise under an ice bath at approximately 8°C. After the addition was complete, the temperature was raised to room temperature, and stirring continued for 5 hours. After the reaction was complete, some ethanol was removed by rotary evaporation, yielding a viscous substance. This substance was dried under vacuum at 60°C for 3 hours to obtain 7.40 g of product, with a yield of 91.19%, designated as antibacterial agent D1.

[0092] Example 21

[0093] Antibacterial agent D (0.01 mol, 7.75 g), prepared using the same method as in Example 19, was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 85 mL of anhydrous ethanol and 15 mL of deionized water were added as solvents, and the mixture was stirred at room temperature to dissolve. Concentrated hydrochloric acid (0.02 mol, 1.70 mL) was added dropwise under an ice bath at approximately 6°C. After the addition was complete, the temperature was raised to room temperature, and stirring continued for 6 hours. After the reaction was complete, some ethanol was removed by rotary evaporation, yielding a viscous substance. This substance was dried under vacuum at 60°C for 4 hours to obtain 7.80 g of product, with a yield of 92.07%, designated as antibacterial agent D2.

[0094] Example 22

[0095] Antimicrobial agent D (0.01 mol, 7.75 g), prepared using the same method as in Example 19, was added to a 250 mL four-necked flask equipped with a mechanical stirrer, thermometer, dropping funnel, and reflux condenser. 90 mL of anhydrous ethanol and 20 mL of deionized water were added as solvents, and the mixture was stirred at room temperature to dissolve. Concentrated hydrochloric acid (0.03 mol, 2.55 mL) was added dropwise under ice bath conditions at approximately 4°C. After the addition was complete, the temperature was raised to room temperature, and stirring continued for 5 hours. After the reaction was complete, some ethanol was removed by rotary evaporation, yielding a viscous substance. This substance was then vacuum dried at 60°C for 4 hours to obtain 8.14 g of the product, with a yield of 92.11%, designated as antimicrobial agent D3.

[0096] Example 23

[0097] The antibacterial effect of the antibacterial agent prepared in the above embodiments was evaluated using the shaking method against Escherichia coli, Staphylococcus aureus, and Candida albicans, with reference to GB / T 20944.3-2008. The control group consisted of a blank sample, which was a standard cotton lining fabric used for color fastness testing, subjected to high-temperature steaming and washing with distilled water.

[0098] (1) Apply antibacterial agents to textiles

[0099] Cut the cotton fabric into 5mm×5mm pieces, weighing 0.75g±0.05g as one sample. Immerse the cotton fabric sample in an antibacterial agent of a certain concentration (0.4g of antibacterial agent dissolved in 10mL of water), with a mass ratio of cotton fabric to antibacterial agent solution of 1:13, for 12 hours, and then dry at 80-100℃.

[0100] (2) Blank sample treatment

[0101] After steaming and washing with distilled water, the cotton fabric was cut into 5mm×5mm pieces to serve as blank samples.

[0102] (3) Sterilize the cotton fabric sample and the blank sample at 121℃ for 30 min.

[0103] (4) Preparation of sample and blank bacterial solution

[0104] The bacterial suspension was diluted to 1.0 × 10⁵ CFU / ml with nutrient broth and phosphate buffered solution (PBS). Sterilized cotton fabric was cut into pieces and added to the diluted bacterial suspension liquid culture medium. The mixture was then cultured for 18 h in a shaker at 37 °C and 150 r / min.

[0105] (5) Dilute to 1.0×10 5 CFU / ml bacterial suspension was then subjected to 10, 10 2 and 10 3 Three-stage dilution was performed, with the bacterial suspension from each stage serving as the sample. 1 mL of bacterial suspension was transferred from each sample, diluted, and then transferred to a petri dish. Agar medium was poured in, shaken evenly, and after the medium cooled, the plate was inverted and placed in a biochemical incubator at 37°C for 48 hours (72 hours for Candida albicans).

[0106] (6) After completion, count the viable bacteria on the plate. The inhibition rate is calculated based on the number of colonies and the following formula.

[0107]

[0108] Where Y represents the antibacterial rate; W t Q represents the number of viable bacteria on the blank sample; t The number of live bacteria on the test sample.

[0109] The experimental results are shown in Table 1.

[0110] Table 1: Antibacterial properties of different antibacterial agents

[0111]

[0112] Experimental results show that (1) except for antibacterial agents A, B, C, and D, which have an antibacterial rate of about 85% against Candida albicans, the other effects are all greater than 96.2%; in particular, antibacterial agents B1, B2, B3, C1, C2, C3, D1, D2, and D3, which are within the scope of patent protection, all have an antibacterial effect of more than 97.8% against the three bacteria, showing excellent broad-spectrum bactericidal performance. (2) This indicates that the multi-cationic quaternary ammonium salt structure constructed in this invention can effectively destroy the cell membrane structure of microorganisms and achieve efficient bactericidal effect; after hydrochlorination, its spectral antibacterial properties are further improved.

[0113] Example 24

[0114] The water resistance test shall be conducted in accordance with the standard GB / T 3921-2008, and the steps are as follows.

[0115] (1) Prepare a neutral soap solution with a concentration of 2 g / L.

[0116] (2) Measure 50 mL of neutral soap detergent into a steel bottle, add 10 steel balls with a diameter of 5 mm, and put in 1 g of cotton fabric sample to be tested.

[0117] (3) The stirring speed is set to 40 r / min, the washing temperature is 40℃, and the washing time is 45 min.

[0118] (4) Take out the washed cotton fabric, wash it twice with deionized water and then air dry it at room temperature as a washing cycle. This washing degree is 5 times that of household washing.

[0119] The experimental results are shown in Table 2.

[0120] Table 2: Antibacterial properties of different antibacterial agents after washing

[0121]

[0122] The experimental results showed that: (1) With the increase of the number of washes, the antibacterial rate of each sample gradually decreased, but the antibacterial effects of antibacterial agents B1, B2, B3, C1, C2, C3, D1, D2, and D3 on the three bacteria remained above 91.5%. (2) Compared with antibacterial agents B, C, and D, the antibacterial rate of antibacterial agents A to A3 decreased significantly. This may be because antibacterial agents B, C, and D contain epoxy groups, which can undergo ring-opening reactions with cellulose hydroxyl groups to form stable covalent bonds, thereby significantly improving the wash fastness. (3) The water resistance of antibacterial agent A decreased from antibacterial agent A to antibacterial agent A3. The same effect can be seen in antibacterial agents B, C, and D. This should be because the acidity and solubility in water gradually increase with the increase of hydrochloric acid acidification.

[0123] Example 25

[0124] Wrinkle resistance test: The wrinkle resistance test is conducted in accordance with GB / T 3819-1997 "Textiles - Determination of Crease Recovery - Recovery Angle Method", using the horizontal method. The steps are as follows:

[0125] (1) The sample is a rectangle with a size of 40mm×15mm. Fold it with both ends aligned in the length direction of the sample, then clamp it with wide-nose pliers. The clamping position should not be more than 5mm away from the end of the cloth. Move it to a flat plate marked with 15mm×20mm to make the sample correctly positioned.

[0126] (2) Then gently apply a pressure hammer with a pressure load of 10N for 5min±5s.

[0127] (3) Remove the load and transfer the wide-mouth clamp holding the sample to the sample clamp of the recovery angle measuring device, so that one wing of the sample is clamped and the other wing hangs freely. Continuously adjust the sample clamp so that the hanging free wing always remains in a vertical position.

[0128] (4) Five minutes after the sample is unloaded from the pressure load device, the crease recovery angle is read and the reading is taken to the nearest 1. If the free wing is slightly curled or twisted, the vertical plane passing through the center of the wing and the axis of the scale is used as the reference for the crease recovery angle reading (the sum of the longitudinal and latitudinal directions).

[0129] The experimental results are shown in Table 3.

[0130] Table 3: Anti-wrinkle properties of different antibacterial agents

[0131]

[0132] Experimental results show that antibacterial agent series A contains only a benzyl quaternary ammonium salt structure and lacks active groups that can covalently react with fibers. Its improved wrinkle resistance mainly stems from the electrostatic adsorption of cations with fibers; therefore, although the improvement is approximately 25° compared to the control, the effect is limited. Antibacterial agents series B, C, and D introduce one, two, and three epoxy groups, respectively, which can undergo ring-opening reactions with hydroxyl groups on the fabric to form ether crosslinks. Therefore, the wrinkle resistance gradually increases with the increase in the number of epoxy groups. From A to A3, B to B3, C to C3, and D to D3, due to the increased hygroscopicity and hydrophilicity of the hydrochloride structure, the reactivity with fibers decreases, thus exhibiting a pattern where wrinkle resistance decreases with increasing salinization.

[0133] The above results demonstrate that the antibacterial agent provided by this invention has a structure of multi-quaternary ammonium salt combined with hydrochloride, exhibiting stable broad-spectrum antibacterial activity. Furthermore, by leveraging the stabilizing effect of epoxy groups or their ring-opening derivatives forming with cellulose molecules, the binding strength of the antibacterial component on the fiber is improved, thus maintaining excellent antibacterial properties even under washing conditions. The antibacterial agent molecule possesses a large skeleton structure centered on a triazine ring, extending in a tri-directional direction, which, while imparting excellent antibacterial properties to the fabric, also enhances its wrinkle resistance and dimensional stability, achieving a dual function of antibacterial and wrinkle resistance.

Claims

1. A type of antibacterial agent for textiles with anti-wrinkle function, characterized in that, The multi-quaternary ammonium salt antibacterial agent for textiles has the following general structural formula: ， Where R1, R2, and R3 are alkyl groups of haloalkanes, which can be the same or different; n represents the number of amino groups in the molecule that form hydrochloride salts, and the value ranges from 1 to 3.

2. A method for preparing a multi-quaternary ammonium salt textile antibacterial agent with anti-wrinkle function according to claim 1, characterized in that, The preparation method steps are as follows: (1) Under the action of an acid-binding agent, anhydrous piperazine reacts with cyanuric chloride to generate 2,4,6-tripiperazinyltriazine; (2) Under the action of an acid-binding agent, 2,4,6-tripiperazinyltriazine reacts with benzyl chloride to generate 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine; (3) 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine reacts with haloalkanes to prepare quaternary ammonium salt compounds; (4) The quaternary ammonium salt compound obtained in step (3) reacts with hydrochloric acid to form a salt, thereby obtaining a multi-quaternary ammonium salt textile antibacterial agent with anti-wrinkle function.

3. The method for preparing the anti-wrinkle multi-quaternary ammonium salt textile antibacterial agent according to claim 2, characterized in that, In step (1), the molar ratio of anhydrous piperazine to cyanuric chloride is 3.5:1 to 6:

1.

4. The method for preparing the anti-wrinkle multi-quaternary ammonium salt textile antibacterial agent according to claim 2, characterized in that, In step (2), the molar ratio of benzyl chloride to 2,4,6-tripiperazine triazine is 3.2:1 to 6:1, the reaction temperature is 100 to 150°C, and the reaction time is 8 to 10 h.

5. The method for preparing the anti-wrinkle multi-quaternary ammonium salt textile antibacterial agent according to claim 2, characterized in that, In steps (1) and (2), the acid-binding agent is one of the following: triethylamine, pyridine, sodium hydroxide, potassium hydroxide, sodium carbonate, and potassium carbonate.

6. The method for preparing the antibacterial agent for multi-quaternary ammonium salt textiles with anti-wrinkle function according to claim 2, characterized in that, In step (3), the haloalkane is one or a mixture of several of benzyl chloride, epichlorohydrin, chloroacetamide, and 2-chloroethanol, wherein benzyl chloride is not used alone.

7. The method for preparing the antibacterial agent for multi-quaternary ammonium salt textiles with anti-wrinkle function according to claim 2, characterized in that, In step (3), the molar ratio of haloalkane to 2,4,6-tris(4-benzylpiperazin-1-yl)-1,3,5-triazine is 3.2:1 to 5:1; the reaction temperature is 50 to 100 °C.

8. The method for preparing the anti-wrinkle multi-quaternary ammonium salt textile antibacterial agent according to claim 2, characterized in that, In step (4), the number of tertiary amine N atoms in the quaternary ammonium salt compound molecule that form salt with hydrochloric acid is controlled between 1 and 3; the molar amount of hydrochloric acid is determined by the molar amount of hydrochloric acid to be generated as needed, and the overall error is controlled within ±10%.

9. The application of a multi-quaternary ammonium salt antibacterial agent for textiles with anti-wrinkle function according to claim 1, characterized in that, The antibacterial agent is used to prepare textiles that have both antibacterial and wrinkle-resistant properties.

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