Preparation method of antibacterial modified fiber for textile fabric

Abstract

The present invention relates to the field of fiber technology, and discloses a preparation method of an antibacterial modified fiber for textile fabrics. In the present invention, nylon 6 and copper-tea polyphenol-based hyperbranched polyamide are added to formic acid. After stirring, electrospinning is carried out by an electrospinning machine to obtain an antibacterial modified fiber for textile fabrics. The hyperbranched polyamide has good compatibility with nylon 6 and contains a three-dimensional dendritic hyperbranched molecular chain, which has a good toughening effect on nylon 6 fibers. While improving the fiber elongation at break, the fiber also maintains good breaking strength. The copper-tea polyphenol-based hyperbranched polyamide contains tea polyphenol active antibacterial substances and antibacterial copper ions, significantly improving the antibacterial performance of the fiber. At the same time, the copper ions form a tight and firm coordination with tea polyphenols and catechol-based hyperbranched polyamide, and it is difficult for the copper ions and tea polyphenols to be eluted from the fiber matrix, so that the fiber still maintains excellent antibacterial performance.

Description

Technical Field

[0001] The present invention relates to the technical field of fibers, and specifically to a preparation method of an antibacterial modified fiber for textile fabrics. Background Art

[0002] Nylon fibers are widely used in textile fabrics, clothing, etc. With the continuous improvement of people's living standards, there is a higher demand for high-end textiles and clothing, and antibacterial fabric products have emerged. Usually, antibacterial agents are added to fibers to make antibacterial textile fabrics. Traditional antibacterial agents include inorganic antibacterial agents such as copper ions and nano silver, and natural antibacterial agents such as tea polyphenols and chitosan.

[0003] Tea polyphenols contain rich substances such as catechins, anthocyanins, and flavonoids, have good biocompatibility, and excellent antibacterial properties, and have important applications in fibers, textiles, dressings, plastics, etc. Chinese patent application document CN116479655A discloses a preparation method of a biomass antibacterial modified polyester fabric. The hydroxyl-modified polyester fabric and acyl chloride-functionalized cellulose are reacted, and then reacted with a tea polyphenol-copper complex to obtain an antibacterial modified polyester fabric with good antibacterial effect. However, the preparation methods of the hydroxyl-modified polyester fabric and acyl chloride-functionalized cellulose in this patent are relatively complex, and the mechanical properties of the fibers and their fabrics are not improved. Summary of the Invention

[0004] The present invention provides an antibacterial modified fiber for textile fabrics, which solves the problems of poor mechanical properties and antibacterial properties of nylon fibers.

[0005] The technical solution of the present invention is: a preparation method of an antibacterial modified fiber for textile fabrics:

[0006] (1) In an ice-water bath, tris(2-aminoethyl)amine and a diacyl chloride compound are added to N,N-dimethylformamide, and polymerization reaction is carried out with stirring in a nitrogen atmosphere. Then 3,4-dihydroxybenzaldehyde is added, glacial acetic acid is dropped, and Schiff base reaction is carried out with stirring. The solution is poured into ethanol, filtered by suction, washed successively with ethanol and water, and dried to obtain a catechol-based hyperbranched polyamide. The reaction formula is:

[0007]

[0008] (2) Catechol-based hyperbranched polyamide is added to N,N-dimethylformamide, and after stirring, tea polyphenols, copper salt, and water are added, and reaction is carried out with stirring. The solution is poured into ethanol, filtered by suction, washed successively with ethanol and water, and dried to obtain a copper-tea polyphenol-based hyperbranched polyamide. The reaction formula is:

[0009]

[0010] (3) Add nylon 6 and copper - tea polyphenol - based hyperbranched polyamide with a mass ratio of 100:(1 - 4) to formic acid. After stirring, inject it into a syringe and perform electrospinning through an electrospinning machine. Control the voltage at 14 - 18 kV, the flow rate at 0.2 - 0.6 mL / h, and the receiving distance at 15 - 20 cm to obtain antibacterial modified fibers for textile fabrics.

[0011] Further, the molar ratio of tris(2 - aminoethyl)amine, diacyl chloride compound, and 3,4 - dihydroxybenzaldehyde in (1) is (0.68 - 0.72):1:(0.04 - 0.12).

[0012] Further, the diacyl chloride compound is terephthaloyl chloride, isophthaloyl chloride, or [1,1'-biphenyl]-4,4'-dicarbonyl chloride.

[0013] Further, the polymerization reaction in (1) is carried out at 20 - 25 °C for 18 - 24 h, and the Schiff base reaction is carried out at 50 - 70 °C for 6 - 10 h.

[0014] Further, the mass ratio of catechol - based hyperbranched polyamide, tea polyphenols, and copper salt in (2) is 100:(7 - 22):(2 - 7).

[0015] Further, the copper salt is cuprous chloride or copper sulfate.

[0016] Further, the reaction in (2) is carried out at 50 - 65 °C for 7 - 12 h.

[0017] The technical effects of the present invention: Tea polyphenols contain rich bioactive antibacterial components such as catechins and anthocyanins, and contain catechol groups. The present invention utilizes the coordination of the catechol groups of catechol - based hyperbranched polyamide and tea polyphenols with copper ions to obtain copper - tea polyphenol - based hyperbranched polyamide, and then performs electrospinning with nylon 6 to obtain antibacterial modified fibers for textile fabrics. The main chain of the hyperbranched polyamide molecule contains the same amide bond structural unit as nylon 6 polyamide, has good compatibility with nylon 6, and at the same time contains a three - dimensional dendritic hyperbranched molecular chain, which forms a physical entanglement with the nylon 6 molecular chain, has a good toughening effect on nylon 6 fibers, and while increasing the fiber elongation at break, also enables the fiber to maintain good breaking strength.

[0018] The copper-tea polyphenol-based hyperbranched polyamide of the present invention contains tea polyphenol active antibacterial substances and antibacterial copper ions, significantly improving the antibacterial performance of the fiber. At the same time, the copper ions form a tight and firm coordination with the tea polyphenols and the catechol groups in the catechol-based hyperbranched polyamide. Since the hyperbranched polyamide is a macromolecular polymer and it is difficult to migrate and elute from the fiber matrix, and the strong coordination among the copper ions, tea polyphenols, and catechol-based hyperbranched polyamide makes it difficult for the copper ions and tea polyphenols to elute from the fiber matrix even after multiple washings, so that the fiber still maintains excellent antibacterial performance. Detailed implementation manners

[0019] The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, these embodiments are provided to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0020] Nylon 6, model number J2700, Ningbo Senhong Plastic Co., Ltd. Tea polyphenols, with an effective ingredient content of 99%, Xi'an Musen Bioengineering Co., Ltd.

[0021] Example 1: Preparation of antibacterial modified fibers for textile fabrics.

[0022] (1) In an ice-water bath, 3.6 mol of tris(2-aminoethyl)amine and 5 mol of terephthaloyl chloride were added to 140 mL of N,N-dimethylformamide. Under a nitrogen atmosphere, the polymerization reaction was carried out with stirring at 20 °C for 24 h. Then, 0.2 mol of 3,4-dihydroxybenzaldehyde was added, and 0.16 mL of glacial acetic acid was added dropwise. The Schiff base reaction was carried out with stirring at 60 °C for 6 h. The solution was poured into ethanol, filtered by suction, washed successively with ethanol and water, and dried to obtain catechol-based hyperbranched polyamide.

[0023] (2) 3 g of catechol-based hyperbranched polyamide was added to 30 mL of N,N-dimethylformamide. After stirring, 0.21 g of tea polyphenols, 0.06 g of cuprous chloride, and 5 mL of water were added. The coordination reaction was carried out with stirring at 50 °C for 10 h. The solution was poured into ethanol, filtered by suction, washed successively with ethanol and water, and dried to obtain copper-tea polyphenol-based hyperbranched polyamide.

[0024] (3) 100 g of nylon 6 and 1 g of copper-tea polyphenol-based hyperbranched polyamide were added to 500 mL of formic acid. After stirring, it was injected into a syringe and spun by an electrospinning machine. The voltage was controlled at 14 kV, the flow rate was 0.6 mL / h, and the receiving distance was 20 cm to obtain antibacterial modified fibers for textile fabrics.

[0025] Example 2: Preparation of antibacterial modified fibers for textile fabrics.

[0026] (1) In an ice-water bath, 3.4 mol of tris(2-aminoethyl)amine and 5 mol of [1,1'-biphenyl]-4,4'-dicarbonyl chloride were added to 180 mL of N,N-dimethylformamide. Under a nitrogen atmosphere, the polymerization reaction was carried out with stirring at 25 °C for 18 h. Then, 0.4 mol of 3,4-dihydroxybenzaldehyde was added, and 0.35 mL of glacial acetic acid was added dropwise. The Schiff base reaction was carried out with stirring at 70 °C for 6 h. The solution was poured into ethanol, filtered by suction, washed successively with ethanol and water, and dried to obtain catechol-based hyperbranched polyamide.

[0027] (2) 3 g of catechol-based hyperbranched polyamide was added to 40 mL of N,N-dimethylformamide. After stirring, 0.44 g of tea polyphenols, 0.14 g of copper chloride, and 8 mL of water were added. The coordination reaction was carried out with stirring at 65 °C for 7 h. The solution was poured into ethanol, filtered by suction, washed successively with ethanol and water, and dried to obtain copper-tea polyphenol-based hyperbranched polyamide.

[0028] (3) 100 g of nylon 6 and 2.5 g of copper-tea polyphenol-based hyperbranched polyamide were added to 560 mL of formic acid. After stirring, the mixture was injected into a syringe and spun by an electrospinning machine. The voltage was controlled at 14 kV, the flow rate was 0.3 mL / h, and the receiving distance was 20 cm to obtain antibacterial modified fibers for textile fabrics.

[0029] Example 3: Preparation of antibacterial modified fibers for textile fabrics.

[0030] (1) In an ice-water bath, 3.6 mol of tris(2-aminoethyl)amine and 5 mol of isophthaloyl chloride were added to 180 mL of N,N-dimethylformamide. Under a nitrogen atmosphere, the polymerization reaction was carried out with stirring at 20 °C for 24 h. Then, 0.6 mol of 3,4-dihydroxybenzaldehyde was added, and 0.5 mL of glacial acetic acid was added dropwise. The Schiff base reaction was carried out with stirring at 50 °C for 10 h. The solution was poured into ethanol, filtered by suction, washed successively with ethanol and water, and dried to obtain catechol-based hyperbranched polyamide.

[0031] (2) 3 g of catechol-based hyperbranched polyamide was added to 40 mL of N,N-dimethylformamide. After stirring, 0.66 g of tea polyphenols, 0.21 g of copper sulfate, and 8 mL of water were added. The coordination reaction was carried out with stirring at 60 °C for 12 h. The solution was poured into ethanol, filtered by suction, washed successively with ethanol and water, and dried to obtain copper-tea polyphenol-based hyperbranched polyamide.

[0032] (3) 100 g of nylon 6 and 4 g of copper-tea polyphenol-based hyperbranched polyamide were added to 600 mL of formic acid. After stirring, the mixture was injected into a syringe and spun by an electrospinning machine. The voltage was controlled at 18 kV, the flow rate was 0.2 mL / h, and the receiving distance was 15 cm to obtain antibacterial modified fibers for textile fabrics.

[0033] Comparative Example 1: The difference between this comparative example and Example 1 is that copper-tea polyphenol-based hyperbranched polyamide is not added.

[0034] (1) Add 100 g of nylon 6 to 500 mL of formic acid, stir and inject it into a syringe, and perform electrospinning through an electrospinning machine, controlling the voltage at 14 kV, the flow rate at 0.6 mL / h, and the receiving distance at 20 cm to obtain textile fabric fibers.

[0035] Comparative Example 2: The difference between this comparative example and Example 1 is that catechol-based hyperbranched polyamide is used instead of copper-tea polyphenol-based hyperbranched polyamide.

[0036] (1) Add 100 g of nylon 6 and 1 g of catechol-based hyperbranched polyamide to 500 mL of formic acid, stir and inject it into a syringe, and perform electrospinning through an electrospinning machine, controlling the voltage at 14 kV, the flow rate at 0.6 mL / h, and the receiving distance at 20 cm to obtain textile fabric fibers.

[0037] Comparative Example 3: The difference between this comparative example and Example 1 is that tea polyphenols are not added when preparing copper-based hyperbranched polyamide.

[0038] (1) Add 3 g of catechol-based hyperbranched polyamide to 30 mL of N,N-dimethylformamide, stir and then add 0.06 g of cuprous chloride and 5 mL of water, stir and react at 50 °C for 10 h, pour the solution into ethanol, filter by suction, wash successively with ethanol and water, and dry to obtain copper-based hyperbranched polyamide.

[0039] (2) Add 100 g of nylon 6 and 1 g of copper-based hyperbranched polyamide to 500 mL of formic acid, stir and inject it into a syringe, and perform electrospinning through an electrospinning machine, controlling the voltage at 14 kV, the flow rate at 0.6 mL / h, and the receiving distance at 20 cm to obtain antibacterial modified fibers for textile fabrics.

[0040] Comparative Example 4: The main difference between this comparative example and Example 1 is that cuprous chloride is not added when preparing tea polyphenol-based hyperbranched polyamide.

[0041] (1) Add 3 g of catechol-based hyperbranched polyamide to 30 mL of N,N-dimethylformamide, stir and then add 0.21 g of tea polyphenols and 5 mL of water, mix at 50 °C for 10 h, and dry to remove N,N-dimethylformamide to obtain tea polyphenol-based hyperbranched polyamide.

[0042] (2) Add 100 g of nylon 6 and 1 g of tea polyphenol-based hyperbranched polyamide to 500 mL of formic acid, stir and inject it into a syringe, and perform electrospinning through an electrospinning machine, controlling the voltage at 14 kV, the flow rate at 0.6 mL / h, and the receiving distance at 20 cm to obtain antibacterial modified fibers for textile fabrics.

[0043] Comparative Example 5: The main difference between this comparative example and Example 1 is that when preparing the copper-tea polyphenol-based hyperbranched polyamide, hyperbranched polyamide is used instead of catechol-based hyperbranched polyamide.

[0044] (1) In an ice-water bath, 3.6 mol of tris(2-aminoethyl)amine and 5 mol of terephthaloyl chloride were added to 140 mL of N,N-dimethylformamide. Under a nitrogen atmosphere, the polymerization reaction was carried out with stirring at 20 °C for 24 h. The solution was poured into ethanol, filtered by suction, washed successively with ethanol and water, and dried to obtain hyperbranched polyamide.

[0045] (2) 3 g of hyperbranched polyamide was added to 30 mL of N,N-dimethylformamide. After stirring, 0.21 g of tea polyphenols, 0.06 g of copper chloride, and 5 mL of water were added. The coordination reaction was carried out with stirring at 50 °C for 10 h. The solution was poured into ethanol, filtered by suction, and dried to obtain copper-tea polyphenol-based hyperbranched polyamide.

[0046] (3) 100 g of nylon 6 and 1 g of copper-tea polyphenol-based hyperbranched polyamide were added to 500 mL of formic acid. After stirring, it was injected into a syringe and spun by an electrospinning machine. The voltage was controlled at 14 kV, the flow rate was 0.6 mL / h, and the receiving distance was 20 cm to obtain antibacterial modified fibers for textile fabrics.

[0047] The tensile fracture properties were tested according to the national standard GB / T 14337-2022.

[0048] The antibacterial properties were tested according to the national standard GB / T 20944.3-2008. The fibers were washed and dried 50 times according to the national standard GB / T 8629-2017. Then the antibacterial properties were tested again. Antibacterial rate = (W t -Q t ) / W t × 100%. W t is the average value of the viable bacteria concentration after 18 h of oscillating contact with the control sample (Comparative Example 1). Q t is the average value of the viable bacteria concentration after 18 h of oscillating contact with the antibacterial sample. Each group of specimens was tested 3 times and the average value was taken.

[0049] Table 1

[0050]

[0051] Table 2

[0052]

[0053] After testing, compared with Comparative Example 1, copper-tea polyphenol-based hyperbranched polyamide was added to the nylon fibers in Examples 1-3. Its molecular main chain contains an amide bond structural unit identical to that of nylon 6 polyamide, and it has good compatibility with nylon 6. At the same time, it contains a three-dimensional dendritic hyperbranched molecular chain, which forms a physical entanglement with the nylon 6 molecular chain, and has a good toughening effect on nylon 6 fibers. While increasing the fiber elongation at break, the fiber also maintains good breaking strength. And it contains tea polyphenol active antibacterial substances and antibacterial copper ions, significantly improving the antibacterial performance of the fiber. At the same time, copper ions form a tight and firm coordination interaction with tea polyphenols and catechol groups in the catechol-based hyperbranched polyamide. Since the hyperbranched polyamide is a macromolecular polymer, it is difficult to migrate and elute from the fiber matrix. And the strong coordination interaction formed by copper ions, tea polyphenols, and catechol-based hyperbranched polyamide makes it difficult for copper ions and tea polyphenols to elute from the fiber matrix after multiple washes, so that the fiber still maintains excellent antibacterial performance.

[0054] The catechol-based hyperbranched polyamide of Comparative Example 2 does not contain tea polyphenols and copper ions. When added to nylon 6 fibers, it cannot effectively improve the antibacterial performance of the fibers.

[0055] The copper-based hyperbranched polyamide prepared in Comparative Example 3 does not contain tea polyphenols, resulting in a lower antibacterial performance of nylon 6 fibers. Copper ions form a stable coordination interaction with the catechol structure of the hyperbranched polyamide. After multiple washes, it is difficult for copper ions to migrate and elute, and the fiber still maintains good antibacterial rate and antibacterial performance.

[0056] When preparing the tea polyphenol-based hyperbranched polyamide in Comparative Example 4, cuprous chloride was not added and it does not contain antibacterial copper ions, so the antibacterial performance of nylon 6 fibers is lower. And tea polyphenols and hyperbranched polyamide cannot form a stable and firm interaction. After the fiber is washed multiple times, tea polyphenols are easily eluted, resulting in a significant decrease in the antibacterial rate of the fiber.

[0057] The hyperbranched polyamide of Comparative Example 5 does not contain catechol groups and cannot form a coordination interaction with tea polyphenols and copper ions. After multiple washes, tea polyphenols and copper ions are easily migrated and eluted, resulting in a significant decrease in the antibacterial rate of the fiber.

[0058] The above is only a preferred specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Any changes or substitutions that can be easily thought of by those skilled in the art within the technical scope disclosed by the present invention should be covered by the protection scope of the present invention. Therefore, the protection scope of the present invention should be subject to the protection scope of the claims.

Claims

1. A method for preparing antibacterial modified fibers for textile fabrics, characterized in that: The preparation method is: (1) In an ice water bath, tris(2-aminoethyl)amine and a diacyl chloride compound are added to N,N-dimethylformamide, and the mixture is stirred in a nitrogen atmosphere to carry out a polymerization reaction. Then, 3,4-dihydroxybenzaldehyde is added, glacial acetic acid is added dropwise, and the mixture is stirred to carry out a Schiff base reaction. The solution is poured into ethanol, filtered, washed, and dried to obtain a catechol-based hyperbranched polyamide. (2) adding catechol-based hyperbranched polyamide to N,N-dimethylformamide, adding tea polyphenols, copper salt, and water after stirring, stirring to react, pouring the solution into ethanol, filtering, washing, and drying to obtain copper-tea polyphenol-based hyperbranched polyamide; (3) Add nylon 6 and copper-tea polyphenol-based hyperbranched polyamide to formic acid, stir and inject into a syringe, and spin through an electrospinning machine to obtain antibacterial modified fibers for textile fabrics.

2. The method for preparing antibacterial modified fiber for textile fabrics according to claim 1, characterized in that: The molar ratio of tris(2-aminoethyl)amine, diacyl chloride compound and 3,4-dihydroxybenzaldehyde in (1) is (0.68-0.72):1:(0.04-0.12).

3. The method for preparing antibacterial modified fiber for textile fabrics according to claim 2, characterized in that: The diacyl chloride compound is terephthaloyl chloride, isophthaloyl chloride or [1,1'-biphenyl]-4,4'-diacyl chloride.

4. The method for preparing antibacterial modified fiber for textile fabrics according to claim 1, characterized in that: The polymerization reaction in (1) is carried out at 20-25°C for 18-24 hours, and the Schiff base reaction is carried out at 50-70°C for 6-10 hours.

5. The method for preparing antibacterial modified fiber for textile fabrics according to claim 1, characterized in that: The mass ratio of catechol-based hyperbranched polyamide, tea polyphenols and copper salt in (2) is 100:(7-22):(2-7).

6. The method for preparing antibacterial modified fiber for textile fabrics according to claim 5, characterized in that: The copper salt is cuprous chloride or copper sulfate.

7. The method for preparing antibacterial modified fiber for textile fabrics according to claim 1, characterized in that: The reaction in (2) is carried out at 50-65°C for 7-12 hours.

8. The method for preparing antibacterial modified fiber for textile fabrics according to claim 1, characterized in that: The mass ratio of nylon 6 and copper-tea polyphenol-based hyperbranched polyamide in (3) is 100:(1-4).

9. The method for preparing antibacterial modified fiber for textile fabrics according to claim 1, characterized in that: The voltage during spinning in (3) is 14-18 kV, the flow rate is 0.2-0.6 mL / h, and the receiving distance is 15-20 cm.

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