Antibacterial fiber and manufacturing process
By preparing succinate-based lactate-modified nano-titanium dioxide blended with polylactic acid and then using electrospinning technology to prepare antibacterial fibers, the problems of low antibacterial performance and poor mechanical properties of polylactic acid fibers were solved, achieving high-efficiency antibacterial properties and improved mechanical properties of the fibers.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- TIANJIN YIKANG CENTURY ANTIBACTERIAL NEW MATERIAL TECH CO LTD
- Filing Date
- 2026-02-12
- Publication Date
- 2026-06-12
Smart Images
Figure SMS_3 
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Abstract
Description
Technical Field
[0001] This invention relates to the field of fiber technology, specifically to an antibacterial fiber and its preparation process. Background Technology
[0002] Polylactic acid (PLA) and its fiber products are widely used in clothing fabrics and medical supplies due to their good biocompatibility, environmental friendliness, biodegradability, and excellent thermal stability. To better utilize PLA fibers in medical applications such as wound dressings, it is necessary to improve their antibacterial and mechanical properties. A common method is to add antibacterial agents, such as nano-silver and nano-titanium dioxide. Among these, nano-titanium dioxide exhibits strong photocatalytic properties, excellent antibacterial performance, and high mechanical strength, making it important for applications in fibers and plastics.
[0003] Improving the dispersibility of nano-titanium dioxide can enhance its antibacterial and other properties. Patent application CN119433752A discloses grafting polylactic acid and PLA-TiO2-N / SiO2 onto titanium dioxide, resulting in polylactic acid fibers with good UV resistance and heat resistance. However, this patent does not address the issue of poor mechanical properties in polylactic acid fibers. Summary of the Invention
[0004] This invention solves the problem of low antibacterial properties of polylactic acid fibers and improves the mechanical properties of polylactic acid fibers.
[0005] Technical solution: An antibacterial fiber and its preparation process, wherein the antibacterial fiber comprises polylactic acid and modified titanium dioxide in a mass ratio of 100:(1-5);
[0006] The preparation process of antibacterial fibers is as follows:
[0007] (1) Add lactate, succinic anhydride, and 4-dimethylaminopyridine to the reaction solvent. After the reaction, dilute with water and adjust the pH to 3-4 by adding hydrochloric acid solution. After stirring, allow the mixture to stand and separate into layers. Rotary evaporate the organic phase and separate by column chromatography to obtain succinic acid lactate. The reaction formula is:
[0008] .
[0009] (2) Add nano-titanium dioxide to the solvent, disperse it in an ultrasonic instrument, then add succinate-based lactate, stir to modify, filter, wash with ethanol aqueous solution, and dry to obtain modified titanium dioxide.
[0010] (3) Add modified titanium dioxide and polylactic acid to the spinning solvent, stir and disperse, and let stand to degas to obtain spinning solution. Pour into a syringe and spin through an electrostatic spinning machine to obtain antibacterial fiber.
[0011] Preferably, the reaction solvent in (1) is dichloromethane or trichloromethane.
[0012] Preferably, the reaction in (1) is stirred at 20-40℃ for 4-6 hours.
[0013] Preferably, the molar ratio of lactate, succinic anhydride and 4-dimethylaminopyridine in (1) is 1:(1.4-1.8):(0.3-0.4).
[0014] Preferably, the structural formula of the lactate in (1) is as follows: , where a is 1-4.
[0015] Preferably, the solvent in (2) includes any one or a combination of water, ethanol, isopropanol, and toluene.
[0016] Preferably, in (2), the mass ratio of nano-titanium dioxide to succinate-based lactate is 100:(3-8).
[0017] Preferably, the temperature during modification in (2) is 80-100℃ and the time is 3-5h.
[0018] Preferably, the spinning solvent in (3) is any one or more of N,N-dimethylformamide, chloroform, and dichloromethane.
[0019] Preferably, in (3), the voltage during spinning is 18-24kV and the flow rate of the spinning solution is 0.4-1mL / h.
[0020] The beneficial technical effects of this invention are as follows: The carboxyl groups of succinate-based lactate interact with the hydroxyl groups on the surface of nano-titanium dioxide, thereby effectively modifying the surface of the nano-titanium dioxide. Then, it is blended with polylactic acid (PLA) and electrospun to obtain antibacterial fibers. The organically modified titanium dioxide is less prone to agglomeration, exposing more antibacterial sites and further improving the antibacterial rate of the fiber. Simultaneously, the succinate-based lactate contains ester groups and lactate structures similar to PLA, significantly improving the compatibility between nano-titanium dioxide and PLA, ensuring uniform dispersion in the fiber matrix, and enhancing the tensile strength and elongation at break of the PLA fiber, resulting in improved mechanical properties. Detailed Implementation
[0021] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.
[0022] The following polylactic acid (PLA) is model number Haizheng REVODE110, manufactured by Jinan Changyingda Chemical Co., Ltd. The nano-titanium dioxide has an average particle size of 35nm and is manufactured by Shijiazhuang Jinghuang Technology Co., Ltd.
[0023] Example 1:
[0024] (1) Add 3 mmol of methyl lactate (CAS No. 547-64-8), 5.4 mmol of succinic anhydride and 0.9 mmol of 4-dimethylaminopyridine to 15 mL of dichloromethane. Stir the reaction at 20 °C for 6 h. Dilute with water and adjust the pH to 3 by adding 15% hydrochloric acid solution. After stirring, allow the mixture to stand and separate into layers. Evaporate the organic phase by rotary evaporation and separate by silica gel column chromatography. The mobile phase is a mixture of ethyl acetate and petroleum ether to obtain succinate lactate.
[0025] (2) Add 5g of nano titanium dioxide to 70mL of toluene, sonicate in an ultrasonic instrument for 20min, then add 0.22g of succinate lactate, heat to 100℃, stir, reflux and modify for 3h, filter, wash with 80% ethanol aqueous solution, dry, and obtain modified titanium dioxide.
[0026] (3) Add 2g of modified titanium dioxide and 200g of polylactic acid to a mixed solvent of 0.6L N,N-dimethylformamide and 1.4L dichloromethane. After stirring and dispersing, let stand to remove bubbles to obtain a spinning solution. Pour the solution into a syringe and spin it using an electrospinning machine. The spinning voltage is 20kV and the spinning solution flow rate is 0.6mL / h to obtain antibacterial fibers. Collect the fibers on a receiver at a distance of 18cm to form a fiber membrane.
[0027] Example 2:
[0028] (1) Add 3 mmol of butyl lactate (CAS No. 138-22-7), 4.2 mmol of succinic anhydride and 1.2 mmol of 4-dimethylaminopyridine to 15 mL of chloroform. Stir the reaction at 40 °C for 4 h. Dilute with water and adjust the pH to 4 by adding 10% hydrochloric acid solution. After stirring, allow the mixture to stand and separate into layers. Evaporate the organic phase by rotary evaporation and separate by silica gel column chromatography. The mobile phase is a mixture of ethyl acetate and petroleum ether to obtain succinate lactate.
[0029] (2) Add 5g of nano titanium dioxide to a mixed solvent of 50mL ethanol and 20mL water, sonicate for 30min in an ultrasonic instrument, then add 0.4g of succinate-based lactate, heat to 80℃, stir, reflux and modify for 5h, filter, wash with 80% ethanol aqueous solution, and dry to obtain modified titanium dioxide.
[0030] (3) Add 5g of modified titanium dioxide and 200g of polylactic acid to a mixed solvent of 0.6L N,N-dimethylformamide and 1.4L chloroform. After stirring and dispersing, let stand to remove bubbles to obtain a spinning solution. Pour the solution into a syringe and spin it using an electrospinning machine. The spinning voltage is 18kV and the spinning solution flow rate is 1mL / h to obtain antibacterial fibers. Collect the fibers on a receiver at a distance of 18cm to form a fiber membrane.
[0031] Example 3:
[0032] (1) Add 3 mmol of ethyl lactate (CAS No. 97-64-3), 3.9 mmol of succinic anhydride and 1.2 mmol of 4-dimethylaminopyridine to 15 mL of chloroform. Stir the reaction at 30 °C for 6 h. Dilute with water and adjust the pH to 4 by adding 10% hydrochloric acid solution. After stirring, allow the mixture to stand and separate into layers. Evaporate the organic phase by rotary evaporation and separate by silica gel column chromatography. The mobile phase is a mixture of ethyl acetate and petroleum ether to obtain succinate lactate.
[0033] (2) Add 5g of nano titanium dioxide to 70mL of isopropanol, sonicate for 30min in an ultrasonic instrument, then add 0.15g of succinate lactate, heat to 80℃, stir, reflux and modify for 4h, filter, wash with 80% ethanol aqueous solution, dry, and obtain modified titanium dioxide.
[0034] (2) Add 8g of modified titanium dioxide and 200g of polylactic acid to a mixed solvent of 0.6L N,N-dimethylformamide and 1.5L dichloromethane. After stirring and dispersing, let stand to remove bubbles to obtain a spinning solution. Pour the solution into a syringe and spin it using an electrospinning machine. The spinning voltage is 20kV and the spinning solution flow rate is 0.4mL / h to obtain antibacterial fibers. Collect the fibers on a receiver at a distance of 18cm to form a fiber membrane.
[0035] Example 4:
[0036] (1) Add 5g of nano titanium dioxide to 80mL of toluene, sonicate in an ultrasonic instrument for 30min, then add 0.3g of succinate-based lactate (the same preparation process as in Example 1), heat to 100℃, stir, reflux and modify for 3h, filter, wash with 80% ethanol aqueous solution, and dry to obtain modified titanium dioxide.
[0037] (2) Add 10g of modified titanium dioxide and 200g of polylactic acid to a mixed solvent of 0.7L N,N-dimethylformamide and 1.5L chloroform. After stirring and dispersing, let stand to remove bubbles to obtain a spinning solution. Pour the solution into a syringe and spin it through an electrospinning machine. The spinning voltage is 24kV and the spinning solution flow rate is 0.6mL / h to obtain antibacterial fibers. Collect the fibers on a receiver at a distance of 18cm to form a fiber membrane.
[0038] Comparative Example 1: (1) Add 2g of nano titanium dioxide and 200g of polylactic acid to a mixed solvent of 0.6L N,N-dimethylformamide and 1.4L dichloromethane. After stirring and dispersing, let stand to remove bubbles to obtain a spinning solution. Pour the solution into a syringe and spin it through an electrospinning machine. The spinning voltage is 20kV and the spinning solution flow rate is 0.6mL / h to obtain antibacterial fibers. Collect the fibers on a receiver at a distance of 18cm to form a fiber membrane.
[0039] Comparative Example 2: (1) Add 5g of nano titanium dioxide to 70mL of toluene, sonicate for 20min in an ultrasonic instrument, then add 0.22g of methyl lactate, heat to 100℃, stir, reflux and modify for 3h, filter, wash with 80% ethanol aqueous solution, dry, and obtain modified titanium dioxide.
[0040] (2) Add 2g of modified titanium dioxide and 200g of polylactic acid to a mixed solvent of 0.6L N,N-dimethylformamide and 1.4L dichloromethane. After stirring and dispersing, let stand to remove bubbles to obtain a spinning solution. Pour the solution into a syringe and spin it using an electrospinning machine. The spinning voltage is 20kV and the spinning solution flow rate is 0.6mL / h to obtain antibacterial fibers. Collect the fibers on a receiver at a distance of 18cm to form a fiber membrane.
[0041] Comparative Example 3: (1) Add 5g of nano titanium dioxide to 70mL of toluene, ultrasonically disperse it in an ultrasonic instrument for 20min, then add 0.22g of stearic acid, heat to 100℃, stir, condense and reflux for 3h to modify it, filter it and wash it with 80% ethanol aqueous solution, dry it to obtain modified titanium dioxide.
[0042] (2) Add 2g of modified titanium dioxide and 200g of polylactic acid to a mixed solvent of 0.6L N,N-dimethylformamide and 1.4L dichloromethane. After stirring and dispersing, let stand to remove bubbles to obtain a spinning solution. Pour the solution into a syringe and spin it using an electrospinning machine. The spinning voltage is 20kV and the spinning solution flow rate is 0.6mL / h to obtain antibacterial fibers. Collect the fibers on a receiver at a distance of 18cm to form a fiber membrane.
[0043] Comparative Example 4: (1) Add 5g of nano titanium dioxide to 70mL of toluene, disperse it in an ultrasonic instrument for 20min, then add 0.22g of monomethyl succinate (CAS No. 3878-55-5), heat to 100℃, stir, condense and reflux for 3h to modify, filter and wash with 80% ethanol aqueous solution, dry to obtain modified titanium dioxide.
[0044] (2) Add 2g of modified titanium dioxide and 200g of polylactic acid to a mixed solvent of 0.6L N,N-dimethylformamide and 1.4L dichloromethane. After stirring and dispersing, let stand to remove bubbles to obtain a spinning solution. Pour the solution into a syringe and spin it using an electrospinning machine. The spinning voltage is 20kV and the spinning solution flow rate is 0.6mL / h to obtain antibacterial fibers. Collect the fibers on a receiver at a distance of 18cm to form a fiber membrane.
[0045] The antibacterial properties of the fibers were tested according to GB / T 20944.3-2008 standard. The fibers of Examples 1-4 and Comparative Examples 1-4 were used as antibacterial fiber samples.
[0046] Add 2g of modified titanium dioxide and 200g of polylactic acid to a mixed solvent of 0.6L N,N-dimethylformamide and 1.4L dichloromethane. After stirring and dispersing, allow the mixture to stand to remove bubbles to obtain a spinning solution. Pour the solution into a syringe and spin it using an electrospinning machine at a voltage of 20kV and a flow rate of 0.6mL / h to obtain a polylactic acid fiber control sample.
[0047] Antibacterial rate Y = (WQ) / W × 100%, where W is the concentration of viable bacteria (cfu / mL) in the flask after shaking contact with the polylactic acid fiber control sample, and Q is the concentration of viable bacteria (cfu / mL) in the flask after shaking contact with the antibacterial fiber sample.
[0048] The mechanical properties of the fiber membrane were tested using an electronic universal testing machine. The sample size was 50 mm × 8 mm, the distance between the clamps was 10 mm, the tensile rate was 20 mm / min, the test temperature was 25 ℃, the relative humidity was 65%, and each group of samples was tested 5 times, and the average value was taken.
[0049] Table 1 Properties of Fibers and Fiber Membranes
[0050]
[0051] Table 1 shows that the nano-titanium dioxide in Comparative Example 1 is prone to agglomeration, has poor compatibility with polylactic acid (PLA), and exhibits poor dispersibility in PLA fibers, resulting in a low antibacterial rate. Furthermore, the fiber membrane exhibits low tensile strength and elongation at break. Examples 1-4 utilize the interaction between the carboxyl groups of succinate-based lactate and the hydroxyl groups on the surface of nano-titanium dioxide, achieving excellent surface modification. The organically modified titanium dioxide is less prone to agglomeration, exposing more antibacterial sites and further improving the fiber's antibacterial rate. Simultaneously, the succinate-based lactate contains ester groups and lactate structures similar to PLA. This significantly improves the compatibility of nano-titanium dioxide and polylactic acid, allowing them to be uniformly dispersed in the fiber matrix. This greatly enhances the mechanical properties of the fiber, resulting in a significant increase in the tensile strength and elongation at break of the fiber membrane.
[0052] Comparative Example 2: Methyl lactate does not contain carboxyl groups, resulting in poor surface modification of nano-titanium dioxide and low antibacterial rate and mechanical properties of the fibers and fiber membranes.
[0053] Comparative Examples 3 and 4 utilized conventional stearic acid and monomethyl succinate to modify the surface of nano-titanium dioxide. The modification effect of both was lower than that of the succinate-based lactate in the Examples, and the antibacterial rate and mechanical properties of the fibers and fiber membranes were significantly lower than those in Example 1.
[0054] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to the specific implementations described. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims
1. An antibacterial fiber, characterized by, The antibacterial fiber comprises polylactic acid and modified titanium dioxide in a mass ratio of 100:(1-5); The preparation process of antibacterial fiber is as follows: Add modified titanium dioxide and polylactic acid to the spinning solvent, stir and disperse, let stand to degas, and obtain spinning solution. Pour the solution into a syringe and spin it through an electrostatic spinning machine to obtain antibacterial fiber. The preparation process of the modified titanium dioxide is as follows: nano titanium dioxide is added to a solvent, ultrasonically dispersed in an ultrasonic instrument, then succinate lactate is added, stirred and modified, filtered, washed, and dried to obtain modified titanium dioxide. The structural formula of the succinate-based lactylate is , a is 1-4; The mass ratio of nano-titanium dioxide to succinate-based lactate is 100:(3-8). The succinate-based lactate is prepared by the following process: lactate, succinic anhydride, and 4-dimethylaminopyridine are added to the reaction solvent in a molar ratio of 1:(1.4-1.8):(0.3-0.4), and the mixture is stirred at 20-40℃ for 4-6 hours. Water is added for dilution, and hydrochloric acid solution is added dropwise to adjust the pH to 3-4. After stirring, the mixture is allowed to stand and separate into layers. The organic phase is then evaporated by rotary evaporation and separated by column chromatography to obtain the succinate-based lactate. The modification was performed at a temperature of 80-100℃ for 3-5 hours. The structural formula of the lactate ester is , a is 1-4.
2. The antibacterial fiber according to claim 1, characterized by, The solvent includes any one or a combination of water, ethanol, isopropanol, and toluene.
3. The antibacterial fiber according to claim 1, characterized by, The reaction solvent is dichloromethane or trichloromethane.
4. A process for the preparation of an antibacterial fibre as claimed in any one of claims 1 to 3, characterised in that, The preparation process is as follows: Modified titanium dioxide and polylactic acid are added to the spinning solvent, stirred and dispersed, and then allowed to stand to remove bubbles to obtain the spinning solution. The solution is poured into a syringe and spun by an electrostatic spinning machine to obtain antibacterial fibers.
5. The process for the preparation of an antibacterial fiber according to claim 4, characterized in that, The spinning solvent is any one or more of N,N-dimethylformamide, chloroform, and dichloromethane.
6. The preparation process of the antibacterial fiber according to claim 5, characterized in that, The voltage during spinning is 18-24kV, and the flow rate of the spinning solution is 0.4-1mL / h.