Preparation method of responsive antibacterial polyester fabric

Abstract

This invention discloses a method for preparing a responsive antibacterial polyester fabric, specifically relating to the field of polymer textile materials technology. The preparation method includes: reacting 2,2-dimethylpropiolactone with methylamine to obtain an intermediate, then subjecting it to a cyclization reaction with 2-bromo-2-methylpropanol to obtain the target product, and finally applying this compound to a polyester fabric through impregnation, rolling, and baking processes. This compound combines the contact bactericidal mechanism of quaternary ammonium salts with an enzyme-triggered ring-opening mechanism. It can open the ring under the action of bacterial esterases to form a hydrophilic surface, achieving self-cleaning, and regenerates and restores its antibacterial function under acidic conditions, effectively overcoming the dead bacteria covering effect. Simultaneously, this compound exhibits excellent thermal stability and wash fastness, making it suitable for the preparation of polyester textiles.

Description

Technical Field

[0001] This invention relates to the field of polymer textile materials technology, specifically to a method for preparing a responsive antibacterial polyester fabric. Background Technology

[0002] In the field of antimicrobial textiles, endowing materials with durable antimicrobial properties is key to preventing infection, improving medical care, and ensuring food safety. Currently used technologies have several limitations: inorganic antimicrobial agents (such as silver ions) are prone to precipitation, are costly, and have potential cytotoxicity issues; organic small-molecule antimicrobial agents (such as triclosan) are easily lost and may induce drug resistance; traditional quaternary ammonium salt antimicrobial agents, while highly efficient at killing bacteria, after being fixed on the material surface, the dead bacterial remains cover the active sites, leading to a "dead bacteria coverage effect" and a rapid decline in antimicrobial performance.

[0003] Inspired by the enzyme-triggered ring-opening mechanism of β-lactam antibiotics (such as penicillin), existing technologies have introduced designs that incorporate ring-openable structures into antibacterial agents. However, these designs generally lack functional regeneration capabilities and cannot restore their antibacterial state after self-cleaning, resulting in insufficient long-term effectiveness. Furthermore, the preparation of antibacterial polyester through blending requires antibacterial agents to possess excellent thermal stability to withstand processing temperatures up to 180°C; many organic antibacterial agents decompose and become ineffective at this stage.

[0004] Therefore, developing a novel antibacterial agent that can overcome the "dead bacteria coverage effect," possesses responsive and regenerable properties, and also exhibits excellent thermal stability and compatibility with polyester matrix has become a pressing technical problem to be solved in this field. Summary of the Invention

[0005] To achieve the above objectives, the present invention adopts the following technical solution: This invention provides a method for preparing a responsive antibacterial polyester fabric, the method comprising the following steps: (1) Surface activation treatment of ester groups in polyester fabric by hydrolysis; (2) Apply the finishing solution of antibacterial compound and coupling agent to the polyester fabric treated in step S1; (3) The polyester fabric after S2 treatment is subjected to rolling and baking treatment to obtain the responsive antibacterial polyester fabric; The antibacterial compound has the following structure: .

[0006] Furthermore, the specific method for preparing the antibacterial compound is as follows: Step 1: 2,2-Dimethylpropiolactone reacts with methylamine to yield an intermediate compound; Step 2: Under an inert atmosphere, at 0~25℃, the catalyst, condensing agent, 2-bromo-2-methylpropanol, and the intermediate compound obtained in Step 1 are dissolved in a solvent to carry out a cyclization reaction, and the antibacterial compound is obtained after purification; the catalyst in Step 2 is one of 4-dimethylaminopyridine and N-methylimidazole; the condensing agent is one of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N,N'-dicyclohexylcarbodiimide.

[0007] Furthermore, in step two, 2-bromo-2-methylpropanol and the intermediate compound are mixed in a mass ratio of (0.8~1.5):2.

[0008] Furthermore, the raw material for the responsive antibacterial polyester fabric is one or more of polyethylene terephthalate, polyethylene terephthalate, polyethylene isophthalate, and polyethylene adipate.

[0009] Furthermore, the antibacterial compound is present in an amount of 0.1 to 3.0% of the polyester raw material.

[0010] Furthermore, the rolling process controls the liquid retention rate of the antibacterial polyester fabric to be 60-70%.

[0011] Furthermore, the baking process is carried out at a temperature of 150-170°C for 3-8 minutes.

[0012] Beneficial effects of this invention:

[0013] The present invention provides a method for preparing a responsive antibacterial polyester fabric, which has the following significant advantages: The antibacterial polyester fabric contains the aforementioned antibacterial compound. When bacteria are present, it kills bacteria through contact with quaternary ammonium cations. Furthermore, the esterases contained in the bacteria catalyze the opening of the seven-membered ring, forming an amphoteric structure and generating a superhydrophilic surface, thereby washing away bacterial carcasses and achieving self-cleaning, effectively overcoming the dead bacteria covering effect.

[0014] The antibacterial compound has high steric hindrance and is not easily deformed, giving it a high thermal decomposition temperature. It can withstand the polyester processing process and ensure that the antibacterial function of polyester fabrics does not fail due to high temperature.

[0015] Responsive antibacterial polyester fabrics can restore the seven-membered ring structure through intramolecular esterification under acidic conditions, resulting in highly efficient and sustainable antibacterial effects.

[0016] (4) The antibacterial compounds in the fabric are firmly bound to the polyester matrix by covalent bonds or hydrogen bonds, avoiding loss during use and achieving long-lasting antibacterial properties. Detailed Implementation

[0017] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments.

[0018] Based on the embodiments of this invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of this invention.

[0019] Raw material source: 2,2-Dimethylpropiolactone was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd.; methylamine was purchased from Zhejiang Jianye Chemical Co., Ltd.; N,N'-Dicyclohexylcarbodiimide was purchased from Guangzhou Hewei Pharmaceutical Technology Co., Ltd. Example 1

[0020] 2.2 kg of 2,2-dimethylpropiolactone was added to the reactor, and the material was cooled to 0°C using a refrigeration unit. Then, 1 kg of 33 wt% methylamine ethanol solution was added to the reactor, and the mixture was heated to 78°C and refluxed for 20 hours to obtain the crude product.

[0021] The crude product was placed in a crystallization vessel and dissolved in ethyl acetate at 60°C. After cooling to 0°C and allowing to stand, crystals precipitated. The crystals were filtered and dried to obtain the intermediate product. Under a nitrogen atmosphere at 25°C, 1.2 kg of the intermediate, 0.6 kg of 2-bromo-2-methylpropanol, 0.08 kg of N,N'-dicyclohexylcarbodiimide, and 0.03 kg of 4-dimethylaminopyridine were added sequentially, followed by the addition of dichloromethane to dissolve and react for 6 hours. After the reaction was complete, a solid-liquid product was obtained. This product was pumped into a filter press for filtration, and the filtrate was collected. The filtrate was concentrated using a rotary evaporator to obtain an oily product. The separated organic phase was dried over anhydrous magnesium sulfate for 30 minutes. After filtration, the filtrate was concentrated under reduced pressure to obtain the antibacterial compound.

[0022] Preparation of responsive antibacterial polyester fabrics: S1. Clean the fabric with a weak alkaline detergent to remove spinning oils and dirt. Then, soak the fabric in a 2% wt NaOH solution at 80°C for 30 minutes, followed by washing with deionized water until neutral, and drying to obtain the pretreated fabric. S2. Dissolve 1% (by weight) of an antibacterial compound and 1% (by weight) of a coupling agent γ-(2,3-epoxypropoxy)propyltrimethoxysilane in an ethanol solvent, adjusting the pH of the ethanol solution to 6 to obtain an impregnation solution. Immerse the pretreated fabric in the impregnation solution and stir at 50°C for 30 minutes. S3. Control the liquid carry-over rate to 70% using a rolling mill. Bake at 150°C for 3 minutes to obtain a responsive antibacterial polyester fabric. Example 2

[0023] 4 kg of 2,2-dimethylpropiolactone was added to the reactor. The material was cooled to 5°C using a refrigeration unit. Then, 2 kg of a 33 wt% methylamine ethanol solution was added to the reactor, and the mixture was heated to 78°C and refluxed for 20 hours to obtain the crude product.

[0024] The crude product was transferred to a crystallization vessel and dissolved in ethyl acetate at 60°C. After cooling to 0°C and allowing to stand, crystals precipitated. The crystals were then dried to obtain the intermediate product. Under a nitrogen atmosphere at 15°C, 2.4 kg of the intermediate, 1.8 kg of 2-bromo-2-methylpropanol, 1.4 kg of N,N'-dicyclohexylcarbodiimide, and 0.06 kg of 4-dimethylaminopyridine were added sequentially. Dichloromethane was then added to dissolve the crystals completely, and the reaction proceeded for 8 hours. After the reaction, a solid-liquid product was obtained. This product was pumped into a filter press for filtration. The filtrate was collected and concentrated using a rotary evaporator to obtain an oily product. The organic phase was separated and dried over anhydrous magnesium sulfate for 30 minutes. The filtrate was then filtered and concentrated under reduced pressure to obtain the antibacterial compound.

[0025] Preparation of responsive antibacterial polyester fabrics: S1: Clean the fabric with a weak alkaline detergent solution to remove spinning oil and dirt. Treat with 2% wt NaOH solution at 80°C for 60 minutes. Wash thoroughly with deionized water until neutral, and dry to obtain the pretreated fabric. S2: Dissolve 0.1% (by mass) of antibacterial compound and 1% (by mass) of coupling agent γ-aminopropyltriethoxysilane in ethanol solvent. Adjust the pH of the impregnation solution to 4 to obtain the impregnation solution. Immerse the pretreated fabric in the impregnation solution and stir at 80°C for 30 minutes. S3: Remove the fabric, control the liquid carry-over rate at 60% using a rolling mill, and bake at 170°C for 5 minutes to obtain the responsive antibacterial polyester fabric. Example 3

[0026] 4 kg of 2,2-dimethylpropiolactone was added to the reactor and cooled to 5°C using a refrigeration unit. Then, 2 kg of 33 wt% methylamine ethanol solution was added to the reactor, and the mixture was heated to 78°C and refluxed for 20 hours to obtain the crude product.

[0027] The crude product was transferred to a crystallization vessel and dissolved in ethyl acetate at 60°C. The mixture was cooled to 5°C and allowed to stand to precipitate crystals. The crystals were then dried under vacuum to obtain the intermediate product. Under a nitrogen atmosphere at 0°C, 1.0 kg of the intermediate, 0.4 kg of 2-bromo-2-methylpropanol, 0.06 kg of N,N'-dicyclohexylcarbodiimide, and 0.04 kg of 4-dimethylaminopyridine were added sequentially, followed by the addition of dichloromethane to dissolve the crystals completely. The reaction proceeded for 6 hours to obtain a solid-liquid product. After the reaction was complete, the solid-liquid product was pumped into a filter press for filtration, and the filtrate was collected. The filtrate rich in the product was concentrated in a rotary evaporator to obtain an oily product. The separated organic phase was dried with anhydrous magnesium sulfate for 30 minutes. The desiccant was removed by filtration, and the filtrate was concentrated under reduced pressure to obtain the antibacterial compound.

[0028] Preparation of responsive antibacterial polyester fabrics: S1. Clean the fabric with a weakly alkaline detergent solution to remove spinning oils and dirt. Treat with a 1.5% wt NaOH solution at 80°C for 60 minutes, wash thoroughly with deionized water until neutral, and then dry to obtain the pretreated fabric. S2. Dissolve 3% (by mass) of antibacterial compound and 2% (by mass) of γ-(2,3-epoxypropoxy)propyltrimethoxysilane in an ethanol solvent. Adjust the pH of the impregnation solution to 5. Immerse the pretreated fabric in the impregnation solution and stir at 80°C for 60 minutes. S3. Remove the fabric, control the liquid carry-over rate at 70% using a rolling mill, and bake at 170°C for 8 minutes to obtain the responsive antibacterial polyester fabric.

[0029] Comparative Example 1: The performance of the polyester fabric was tested using commercially available antibacterial polyester fabric.

[0030] Comparative Example 2, compared to Example 1, replaced 2-bromo-2-methylpropanol with 1-bromoalkane. The 7-membered ring structure was used to verify enzyme-triggered ring-opening and self-cleaning properties.

[0031] Performance testing: (Example 1) Regeneration performance testing 100 mg of the compound obtained in Example 1 was dissolved in 10 mL of phosphate buffer at pH 7.4, and 1 mg / mL porcine liver esterase was added. The mixture was incubated in a 37°C water bath with a shaker for 4 hours. HPLC monitoring was performed until the starting peak (Rt = 8.5 min) completely disappeared, indicating complete ring-opening. The resulting solution was freeze-dried to obtain the ring-opened product.

[0032] The ring-opening product was soaked in acetic acid for 20 h in a 10 mL solution with a bath ratio of 1:20 and allowed to stand at room temperature. HPLC monitoring showed that the peak area recovery of the starting material was measured after 6 hours.

[0033] Antibacterial properties: Refer to GB / T 20944.3-2008 (shaking method). Results: The antibacterial rate against Staphylococcus aureus was 96.21%, and the antibacterial rate against Escherichia coli was 94.1%. The lower of the two antibacterial rates was taken.

[0034] Cleanliness validation: The results of the "plate count method" test were obtained, using raw polyester as a control sample. The concentration of E. coli adhering to the raw polyester and the concentration of E. coli adhering to the antibacterial polyester after alkaline treatment were measured. The results were calculated by comparing the difference with the concentration of E. coli adhering to the raw polyester.

[0035] Wash fastness: After 50 accelerated washes according to AATCC 135 standard, the antibacterial rate of the fabric remained at 96%. Test results and data are shown in Table 1. Table 1

[0036] As shown in Table 1, the regeneration performance of Examples 1-3 is approximately 70%, indicating that after enzyme-triggered ring-opening, the compounds can effectively restore the original antibacterial structure and achieve functional regeneration under acidic conditions. This verifies the "sterilization-ring-opening-self-cleaning-regeneration" cycle mechanism.

[0037] Comparative Examples 1 and 2: Regeneration performance was not tested because Comparative Example 1 (commercially available antibacterial polyester) lacked a ring-opening design, and Comparative Example 2 (acyclic reaction) did not form a seven-membered ring structure, thus making regeneration impossible.

[0038] Antibacterial rate: Examples 1-3: The antibacterial rate is higher than 92% (92.5%-94.5%), which meets the requirements for medical antibacterial use.

[0039] Comparative Example 1: The antibacterial rate was high (96.3%), but the wash fastness was poor (88%), indicating that the antibacterial agent was easily lost, mainly due to the durability problem of inorganic antibacterial agents or small molecule organic antibacterial agents.

[0040] Comparative Example 2: The antibacterial rate was low (88.2%), due to the lack of responsiveness of the compound caused by non-cyclization, resulting in a decrease in bactericidal efficiency.

[0041] Cleaning performance: Examples 1-3: The cleaning performance is as high as 96%-98%, proving that the compound forms an amphoteric structure under the triggering of esterase, producing a superhydrophilic surface that can effectively wash away bacterial carcasses.

[0042] Comparative Example 2: Due to the non-circular structure, self-cleaning is not possible, and the presence of bacterial carcasses leads to performance degradation.

[0043] Wash fastness: Examples 1-3 and Comparative Example 2 all showed a wash fastness of 96%, indicating that the compound forms covalent bonds or strong hydrogen bonds with the polyester matrix through carboxyl groups, providing strong anchoring and resistance to repeated washing.

[0044] Comparative Example 1: The wash fastness was low (88%), indicating that the antibacterial agent in commercially available products is easily lost during washing, affecting its long-lasting effect.

[0045] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and variations can be made to these embodiments without departing from the principles and spirit of the invention.

Claims

1. A method for preparing a responsive antibacterial polyester fabric, characterized in that, The preparation method includes the following steps: S1: Surface activation treatment of ester groups in hydrolyzed polyester fabric; S2: Apply the finishing solution of antibacterial compound and coupling agent to the polyester fabric treated in step S1; S3: The polyester fabric treated in S2 is subjected to rolling and baking treatments to obtain the responsive antibacterial polyester fabric. The antibacterial compound has the following structure: .

2. The method for preparing the responsive antibacterial polyester fabric according to claim 1, characterized in that, The method for preparing the antibacterial compound includes the following steps: Step 1: 2,2-Dimethylpropiolactone reacts with methylamine to yield an intermediate compound; Step 2: Under an inert atmosphere, at 0~25℃, the catalyst, condensing agent, 2-bromo-2-methylpropanol, and the intermediate compound obtained in Step 1 are dissolved in a solvent to carry out a cyclization reaction, and the antibacterial compound is obtained after purification; the catalyst in Step 2 is one of 4-dimethylaminopyridine and N-methylimidazole; the condensing agent is one of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and N,N'-dicyclohexylcarbodiimide.

3. The method for preparing the responsive antibacterial polyester fabric according to claim 2, characterized in that, In step two, 2-bromo-2-methylpropanol and the intermediate compound are mixed at a mass ratio of (0.8~1.5):

2.

4. The method for preparing the responsive antibacterial polyester fabric according to claim 1, characterized in that, The responsive antibacterial polyester fabric is made from one or more of polyethylene terephthalate, polyethylene terephthalate, polyethylene isophthalate, and polyethylene adipate.

5. The method for preparing the responsive antibacterial polyester fabric according to claim 1, characterized in that, The antibacterial compound is present in an amount of 0.1 to 3.0% of the polyester raw material.

6. The method for preparing the responsive antibacterial polyester fabric according to claim 1, characterized in that, The rolling process controls the liquid retention rate of the responsive antibacterial polyester fabric to be 60-70%.

7. The method for preparing the responsive antibacterial polyester fabric according to claim 1, characterized in that, The baking process is carried out at a temperature of 150-170°C for 3-8 minutes.

Images