Preparation method of antibacterial moisture-permeable polyamide fiber and antibacterial moisture-permeable polyamide fiber

Abstract

The invention discloses a preparation method of an antibacterial moisture-permeable polyamide fiber and the antibacterial moisture-permeable polyamide fiber, and relates to the technical field of polyamide fibers. When the antibacterial moisture-permeable polyamide fiber is prepared, pretreated carbon nanotubes, ferric trichloride, sodium acetate trihydrate and diallyl disulfide are subjected to a microwave-assisted heating reaction, and carbon nanotube loaded nano iron sulfide is prepared; the preparation method comprises the following steps: modifying carbon nano tube loaded nano iron sulfide by using 3-aminopropyltriethoxysilane to prepare a modified carbon nano tube; mixing the modified carbon nanotubes and a nylon raw material, and performing melt spinning to obtain modified polyamide fibers; the modified polyamide fibers are modified with diethyl (3-aminopropyl) phosphate, 3-pyridylaldehyde and ethyl isocyano acetate, and flame-retardant modified polyamide fibers are prepared; and modifying the flame-retardant modified polyamide fiber with propane sultone to obtain the antibacterial moisture-permeable polyamide fiber. The prepared antibacterial moisture-permeable polyamide fiber has the advantages of being antibacterial, moisture-absorbing, antistatic, flame-retardant and high in tensile strength.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and specifically to a preparation method of antibacterial and moisture-permeable polyamide fibers and the antibacterial and moisture-permeable polyamide fibers. Background Art

[0002] In daily life, it is inevitable to come into contact with various microorganisms. These microorganisms will rapidly reproduce under suitable external conditions and can spread diseases through various channels, affecting normal work and study. And various fiber textile products are undoubtedly good habitats for these microorganisms. During daily wearing, it is inevitable to get stained with sweat, sebum and other various human secretions, and at the same time, it will also be contaminated by dirt in the environment. These dirt are good nutrient sources for various microorganisms, especially under high-temperature and humid conditions, which is a good environment for the reproduction of microorganisms. Therefore, in the process of the reproduction and transmission of pathogenic bacteria, textiles always play an important mediating role. If you don't pay attention to hygiene and disinfection, it is possible to make daily necessities contaminated with germs and cause cross-infection.

[0003] With the rapid development of technology and the continuous improvement of living standards, people's awareness of self-care has also increased day by day, and the requirements for environmental hygiene and clothing functionality are getting higher and higher. People not only hope that textile products have characteristics such as rich colors, beautiful appearance, practicality, health and environmental protection, but also require them to have the function of resisting bacteria and health care. According to the functional clothing market report, consumers' demand for antibacterial clothing is rising rapidly, and so far people's demand remains high. Summary of the Invention

[0004] The purpose of the present invention is to provide a preparation method of antibacterial and moisture-permeable polyamide fibers and the antibacterial and moisture-permeable polyamide fibers to solve the problems existing in the prior art.

[0005] To solve the above technical problems, the present invention provides the following technical solution: An antibacterial and moisture-permeable polyamide fiber, wherein the antibacterial and moisture-permeable polyamide fiber is prepared by modifying a flame-retardant modified polyamide fiber with propanesultone; the flame-retardant modified polyamide fiber is prepared by modifying a modified polyamide fiber with diethyl (3-aminopropyl) phosphate, 3-pyridinecarboxaldehyde, and ethyl isocyanoacetate; the modified polyamide fiber is prepared by melt spinning after mixing modified carbon nanotubes with nylon raw materials; the modified carbon nanotubes are prepared by modifying carbon nanotubes loaded with nano iron sulfide with 3-aminopropyltriethoxysilane; the carbon nanotubes loaded with nano iron sulfide are prepared by reacting pretreated carbon nanotubes with ferric chloride, sodium acetate trihydrate, and diallyl disulfide using microwave-assisted heating.

[0006] As an optimization, the pretreated carbon nanotubes are prepared by heating and reacting carbon nanotubes in concentrated nitric acid.

[0007] As an optimization, the nylon raw material is one of nylon 6, nylon 66, nylon 56, nylon 11, nylon 610, and nylon 612.

[0008] A preparation method of antibacterial and moisture-permeable polyamide fiber includes the following preparation steps: By mass, in a nitrogen atmosphere, 5-6 parts of flame-retardant modified polyamide fiber, 0.25-0.31 part of propanesultone, and 40-50 parts of absolute ethanol are mixed evenly, and stirred and refluxed at 80-85 °C and 75-125 r / min for 28-32 h, filtered, washed alternately with ether and pure water for 3-4 times, and vacuum-dried at 50-60 °C for 10-12 h to obtain the antibacterial and moisture-permeable polyamide fiber.

[0009] As an optimization, the reaction process of the antibacterial and moisture-permeable polyamide fiber is as follows: 。

[0010] As an optimization, the flame-retardant modified polyamide fiber is prepared by mixing 5-6 parts of modified polyamide fiber, 0.4-0.5 part of (3-aminopropyl) diethyl phosphate, 0.18-0.23 part of 3-pyridinecarboxaldehyde, 0.19-0.24 part of ethyl isocyanoacetate, and 80-90 parts of N,N-dimethylformamide evenly by mass, stirring at 100-150 r / min in a closed environment at room temperature for 12-14 h, filtering, washing alternately with absolute ethanol and pure water for 3-4 times, and vacuum-drying at 50-60 °C for 10-12 h.

[0011] As an optimization, the reaction process of the flame-retardant modified polyamide fiber is as follows: 。

[0012] As an optimization, the modified polyamide fiber is prepared by mixing 4-5 parts of modified carbon nanotubes and 50-60 parts of nylon raw material in a mixer at 280-300 °C and 60-70 rpm for 6-8 min, and then transferred to a melt spinning machine for melt spinning at 300-310 °C with a spinneret having 24 holes and 24 filaments as one strand.

[0013] As an optimization, the fiber fineness specification of the melt spinning can be changed by changing the draw line speed.

[0014] As an optimization, the modified carbon nanotubes are prepared by mixing 0.4 - 0.5 parts by mass of carbon nanotubes loaded with nano - iron sulfide, 9 - 10 parts of absolute ethanol, and 1 - 1.2 parts of pure water evenly, ultrasonicating at 40 °C for 25 - 30 min, adding 0.5 - 0.7 parts of 3 - aminopropyltriethoxysilane, refluxing at 75 - 80 °C at 200 - 300 r / min for 6 - 8 h, centrifuging at 8000 - 9000 rpm for 8 - 10 min, removing the liquid, washing with absolute ethanol 3 - 4 times, and vacuum - drying at 50 - 60 °C for 8 - 10 h.

[0015] As an optimization, the carbon nanotubes loaded with nano - iron sulfide are prepared by mixing 2 - 3 parts by mass of ferric chloride, 40 - 50 parts of ethylene glycol, and 8.39 - 12.58 parts of sodium acetate trihydrate evenly, stirring at 200 - 300 r / min at room temperature for 40 - 50 min, adding 4 - 5 parts of pretreated carbon nanotubes, ultrasonicating for 50 - 60 min, adding 0.9 - 1.35 parts of diallyl disulfide and mixing evenly, refluxing with microwave - assisted heating at 90 - 100 W for 18 - 20 min, naturally cooling to room temperature, centrifuging at 7000 - 8000 rpm for 8 - 10 min, removing the liquid, washing alternately with absolute ethanol and pure water 3 - 4 times, and vacuum - drying at 50 - 60 °C for 10 - 12 h.

[0016] As an optimization, the pretreated carbon nanotubes are prepared by dispersing 1 - 2 parts by mass of carbon nanotubes in 15 - 25 parts of concentrated nitric acid, stirring and refluxing at 130 °C at 200 - 300 r / min for 4 - 5 h, centrifuging at 7000 - 8000 rpm for 8 - 10 min, removing the liquid, washing the solid with pure water until neutral, and vacuum - drying at 50 - 60 °C for 10 - 12 h.

[0017] As an optimization, the model of the carbon nanotubes is XFM34, with a diameter of 50 nm.

[0018] Compared with the prior art, the beneficial effects achieved by the present invention are as follows: When preparing the antibacterial and moisture - permeable polyamide fiber, the present invention first heats and reacts carbon nanotubes in concentrated nitric acid to obtain pretreated carbon nanotubes; the pretreated carbon nanotubes react with ferric chloride, sodium acetate trihydrate, and diallyl disulfide using microwave - assisted heating to obtain carbon nanotubes loaded with nano - iron sulfide; the carbon nanotubes loaded with nano - iron sulfide are modified with 3 - aminopropyltriethoxysilane to obtain modified carbon nanotubes; the modified carbon nanotubes are mixed and kneaded with nylon raw materials and then melt - spun to obtain modified polyamide fibers; the modified polyamide fibers are modified with (3 - aminopropyl) diethyl phosphate, 3 - pyridinecarboxaldehyde, and ethyl isocyanoacetate to obtain flame - retardant modified polyamide fibers; the flame - retardant modified polyamide fibers are modified with propanesultone to obtain antibacterial and moisture - permeable polyamide fibers.

[0019] First, carbon nanotubes are acidified in concentrated nitric acid to introduce a large number of carboxyl groups on the surface of the carbon nanotubes, thereby improving the subsequent loading effect of nano iron sulfide. Under the condition of microwave-assisted heating, ferric chloride is used as the iron source and diallyl disulfide is used as the sulfur source to obtain nano iron sulfide and load it onto the pre-modified carbon nanotubes. Microwave-assisted heating helps the nano iron sulfide deposit and load faster. At the same time, its special heating method significantly reduces the reaction time and has a good effect. Diallyl disulfide, as an extract of garlic, has excellent bactericidal effects. However, as an organic sulfur compound, it will emit a pungent odor during use, which limits its application. Here, diallyl disulfide is used as the sulfur source to prepare nano iron sulfide for deposition. Nano iron sulfide also has excellent antibacterial properties. At the same time, after being prepared into nano iron sulfide, it also has good electrical conductivity and a high electron transfer rate. When it is deposited and loaded on the pre-modified carbon nanotubes, the two will play a synergistic role to better improve the antistatic performance.

[0020] Secondly, diethyl (3-aminopropyl) phosphate, 3-pyridinecarboxaldehyde, and ethyl isocyanoacetate undergo Ugi multicomponent reactions with the carboxyl groups on the surface of nylon or the carboxyl groups on the surface of modified carbon nanotubes to introduce the flame retardant element phosphorus on the surface of the modified polyamide fiber and introduce the reactive group pyridine. Subsequently, pyridine groups are sulfonated with propane sultone to obtain zwitterionic groups with sulfonic acid groups and pyridinium cations. The zwitterionic groups modified on the surface have excellent hydrophilic properties, which can effectively improve the hydrophilic properties of the antibacterial and moisture-permeable polyamide fiber and enhance its moisture absorption performance.

[0021] Finally, the pyridinium cations of the present invention also have good antibacterial properties and can form a synergistic antibacterial effect with nano iron sulfide, thereby effectively improving the antibacterial performance. And the sulfonic acid groups and pyridinium cations, as ionic groups, have good electron transfer properties, can effectively reduce the surface resistivity, and improve the antistatic performance. The modified carbon nanotubes form a conductive path inside, and the zwitterionic groups reduce the resistance on the surface. The two play a synergistic role and effectively improve the antistatic performance. At the same time, sulfur, nitrogen, and phosphorus elements work together to achieve a better flame retardant effect. Detailed implementation mode

[0022] Next, the technical solutions in the embodiments of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.

[0023] The information of some raw materials used in all the following examples and comparative examples is as follows: concentrated nitric acid: concentration is 14.5 mol / L; carbon nanotubes: model is XFM34, diameter is 50 nm, purchased from Jiangsu Xianfeng Nano Material Technology Co., Ltd.; nylon raw material: is nylon 66, grade is Clariant Nylon6 / 66608M33-L, purchased from Guangzhou Hongcheng Plasticization Co., Ltd.

[0024] In all the following examples and comparative examples, the fiber thickness specification of the melt spinning is controlled to be 70 denier, and 24 fibers are wound in a circle as one strand. Without special instructions, one strand is used for testing.

[0025] Example 1: A preparation method of antibacterial and moisture-permeable polyamide fiber, the preparation method of the antibacterial and moisture-permeable polyamide fiber includes the following preparation steps: (1) By mass, 1 part of carbon nanotubes is dispersed in 15 parts of concentrated nitric acid, stirred and refluxed at 130 °C and 200 r / min for 5 h, centrifuged at 7000 rpm for 10 min, the liquid is removed, the solid is washed with pure water until neutral, and vacuum dried at 50 °C for 12 h to obtain pretreated carbon nanotubes; (2) By mass, 2 parts of ferric chloride, 40 parts of ethylene glycol, and 8.39 parts of sodium acetate trihydrate are mixed evenly, stirred at 200 r / min for 50 min at room temperature, 4 parts of pretreated carbon nanotubes are added, sonicated for 50 min, 0.9 part of diallyl disulfide is added and mixed evenly, and refluxed and heated with 90 W microwave for 20 min, naturally cooled to room temperature, centrifuged at 7000 rpm for 10 min, the liquid is removed, washed alternately with absolute ethanol and pure water 3 times, and vacuum dried at 50 °C for 12 h to obtain carbon nanotube-supported nano iron sulfide; (3) By mass, 0.4 part of carbon nanotube-supported nano iron sulfide, 9 parts of absolute ethanol, and 1 part of pure water are mixed evenly, sonicated at 40 °C for 25 min, 0.5 part of 3-aminopropyltriethoxysilane is added, and refluxed and reacted at 75 °C at 200 r / min for 8 h, centrifuged at 8000 rpm for 10 min, the liquid is removed, washed with absolute ethanol 3 times, and vacuum dried at 50 °C for 10 h to obtain modified carbon nanotubes; (4) By mass, 4 parts of modified carbon nanotubes and 60 parts of nylon raw material are kneaded in a kneader at 280 °C and 60 rpm for 8 min, transferred to a melt spinning machine, and melt spun at 300 °C with a spinneret having 24 holes and 24 fibers as one strand to obtain modified polyamide fiber; (5) Mix 5 parts of modified polyamide fiber, 0.4 part of diethyl (3-aminopropyl) phosphate, 0.18 part of 3-pyridinecarboxaldehyde, 0.19 part of ethyl isocyanoacetate, and 80 parts of N,N-dimethylformamide evenly. Stir at 100 r / min for 14 h in a sealed environment at room temperature, filter, wash alternately with absolute ethanol and pure water 3 times, and dry in vacuum at 50 °C for 12 h to obtain flame-retardant modified polyamide fiber; (6) Mix 5 parts of flame-retardant modified polyamide fiber, 0.25 part of propanesultone, and 40 parts of absolute ethanol evenly under a nitrogen atmosphere. Stir and reflux at 80 °C and 75 r / min for 32 h, filter, wash alternately with ether and pure water 3 times, and dry in vacuum at 50 °C for 12 h to obtain antibacterial and moisture-permeable polyamide fiber.

[0026] Example 2: A preparation method of antibacterial and moisture-permeable polyamide fiber, the preparation method of the antibacterial and moisture-permeable polyamide fiber includes the following preparation steps: (1) Mix 1.5 parts of carbon nanotubes and 8.5 parts of concentrated nitric acid evenly. Stir and reflux at 130 °C and 250 r / min for 4.5 h, centrifuge at 7500 rpm for 9 min, remove the liquid, wash the solid with pure water until neutral, and dry in vacuum at 55 °C for 11 h to obtain pretreated carbon nanotubes; (2) Mix 2.5 parts of ferric trichloride, 45 parts of ethylene glycol, and 10.49 parts of sodium acetate trihydrate evenly. Stir at 250 r / min for 45 min at room temperature, add 4.5 parts of pretreated carbon nanotubes, ultrasonicate for 55 min, add 1.13 parts of diallyl disulfide and mix evenly. Heat and reflux with 95 W microwave assistance for 19 min, cool naturally to room temperature, centrifuge at 7500 rpm for 9 min, remove the liquid, wash alternately with absolute ethanol and pure water 3 times, and dry in vacuum at 55 °C for 11 h to obtain carbon nanotube-supported nano iron sulfide; (3) Mix 0.45 part of carbon nanotube-supported nano iron sulfide, 9.5 parts of absolute ethanol, and 1.1 part of pure water evenly. Ultrasonicate at 40 °C for 28 min, add 0.6 part of 3-aminopropyltriethoxysilane, reflux and react at 78 °C and 250 r / min for 7 h, centrifuge at 8500 rpm for 9 min, remove the liquid, wash with absolute ethanol 3 times, and dry in vacuum at 55 °C for 9 h to obtain modified carbon nanotubes; (4) Mix 4.5 parts of modified carbon nanotubes and 55 parts of nylon raw materials in a mixer at 290 °C and 65 rpm for 7 min, transfer to a melt spinning machine, and perform melt spinning at 305 °C with a spinneret having 24 holes and 24 filaments as one strand to obtain modified polyamide fiber; (5) By mass parts, 5.5 parts of modified polyamide fiber, 0.45 part of diethyl (3-aminopropyl) phosphate, 0.21 part of 3-pyridinecarboxaldehyde, 0.22 part of ethyl isocyanoacetate, and 85 parts of N,N-dimethylformamide were mixed evenly. At room temperature, in a closed environment, they were stirred at 125 r / min for 13 h, filtered, washed alternately with absolute ethanol and pure water 3 times, and vacuum dried at 55 °C for 11 h to obtain flame-retardant modified polyamide fiber; (6) By mass parts, in a nitrogen atmosphere, 5.5 parts of flame-retardant modified polyamide fiber, 0.28 part of propanesultone, and 45 parts of absolute ethanol were mixed evenly. At 82 °C, they were stirred and refluxed at 100 r / min for 30 h, filtered, washed alternately with ether and pure water 3 times, and vacuum dried at 55 °C for 11 h to obtain antibacterial and moisture-permeable polyamide fiber.

[0027] Example 3: A preparation method of antibacterial and moisture-permeable polyamide fiber, the preparation method of the antibacterial and moisture-permeable polyamide fiber includes the following preparation steps: (1) By mass parts, 2 parts of carbon nanotubes and 9 parts of concentrated nitric acid were mixed evenly. At 130 °C, they were stirred and refluxed at 300 r / min for 4 h, centrifuged at 8000 rpm for 8 min, the liquid was removed, the solid was washed with pure water until neutral, and vacuum dried at 60 °C for 10 h to obtain pretreated carbon nanotubes; (2) By mass parts, 3 parts of ferric chloride, 50 parts of ethylene glycol, and 12.58 parts of sodium acetate trihydrate were mixed evenly. At room temperature, they were stirred at 300 r / min for 40 min, 5 parts of pretreated carbon nanotubes were added, ultrasonicated for 60 min, 1.35 parts of diallyl disulfide were added and mixed evenly, microwave-assisted heating and refluxing were carried out at 100 W for 18 min, naturally cooled to room temperature, centrifuged at 8000 rpm for 8 min, the liquid was removed, washed alternately with absolute ethanol and pure water 4 times, and vacuum dried at 60 °C for 10 h to obtain carbon nanotube-supported nano iron sulfide; (3) By mass parts, 0.5 part of carbon nanotube-supported nano iron sulfide, 10 parts of absolute ethanol, and 1.2 parts of pure water were mixed evenly. At 40 °C, ultrasonicated for 30 min, 0.7 part of 3-aminopropyltriethoxysilane was added, and at 80 °C, reflux reaction was carried out at 300 r / min for 6 h, centrifuged at 9000 rpm for 8 min, the liquid was removed, washed with absolute ethanol 4 times, and vacuum dried at 60 °C for 8 h to obtain modified carbon nanotubes; (4) By mass parts, 5 parts of modified carbon nanotubes and 50 parts of nylon raw materials were kneaded in a kneader at 300 °C and 70 rpm for 6 min, transferred to a melt spinning machine, and melt spun at 310 °C with a spinneret having 24 holes and 24 filaments as one strand to obtain modified polyamide fiber; (5) By mass parts, mix 6 parts of modified polyamide fiber, 0.5 part of diethyl (3-aminopropyl) phosphate, 0.23 part of 3-pyridinecarboxaldehyde, 0.24 part of ethyl isocyanoacetate, and 90 parts of N,N-dimethylformamide evenly. Under room temperature, in a closed environment, stir at 150 r / min for 12 h, filter, wash alternately with absolute ethanol and pure water for 4 times, and dry in vacuum at 60 °C for 10 h to obtain flame-retardant modified polyamide fiber; (6) By mass parts, under a nitrogen atmosphere, mix 6 parts of flame-retardant modified polyamide fiber, 0.31 part of propanesultone, and 50 parts of absolute ethanol evenly. At 85 °C, stir and reflux at 125 r / min for 28 h, filter, wash alternately with ether and pure water for 4 times, and dry in vacuum at 60 °C for 10 h to obtain antibacterial and moisture-permeable polyamide fiber.

[0028] Comparative Example 1: The difference between the preparation method of the antibacterial and moisture-permeable polyamide fiber in Comparative Example 1 and that in Example 2 is that step (2) is not carried out, and step (3) is modified as follows: By mass parts, mix 0.45 part of pretreated carbon nanotubes, 9.5 parts of absolute ethanol, and 1.1 part of pure water evenly. At 40 °C, ultrasonicate for 28 min, add 0.6 part of 3-aminopropyltriethoxysilane, reflux and react at 78 °C at 250 r / min for 7 h, centrifuge at 8500 rpm for 9 min, remove the liquid, wash with absolute ethanol for 3 times, and dry in vacuum at 55 °C for 9 h to obtain modified carbon nanotubes. The remaining steps are the same as those in Example 2.

[0029] Comparative Example 2: The difference between the preparation method of the antibacterial and moisture-permeable polyamide fiber in Comparative Example 2 and that in Example 2 lies in step (2). Step (2) is modified as follows: By mass parts, mix 2.5 parts of ferric chloride, 45 parts of ethylene glycol, and 10.49 parts of sodium acetate trihydrate evenly. At room temperature, stir at 250 r / min for 45 min, add 4.5 parts of pretreated carbon nanotubes, ultrasonicate for 55 min, add 1.13 parts of diallyl disulfide and mix evenly. Carry out hydrothermal reaction at 200 °C for 12 h, naturally cool to room temperature, centrifuge at 7500 rpm for 9 min, remove the liquid, wash alternately with absolute ethanol and pure water for 3 times, and dry in vacuum at 55 °C for 11 h to obtain carbon nanotube-supported nano iron sulfide. The remaining steps are the same as those in Example 2.

[0030] Comparative Example 3: The difference between the preparation method of the antibacterial and moisture-permeable polyamide fiber in Comparative Example 3 and that in Example 2 is that step (3) is not carried out, and step (4) is modified as follows: By mass parts, mix 4.5 parts of carbon nanotube-supported nano iron sulfide and 55 parts of nylon raw materials in a mixer at 290 °C and 65 rpm for 7 min, transfer to a melt spinning machine, and carry out melt spinning at 305 °C with a spinneret having 24 holes and 24 filaments as one strand to obtain modified polyamide fiber. The remaining steps are the same as those in Example 2.

[0031] Comparative Example 4: The preparation method of the antibacterial and moisture-permeable polyamide fiber in Comparative Example 4 is different from that in Example 2 in that steps (1), (2), and (3) are not carried out, and step (4) is modified as follows: By mass, 55 parts of nylon raw materials are kneaded in a kneader at 290 °C and 65 rpm for 7 min, and then transferred to a melt spinning machine. The spinneret has 24 holes, 24 filaments are grouped into one strand, and melt spinning is carried out at 305 °C to obtain polyamide fibers. Step (5) is modified as follows: By mass, 5.5 parts of polyamide fibers, 0.45 part of (3-aminopropyl) diethyl phosphate, 0.21 part of 3-pyridinecarboxaldehyde, 0.22 part of ethyl isocyanoacetate, and 85 parts of N,N-dimethylformamide are mixed evenly. At room temperature, in a closed environment, stir at 125 r / min for 13 h, filter, wash alternately with absolute ethanol and pure water 3 times, and vacuum dry at 55 °C for 11 h to obtain flame-retardant modified polyamide fibers. The remaining steps are the same as in Example 2.

[0032] Comparative Example 5: The preparation method of the antibacterial and moisture-permeable polyamide fiber in Comparative Example 5 is different from that in Example 2 in step (5). Step (5) is modified as follows: By mass, 5.5 parts of modified polyamide fibers, 0.2 part of 1-aminopentane, 0.21 part of 3-pyridinecarboxaldehyde, 0.22 part of ethyl isocyanoacetate, and 85 parts of N,N-dimethylformamide are mixed evenly. At room temperature, in a closed environment, stir at 125 r / min for 13 h, filter, wash alternately with absolute ethanol and pure water 3 times, and vacuum dry at 55 °C for 11 h to obtain flame-retardant modified polyamide fibers. The remaining steps are the same as in Example 2.

[0033] Comparative Example 6: The preparation method of the antibacterial and moisture-permeable polyamide fiber in Comparative Example 6 is different from that in Example 2 in step (5). Step (5) is modified as follows: By mass, 5.5 parts of modified polyamide fibers, 0.45 part of (3-aminopropyl) diethyl phosphate, 0.23 part of phenylacetaldehyde, 0.22 part of ethyl isocyanoacetate, and 85 parts of N,N-dimethylformamide are mixed evenly. At room temperature, in a closed environment, stir at 125 r / min for 13 h, filter, wash alternately with absolute ethanol and pure water 3 times, and vacuum dry at 55 °C for 11 h to obtain flame-retardant modified polyamide fibers. The remaining steps are the same as in Example 2.

[0034] Comparative Example 7: The preparation method of the antibacterial and moisture-permeable polyamide fiber of Comparative Example 7 is different from that of Example 2 in that step (5) is not carried out, and step (6) is modified as follows: by mass, 5.5 parts of modified polyamide fiber, 0.28 part of propanesultone, and 45 parts of absolute ethanol are mixed evenly in a nitrogen atmosphere, stirred and refluxed at 82 °C and 100 r / min for 30 h, filtered, washed alternately with ether and pure water 3 times, and vacuum dried at 55 °C for 11 h to obtain the antibacterial and moisture-permeable polyamide fiber. The remaining steps are the same as those of Example 2.

[0035] Comparative Example 8: The preparation method of the antibacterial and moisture-permeable polyamide fiber of Comparative Example 8 is different from that of Example 2 in that step (6) is not carried out, and step (5) is modified as follows: by mass, 5.5 parts of modified polyamide fiber, 0.45 part of (3-aminopropyl) diethyl phosphate, 0.21 part of 3-pyridinecarboxaldehyde, 0.22 part of ethyl isocyanoacetate, and 85 parts of N,N-dimethylformamide are mixed evenly, and stirred at 125 r / min for 13 h in a closed environment at room temperature, filtered, washed alternately with absolute ethanol and pure water 3 times, and vacuum dried at 55 °C for 11 h to obtain the antibacterial and moisture-permeable polyamide fiber. The remaining steps are the same as those of Example 2.

[0036] Test Example 1: Mechanical property test: Referring to GB / T 14344-2022, the breaking strength of the prepared antibacterial and moisture-permeable polyamide fiber was tested. According to the reference standard, the antibacterial and moisture-permeable polyamide fiber was pre-conditioned in a constant temperature and humidity environment for 16 h first, then the gauge length was set to 250 mm, the tensile speed was set to 500 mm / min, and the test was carried out on a tensile testing machine. The breaking strength was calculated and recorded. Each group was tested 25 times, and the average value was taken for recording.

[0037] Antistatic property test: Referring to GB / T 14342-2015, the volume resistivity of the prepared antibacterial and moisture-permeable polyamide fiber was tested to evaluate its antistatic property. Each group of specimens was tested in parallel 10 times, and the average value was taken for recording.

[0038] Moisture absorption property test: Referring to GB / T 6503-2017, the moisture regain of the prepared antibacterial and moisture-permeable polyamide fiber was tested to evaluate its moisture absorption property. The hot weighing method in the box was adopted. After pre-conditioning in a constant temperature and humidity environment for 6 h, 50 g of the specimen was weighed and put into the oven, dried at 105 °C for 1 h, and then the weight was tested every 10 min until constant weight. The weight at this time was recorded, and the moisture regain was calculated according to the formula in the standard. Each group was tested in parallel with 10 specimens, and the average value was taken for recording.

[0039] Flame retardancy test: Prepare test specimens by the cotton roll method in the following references, and refer to GB / T 5454-1997 to test the limiting oxygen index of the prepared antibacterial and moisture-permeable polyamide fibers. Test 5 specimens in each group and record the average value.

[0040] The references are: Zhang Xinmin, Zhou Zhende, Li Hongjie, etc. Research on the evaluation of flame retardant fibers and their performance characterization methods [J]. Quality and Standardization, 2010, 000(012): 17-20.

[0041] The results are shown in Table 1.

[0042]

[0043] From the comparison of the experimental data of Examples 1-3 and Comparative Examples 1-8 in Table 1, it can be found that the antibacterial and moisture-permeable polyamide fibers prepared by the present invention have good breaking strength, antistatic performance, hygroscopicity and flame retardancy.

[0044] Through the data comparison in the table, the data of Comparative Example 1 show that the nano iron sulfide loaded on the modified carbon nanotubes improves a part of the breaking strength, and at the same time forms a synergistic effect with the carbon nanotubes to improve the antistatic performance, and plays a synergistic flame retardant effect with the flame retardant elements phosphorus and nitrogen, effectively improving the flame retardancy; the data of Comparative Example 2 show that the nano iron sulfide loaded by the microwave-assisted heating method is superior to that loaded by the hydrothermal reaction in all aspects; the data of Comparative Example 3 show that the modification of carbon nanotubes by 3-aminopropyltriethoxysilane improves its dispersion performance in the nylon matrix, effectively avoiding the performance loss caused by agglomeration, and improving the breaking strength and antistatic performance; the data of Comparative Example 4 show that the addition of modified carbon nanotubes improves the breaking strength and flame retardancy, and at the same time greatly improves the antistatic performance and slightly improves the hygroscopicity; the data of Comparative Example 5 show that (3-aminopropyl) diethyl phosphate participates in the Ugi multicomponent reaction to introduce the flame retardant element phosphorus, effectively improving the flame retardancy; the data of Comparative Example 6 show that 3-pyridinecarboxaldehyde participates in the Ugi multicomponent reaction to introduce a pyridine group, which can react with subsequent propanesultone to form an amphoteric ion group, greatly improving the hygroscopicity while also synergistically improving the antistatic performance and flame retardancy; the data of Comparative Example 7 show that the Ugi multicomponent reaction effectively improves the antistatic performance, hygroscopicity and flame retardancy of the antibacterial and moisture-permeable polyamide fibers; the data of Comparative Example 8 show that propanesultone successfully reacts with the pyridine group to form an amphoteric ion group, and the characteristics of the ion group improve the antistatic performance, and at the same time the flame retardant element sulfur also synergistically improves part of the flame retardancy.

[0045] Test Example 2: Antibacterial performance test: Using the oscillation method in GB / T 20944.3-2008, cut 0.75±0.05 g of the prepared antibacterial and moisture-permeable polyamide fiber samples and mix them with the bacterial solution and oscillate for 5 min. Take the oscillated bacterial solution and culture it in the agar medium. Determine the antibacterial rate of the antibacterial and moisture-permeable polyamide fiber against Escherichia coli and Staphylococcus aureus by the number of growing colonies. Each group of samples is tested 5 times, and the average value is recorded.

[0046] The results are shown in Table 2.

[0047]

[0048] From the comparison of the experimental data of Examples 1 to 3 and Comparative Examples 1 to 8 in Table 2, it can be found that the antibacterial and moisture-permeable polyamide fiber prepared by the present invention has good antibacterial performance.

[0049] Through the comparison of the data in the table, the data of Comparative Examples 1 and 4 show that the loading of nano iron sulfide has played a certain antibacterial effect and synergistically improved the antibacterial performance; the data of Comparative Examples 6 and 7 show that after the introduction of pyridine groups, they react with propanesultone to form zwitterionic groups, which have excellent antibacterial performance and greatly improve the antibacterial ability; the data of Comparative Example 8 show that propanesultone reacts with pyridine groups to form zwitterionic groups, which improves the antibacterial performance. At the same time, the antibacterial rate of Comparative Example 8 is higher than that of Comparative Examples 6 and 7 because the pyridine group itself has a certain antibacterial ability, but it is significantly weaker than the performance after forming zwitterionic groups.

[0050] The specific embodiments described above further elaborate on the purpose, technical solution, and beneficial effects of the present invention. It should be understood that the above description is only the specific embodiments of the present invention and is not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included in the protection scope of the present invention.

Claims

1. An antibacterial and moisture-permeable polyamide fiber, characterized in that, The antibacterial and moisture-permeable polyamide fiber is prepared by modifying the flame-retardant modified polyamide fiber with propanesultone; the flame-retardant modified polyamide fiber is prepared by modifying the modified polyamide fiber with diethyl (3-aminopropyl) phosphate, 3-pyridinecarboxaldehyde, and ethyl isocyanoacetate; The modified polyamide fiber is prepared by melt spinning after mixing the modified carbon nanotubes with nylon raw materials; the modified carbon nanotubes are prepared by modifying carbon nanotubes loaded with nano iron sulfide with 3-aminopropyltriethoxysilane; the carbon nanotubes loaded with nano iron sulfide are prepared by reacting pretreated carbon nanotubes with ferric chloride, sodium acetate trihydrate, and diallyl disulfide using microwave-assisted heating.

2. The antibacterial and moisture-permeable polyamide fiber according to claim 1, characterized in that, The pretreated carbon nanotubes are prepared by heating and reacting carbon nanotubes in concentrated nitric acid.

3. The antibacterial and moisture-permeable polyamide fiber according to claim 1, characterized in that, The nylon raw material is one of nylon 6, nylon 66, nylon 56, nylon 11, nylon 610, and nylon 612.

4. A method for preparing antibacterial and moisture-permeable polyamide fiber, characterized in that, It includes the following preparation steps: By mass, in a nitrogen atmosphere, 5-6 parts of flame-retardant modified polyamide fiber, 0.25-0.31 part of propanesultone, and 40-50 parts of absolute ethanol are mixed evenly, stirred and refluxed at 80-85 °C for 28-32 h, filtered, washed alternately with ether and pure water, and dried in vacuum to obtain the antibacterial and moisture-permeable polyamide fiber.

5. The preparation method of an antibacterial and moisture-permeable polyamide fiber according to claim 4, wherein, The flame-retardant modified polyamide fiber is prepared by mixing 5-6 parts of modified polyamide fiber, 0.4-0.5 part of diethyl (3-aminopropyl) phosphate, 0.18-0.23 part of 3-pyridinecarboxaldehyde, 0.19-0.24 part of ethyl isocyanoacetate, and 80-90 parts of N,N-dimethylformamide evenly, stirring in a closed environment at room temperature for 12-14 h, filtering, washing alternately with absolute ethanol and pure water, and drying in vacuum.

6. The preparation method of an antibacterial and moisture-permeable polyamide fiber according to claim 5, characterized in that, The modified polyamide fiber is prepared by mixing 4-5 parts of modified carbon nanotubes and 50-60 parts of nylon raw materials in a mixer at 280-300 °C for 6-8 min, transferring to a melt spinning machine, and melt spinning at 300-310 °C with a spinneret having 24 holes and 24 filaments as one strand.

7. The preparation method of an antibacterial and moisture-permeable polyamide fiber according to claim 6, characterized in that, The modified carbon nanotubes are prepared by mixing 0.4-0.5 part of carbon nanotubes loaded with nano iron sulfide, 9-10 parts of absolute ethanol, and 1-1.2 parts of pure water evenly, ultrasonicating at 40 °C for 25-30 min, adding 0.5-0.7 part of 3-aminopropyltriethoxysilane, refluxing and reacting at 75-80 °C for 6-8 h, centrifuging for 8-10 min, removing the liquid, washing with absolute ethanol, and drying in vacuum.

8. The preparation method of an antibacterial and moisture-permeable polyamide fiber according to claim 7, characterized in that, The carbon nanotubes loaded with nano iron sulfide are prepared by mixing 2-3 parts of ferric chloride, 40-50 parts of ethylene glycol, and 8.39-12.58 parts of sodium acetate trihydrate evenly, stirring at room temperature for 40-50 min, adding 4-5 parts of pretreated carbon nanotubes, ultrasonicating for 50-60 min, adding 0.9-1.35 part of diallyl disulfide and mixing evenly, refluxing with microwave-assisted heating at 90-100 W for 18-20 min, naturally cooling to room temperature, centrifuging for 8-10 min, removing the liquid, washing alternately with absolute ethanol and pure water, and drying in vacuum.

9. The preparation method of an antibacterial and moisture-permeable polyamide fiber according to claim 8, characterized in that, The pretreated carbon nanotubes are prepared by dispersing 1 to 2 parts by mass of carbon nanotubes in 15 to 25 parts by mass of concentrated nitric acid, stirring and refluxing at 130 °C for 4 to 5 h, centrifuging for 8 to 10 min, removing the liquid, washing the solid with pure water until neutral, and drying in vacuum.

10. The preparation method of an antibacterial and moisture-permeable polyamide fiber according to claim 9, characterized in that, The carbon nanotubes have the model number XFM34 and a diameter of 50 nm.

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