Preparation method of antibacterial modified fiber for textile fabric

Abstract

The invention relates to the technical field of fibers, and discloses a preparation method of antibacterial modified fibers for textile fabrics, nylon 6 and copper-tea polyphenol-based hyperbranched polyamide are added into formic acid, the mixture is stirred and then spun by an electrostatic spinning machine, and the antibacterial modified fibers for the textile fabrics are obtained. The hyperbranched polyamide has good compatibility with nylon 6, contains a three-dimensional dendritic hyperbranched molecular chain, has a good toughening effect on nylon 6 fibers, and enables the fibers to maintain good breaking strength while improving the elongation at break of the fibers. The copper-tea polyphenol-based hyperbranched polyamide contains tea polyphenol active antibacterial substances and antibacterial copper ions, so that the antibacterial performance of the fiber is remarkably improved. Meanwhile, the copper ions, the tea polyphenol and the catechol-based hyperbranched polyamide form a tight and firm coordination effect, and the copper ions and the tea polyphenol are also difficult to elute from a fiber matrix, so that the fiber still keeps excellent antibacterial performance.

Description

Technical Field

[0001] The invention relates to the technical field of fibers, in particular to a method for preparing antibacterial modified fibers for textile fabrics. Background Art

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

[0003] Tea polyphenols are rich in catechins, anthocyanins, flavonoids and other substances, have good biocompatibility, and excellent antibacterial properties, and have important applications in fibers, textiles, dressings, plastics, etc. Chinese patent application document CN116479655A discloses a method for preparing biomass antibacterial modified polyester fabrics, in which hydroxyl-modified polyester fabrics and acyl chloride-functionalized cellulose are reacted, and then reacted with tea polyphenol-copper complexes, and the obtained antibacterial modified polyester fabrics have good antibacterial effects. However, the preparation methods of the hydroxyl-modified polyester fabrics and acyl chloride-functionalized cellulose in the patent are relatively complicated, and the mechanical properties of the fibers and fabrics are not improved. Summary of the invention

[0004] The invention provides an antibacterial modified fiber for textile fabrics, which solves the problem that nylon fiber has poor mechanical properties and antibacterial properties.

[0005] The technical solution of the present invention is: a method for preparing antibacterial modified fibers for textile fabrics: (1) In an ice-water bath, add tris(2-aminoethyl)amine and diacyl chloride to N,N-dimethylformamide, stir in a nitrogen atmosphere to carry out polymerization reaction, then add 3,4-dihydroxybenzaldehyde, drop glacial acetic acid, stir to carry out Schiff base reaction, pour the solution into ethanol, filter, wash with ethanol and water in turn, and dry to obtain catechol-based hyperbranched polyamide. The reaction formula is:

[0006] (2) Add catechol-based hyperbranched polyamide to N,N-dimethylformamide, stir, then add tea polyphenols, copper salt, and water, stir to react, pour the solution into ethanol, filter, wash with ethanol and water in turn, and dry to obtain copper-tea polyphenol-based hyperbranched polyamide. The reaction formula is:

[0007] (3) Add nylon 6 and copper-tea polyphenol-based hyperbranched polyamide in a mass ratio of 100:(1-4) to formic acid, inject into a syringe after stirring, and spin through an electrospinning machine with a controlled voltage of 14-18 kV, a flow rate of 0.2-0.6 mL / h, and a receiving distance of 15-20 cm to obtain antibacterial modified fibers for textile fabrics.

[0008] Furthermore, in (1), the molar ratio of tris(2-aminoethyl)amine, diacyl chloride compound, and 3,4-dihydroxybenzaldehyde is (0.68-0.72):1:(0.04-0.12).

[0009] Furthermore, the diacid chloride compound is terephthaloyl chloride, isophthaloyl chloride or [1,1'-biphenyl]-4,4'-diacid chloride.

[0010] Furthermore, 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.

[0011] Furthermore, in (2), the mass ratio of catechol-based hyperbranched polyamide, tea polyphenols and copper salt is 100:(7-22):(2-7).

[0012] Furthermore, the copper salt is cuprous chloride or copper sulfate.

[0013] Furthermore, the reaction in (2) is carried out at 50-65°C for 7-12 hours.

[0014] The technical effect of the present invention is that tea polyphenols contain rich biologically active antibacterial components such as catechins and anthocyanins, and contain catechol groups. The present invention utilizes catechol-based hyperbranched polyamide, the catechol groups of tea polyphenols and copper ions for coordination to obtain copper-tea polyphenol-based hyperbranched polyamide, and then electrostatically spins with nylon 6 to obtain antibacterial modified fibers for textile fabrics. The molecular main chain of the hyperbranched polyamide contains the same amide bond structural unit as nylon 6 polyamide, has good compatibility with nylon 6, and contains three-dimensional dendritic hyperbranched molecular chains, which form a physical entanglement with nylon 6 molecular chains, have a good toughening effect on nylon 6 fibers, and while improving the fiber elongation at break, the fiber also maintains good breaking strength.

[0015] The copper-tea polyphenol-based hyperbranched polyamide of the present invention contains tea polyphenol active antibacterial substances and antibacterial copper ions, which significantly improve the antibacterial properties of the fiber. At the same time, the copper ions form a tight and firm coordination with the catechol groups in the tea polyphenol- and catechol-based hyperbranched polyamides. Since the hyperbranched polyamide is a macromolecular polymer and is difficult to migrate and elute from the fiber matrix, the copper ions, tea polyphenols and catechol-based hyperbranched polyamide form a firm coordination, so that after multiple washings, the copper ions and tea polyphenols are also difficult to elute from the fiber matrix, so that the fiber still maintains excellent antibacterial properties. DETAILED DESCRIPTION

[0016] The present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0017] Nylon 6, model number J2700, Ningbo Senhong Plastics Co., Ltd. Tea polyphenols, active ingredient content 99%. Xi'an Musen Bioengineering Co., Ltd.

[0018] Example 1: Preparation of antibacterial modified fibers for textile fabrics.

[0019] (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, and the polymerization reaction was carried out with stirring at 20°C for 24 h in a nitrogen atmosphere. 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, washed with ethanol and water in sequence, and dried to obtain catechol-based hyperbranched polyamide.

[0020] (2) Add 3 g of catechol-based hyperbranched polyamide to 30 mL of N,N-dimethylformamide, stir, then add 0.21 g of tea polyphenols, 0.06 g of cuprous chloride, and 5 mL of water. Stir at 50 °C for coordination reaction for 10 h. Pour the solution into ethanol, filter, wash with ethanol and water in turn, and dry to obtain copper-tea polyphenol-based hyperbranched polyamide.

[0021] (3) Add 100 g of nylon 6 and 1 g of copper-tea polyphenol-based hyperbranched polyamide to 500 mL of formic acid, stir and inject into a syringe, and spin through an electrospinning machine with a controlled voltage of 14 kV, a flow rate of 0.6 mL / h, and a receiving distance of 20 cm to obtain antibacterial modified fibers for textile fabrics.

[0022] Example 2: Preparation of antibacterial modified fibers for textile fabrics.

[0023] (1) In an ice-water bath, 3.4 mol of tris(2-aminoethyl)amine and 5 mol of [1,1'-biphenyl]-4,4'-diacid chloride were added to 180 mL of N,N-dimethylformamide, and the mixture was stirred at 25°C for polymerization for 18 h in a nitrogen atmosphere. Then, 0.4 mol of 3,4-dihydroxybenzaldehyde was added, and 0.35 mL of glacial acetic acid was added dropwise. The mixture was stirred at 70°C for Schiff base reaction for 6 h. The solution was poured into ethanol, filtered, washed with ethanol and water in sequence, and dried to obtain catechol-based hyperbranched polyamide.

[0024] (2) Add 3 g of catechol-based hyperbranched polyamide to 40 mL of N,N-dimethylformamide, stir, then add 0.44 g of tea polyphenols, 0.14 g of cuprous chloride, and 8 mL of water. Stir at 65 °C for coordination reaction for 7 h. Pour the solution into ethanol, filter, wash with ethanol and water in turn, and dry to obtain copper-tea polyphenol-based hyperbranched polyamide.

[0025] (3) Add 100 g of nylon 6 and 2.5 g of copper-tea polyphenol-based hyperbranched polyamide to 560 mL of formic acid, stir and inject into a syringe, and spin through an electrospinning machine with a controlled voltage of 14 kV, a flow rate of 0.3 mL / h, and a receiving distance of 20 cm to obtain antibacterial modified fibers for textile fabrics.

[0026] Example 3: Preparation of antibacterial modified fibers for textile fabrics.

[0027] (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, and the polymerization reaction was carried out with stirring at 20°C for 24 h in a nitrogen atmosphere. 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, washed with ethanol and water in sequence, and dried to obtain catechol-based hyperbranched polyamide.

[0028] (2) Add 3 g of catechol-based hyperbranched polyamide to 40 mL of N,N-dimethylformamide, stir, then add 0.66 g of tea polyphenols, 0.21 g of copper sulfate, and 8 mL of water. Stir at 60 °C for coordination reaction for 12 h. Pour the solution into ethanol, filter, wash with ethanol and water in turn, and dry to obtain copper-tea polyphenol-based hyperbranched polyamide.

[0029] (3) Add 100 g of nylon 6 and 4 g of copper-tea polyphenol-based hyperbranched polyamide to 600 mL of formic acid, stir and inject into a syringe, and spin through an electrospinning machine with a controlled voltage of 18 kV, a flow rate of 0.2 mL / h, and a receiving distance of 15 cm to obtain antibacterial modified fibers for textile fabrics.

[0030] Comparative Example 1: The difference between this comparative example and Example 1 is that copper-tea polyphenol-based hyperbranched polyamide is not added.

[0031] (1) Add 100 g of nylon 6 to 500 mL of formic acid, stir and inject into a syringe, and spin through an electrospinning machine with a controlled voltage of 14 kV, a flow rate of 0.6 mL / h, and a receiving distance of 20 cm to obtain textile fabric fibers.

[0032] 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.

[0033] (1) Add 100 g of nylon 6 and 1 g of catechol-based hyperbranched polyamide to 500 mL of formic acid, stir and inject into a syringe, and spin through an electrospinning machine with a controlled voltage of 14 kV, a flow rate of 0.6 mL / h, and a receiving distance of 20 cm to obtain textile fabric fibers.

[0034] Comparative Example 3: The difference between this comparative example and Example 1 is that tea polyphenols are not added when preparing the copper-based hyperbranched polyamide.

[0035] (1) Add 3 g of catechol-based hyperbranched polyamide to 30 mL of N,N-dimethylformamide, stir, 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, wash with ethanol and water in turn, and dry to obtain copper-based hyperbranched polyamide.

[0036] (2) Add 100 g of nylon 6 and 1 g of copper-based hyperbranched polyamide to 500 mL of formic acid, stir and inject into a syringe, and spin through an electrospinning machine with a controlled voltage of 14 kV, a flow rate of 0.6 mL / h, and a receiving distance of 20 cm to obtain antibacterial modified fibers for textile fabrics.

[0037] Comparative Example 4: The main difference between this comparative example and Example 1 is that cuprous chloride is not added in the preparation of tea polyphenol-based hyperbranched polyamide.

[0038] (1) Add 3 g of catechol-based hyperbranched polyamide to 30 mL of N,N-dimethylformamide, stir, 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.

[0039] (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 into a syringe, and spin through an electrospinning machine with a controlled voltage of 14 kV, a flow rate of 0.6 mL / h, and a receiving distance of 20 cm to obtain antibacterial modified fibers for textile fabrics.

[0040] 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.

[0041] (1) In an ice-water bath, add 3.6 mol of tri(2-aminoethyl)amine and 5 mol of terephthaloyl chloride to 140 mL of N,N-dimethylformamide, and carry out polymerization reaction at 20°C with stirring for 24 h in a nitrogen atmosphere. Pour the solution into ethanol, filter it, wash it with ethanol and water in turn, and dry it to obtain a hyperbranched polyamide.

[0042] (2) Add 3 g of hyperbranched polyamide to 30 mL of N,N-dimethylformamide, stir, then add 0.21 g of tea polyphenols, 0.06 g of cuprous chloride, and 5 mL of water. Stir at 50 °C for coordination reaction for 10 h. Pour the solution into ethanol, filter, and dry to obtain copper-tea polyphenol-based hyperbranched polyamide.

[0043] (3) Add 100 g of nylon 6 and 1 g of copper-tea polyphenol-based hyperbranched polyamide to 500 mL of formic acid, stir and inject into a syringe, and spin through an electrospinning machine with a controlled voltage of 14 kV, a flow rate of 0.6 mL / h, and a receiving distance of 20 cm to obtain antibacterial modified fibers for textile fabrics.

[0044] The tensile breaking properties are tested according to the national standard GB / T 14337-2022.

[0045] The antibacterial performance was tested according to the national standard GB / T 20944.3-2008. The fiber was washed and dried 50 times according to the national standard GB / T 8629-2017. Then the antibacterial performance was tested again. Antibacterial rate = (W t -Q t ) / W t ×100%. W t It is the average value of the viable bacteria concentration of the control sample (Comparative Example 1) after 18 hours of oscillation contact. t It is the average value of the viable bacteria concentration of the antibacterial sample after 18 hours of oscillating contact. Each group of samples is tested 3 times and the average value is taken.

[0046] Table 1

[0047] Table 2

[0048] After testing, compared with comparative example 1, the nylon fibers of examples 1-3 were added with copper-tea polyphenol-based hyperbranched polyamide, whose main molecular chain contained the same amide bond structural unit as nylon 6 polyamide, and had good compatibility with nylon 6. At the same time, it contained three-dimensional dendritic hyperbranched molecular chains, which formed a physical entanglement with nylon 6 molecular chains, had a good toughening effect on nylon 6 fibers, and improved the fiber elongation at break while maintaining good breaking strength. In addition, it contained tea polyphenol active antibacterial substances and antibacterial copper ions, which significantly improved the antibacterial properties of the fibers. At the same time, copper ions form a tight and strong coordination with the catechol groups in tea polyphenols and catechol-based hyperbranched polyamide. Since hyperbranched polyamide is a large molecular polymer, it is difficult to migrate and elute from the fiber matrix. The copper ions, tea polyphenols and catechol-based hyperbranched polyamide form a strong coordination effect, so that after multiple washings, copper ions and tea polyphenols are also difficult to elute from the fiber matrix, so that the fiber still maintains excellent antibacterial properties.

[0049] The catechol-based hyperbranched polyamide of Comparative Example 2 does not contain tea polyphenols and copper ions, and when added to nylon 6 fibers, it cannot effectively improve the antibacterial properties of the fibers.

[0050] The copper-based hyperbranched polyamide prepared in Comparative Example 3 does not contain tea polyphenols, resulting in low antibacterial properties of nylon 6 fiber. Copper ions form stable coordination interactions with the catechol structure of the hyperbranched polyamide. After multiple washings, copper ions are difficult to migrate and elute, and the fiber still maintains good antibacterial rate and antibacterial properties.

[0051] In comparative example 4, cuprous chloride was not added when preparing tea polyphenol-based hyperbranched polyamide, and no antibacterial copper ions were contained, so the antibacterial property of nylon 6 fiber was low. In addition, tea polyphenol and hyperbranched polyamide could not form a stable and firm interaction, and tea polyphenol was easily eluted after the fiber was washed many times, resulting in a significant decrease in the antibacterial rate of the fiber.

[0052] The hyperbranched polyamide of Comparative Example 5 does not contain catechol groups and cannot form coordination interactions with tea polyphenols and copper ions. After multiple washings, tea polyphenols and copper ions are prone to migration and elution, resulting in a significant decrease in the antibacterial rate of the fiber.

[0053] 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 a person skilled in the art within the technical scope disclosed by the present invention should be included in the protection scope of the present invention. Therefore, the protection scope of the present invention should be based on 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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