A synergistically modified antibacterial and decontaminating wear-resistant polyester fiber and a preparation method thereof

Abstract

The application relates to a synergistically modified antibacterial and detoxifying wear-resistant polyester fiber and a preparation method thereof, and belongs to the technical field of functional polyester fibers. The polyester fiber is prepared by melt spinning of a zinc core copolyester component and modified halloysite nanotubes; the zinc core copolyester is a copolyester obtained by in-situ polymerization of a zinc-based composite antibacterial and detoxifying auxiliary agent in an esterification polycondensation process of polyester; the modified halloysite nanotubes are obtained by modification of a silane coupling agent and tannic acid; the obtained polyester fiber has excellent antibacterial and antiviral properties and wear resistance.

Description

Technical Field

[0001] This invention belongs to the field of functional polyester fiber technology, and relates to a synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber and its preparation method. Background Technology

[0002] Polyester fiber (polyethylene terephthalate, PET) is widely used in various fields such as medical and health care, clothing, and home textiles due to its high mechanical strength, excellent abrasion resistance, and good chemical stability. However, ordinary polyester fiber does not have antibacterial and detoxifying functions. During use, it easily absorbs sweat and dust, breeding bacteria and mold, and may even leave harmful substances such as formaldehyde, causing odors, skin infections, or health hazards, thus limiting its application in high-end functional scenarios.

[0003] To address the aforementioned issues, existing technologies primarily employ antibacterial modification methods to prepare functional polyester fibers, mainly including finishing methods, blending spinning methods, and core-sheath composite spinning methods. Finishing methods attach antibacterial agents to the fiber surface through impregnation, coating, etc., a simple process, but the bonding force between the antibacterial agent and the fiber is weak, resulting in poor wash resistance, insufficient antibacterial durability, and a tendency for fiber mechanical properties to decline due to pretreatment such as strong alkali etching. Blending spinning methods mix antibacterial agents with polyester chips and melt-spin, improving bonding stability, but typically requiring the addition of more than 1% antibacterial agent to ensure antibacterial effects, easily causing agent agglomeration and uneven dispersion, thus affecting fiber spinning performance and mechanical strength. Core-sheath composite spinning methods confine the antibacterial agent to the fiber sheath layer, reducing the amount used, but resulting in slow forming speed, lower fiber strength, and often only possessing a single antibacterial function, failing to achieve detoxification.

[0004] The current application of zinc-based antibacterial agents in polyester modification often suffers from problems such as poor dispersibility, severe agglomeration, and the need for photocatalysis or high content addition to be effective. Furthermore, there is a lack of technical solutions that can simultaneously possess both antibacterial and detoxifying functions while maintaining the original excellent properties of polyester fibers at low addition levels.

[0005] Therefore, there is an urgent need to develop a modified polyester fiber with low content, high dispersion, integrated antibacterial and detoxifying properties, and strong process compatibility. Summary of the Invention

[0006] The purpose of this invention is to provide a synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber and its preparation method. The resulting polyester fiber has excellent antibacterial, antiviral, and wear-resistant properties.

[0007] The objective of this invention can be achieved through the following technical solutions: A synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber, wherein the polyester fiber is obtained by melt spinning of a zinc-core copolyester component and modified halloysite nanotubes; the zinc-core copolyester is obtained by in-situ polymerization of a zinc-based composite antibacterial and detoxifying agent during the esterification polycondensation process of polyester; the modified halloysite nanotubes are obtained by modification with a silane coupling agent and tannic acid. The zinc-based composite antibacterial and detoxifying adjuvant is a stable sol system formed with zinc-based active ingredients as the core and polyols as the dispersion medium. Its content in the zinc core copolyester component is 0.1~0.3%.

[0008] As a preferred embodiment of the present invention, the zinc-based composite antibacterial and detoxifying adjuvant has a particle size of 100-200 nm, the polyol dispersion medium is one or more of ethylene glycol, propylene glycol and glycerin, and the mass ratio of the polyol dispersion medium to the zinc-based active ingredient is (3-5):1.

[0009] As a preferred embodiment of the present invention, the preparation process of the modified halloysite nanotubes is as follows: S21, Pretreated halloysite nanotubes: Halloysite nanotubes were dispersed in dilute hydrochloric acid with a concentration of 1-3 mol / L, stirred at 60-80℃ for 2-4 h, filtered and washed until neutral, and dried in a vacuum oven at 60℃ for 12 h to obtain activated halloysite nanotubes. S22. According to the mass fraction, 10-15 parts of tannic acid, 3-6 parts of 3-isocyanate propyltriethoxysilane, and 0.1-0.3 parts of dibutyltin dilaurate are added to anhydrous N,N-dimethylformamide. Under nitrogen protection, the mixture is stirred at 50-60°C for 10-16 hours. After stirring, the pretreated tannic acid is obtained by rotary evaporation. S23, Covalent grafting: Halloysite nanotubes and pretreated tannic acid were mixed in an ethanol / water solvent with a volume ratio of 95:5. The pH of the solution was adjusted to 4-5 by adding 0.1 mol / L acetic acid. The mixture was stirred at 55-65°C for 6-10 h. The mass ratio of the pretreated tannic acid to halloysite nanotubes was 1:(1.5-3) to obtain the modified halloysite nanotubes.

[0010] A method for preparing synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber includes the following steps: S1. Preparation of zinc core copolyester chips: According to the weight proportions, 100 parts of terephthalic acid and 30-35 parts of ethylene glycol are added to the reactor. Under a nitrogen atmosphere, the mixture is stirred at a speed of 150-200 r / min until homogeneous. Then, the additives and zinc-based composite antibacterial and detoxifying additives are added in sequence. The stirring speed is maintained and the mixture is stirred for 20-30 min. After stirring and mixing, the zinc core copolyester resin is obtained through esterification and polycondensation. S2. Slice preparation: Zinc-core copolyester resin is extruded through an extruder, cooled to room temperature in a cooling water bath, and then cut into polyester chips by a pelletizer. The moisture content of the chips is ≤0.02%. S3, spinning: Polyester chips are fed into a dryer and dried at 120-140°C for 4-6 hours. Modified halloysite nanotubes are then premixed with the polyester chips and heated to 280-290°C to melt. The mixture is then extruded through a spinneret of a spinning machine and subjected to cooling, stretching, crimping, and cutting processes to obtain polyester fiber staples, thus producing the synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber fabric.

[0011] In a preferred embodiment of the present invention, in step S1, the additives are a catalyst, a heat stabilizer, and an antioxidant. The catalyst is antimony trioxide or antimony glycolate, and the amount of catalyst added is 0.02 to 0.05 parts. The heat stabilizer is trimethyl phosphate, and the amount added is 0.01 to 0.03 parts. The antioxidant is a phosphite compound, and the amount added is 0.03 to 0.06 parts.

[0012] As a preferred embodiment of the present invention, in step S1, the esterification conditions are: 240~260℃, 0.2~0.3MPa, and 3~4h.

[0013] As a preferred technical solution of the present invention, in step S1, the conditions for polycondensation are: 275~285℃, vacuum degree ≤100Pa, and time is 4~6h.

[0014] As a preferred embodiment of the present invention, in step S3, the stretching ratio is 3.5 to 4.5 times, and the number of curls is 8 to 12 per 10 cm.

[0015] As a preferred embodiment of the present invention, in step S3, the orifice diameter of the spinneret is 0.2~0.4mm, the cooling air temperature is 20~25℃, and the air velocity is 0.5~1.0m / s.

[0016] As a preferred embodiment of the present invention, in step S3, the modified halloysite nanotubes have a mass percentage of 0.5-2.0% in the fiber.

[0017] In this invention, halloysite nanotubes are first treated with dilute hydrochloric acid to remove impurities and significantly increase the density and reactivity of their surface silanol groups. This provides essential and sufficient chemical anchoring sites for subsequent reactions, a prerequisite for constructing a stable functional structure. Then, through a catalytic reaction, the isocyanate groups of 3-isocyanatepropyltriethoxysilane react with the phenolic hydroxyl groups of tannic acid molecules to obtain pretreated tannic acid. Finally, in a weakly acidic ethanol / water system, the triethoxy groups of the pretreated tannic acid undergo hydrolysis to generate highly reactive silanol groups, which then undergo a dehydration condensation reaction with the silanol groups on the activated halloysite surface to form strong Si-O-Si covalent bonds. This chemically bonds the tannic acid molecules to the halloysite surface, avoiding the migration and elution problems of small-molecule antibacterial agents. Through these treatments, a strong interfacial bond between halloysite nanotubes and the polyester matrix is ​​achieved, avoiding the performance degradation and functional loss caused by weak interfaces in traditional fillers. This allows the nano-reinforcing effect to be fully utilized, improving fiber abrasion resistance without compromising the original excellent mechanical properties of the polyester.

[0018] After mixing and spinning modified halloysite nanotubes with polyester chips prepolymerized with zinc-based antibacterial additives, the resulting polyester fibers exhibit a synergistic effect in the time dimension. The tannic acid on the surface of the fibers provides the ability to rapidly contact and kill bacteria and adsorb and enrich pollutants. This synergizes with the photocatalytic long-lasting protection provided by the zinc-based composite antibacterial and detoxifying additives. On the one hand, bacteria and organic toxins are enriched on the fiber surface and around the zinc-based composite antibacterial and detoxifying additives through adsorption, which greatly increases the local substrate concentration of the photocatalytic reaction of the zinc-based composite antibacterial and detoxifying additives. This significantly improves the overall antibacterial and detoxifying efficiency, achieves deep catalytic degradation of residual organic matter and viruses, and broadens the antibacterial spectrum.

[0019] The beneficial effects of this invention are: (1) This invention differs from traditional finishing or conventional blending spinning technology. In the polyester polymerization stage, a zinc-based composite antibacterial and detoxifying agent is introduced, which is chemically embedded into the polyester macromolecular chain network. The amount added is only 0.1~0.3% to achieve an antibacterial and detoxifying rate of >99.9%. At the same time, the low content can avoid damage to the polyester molecular chain structure and does not affect the original properties of the polyester. A polyol system sol is used as the dispersion medium of the zinc-based active ingredient to improve the compatibility with the polyester polymerization raw materials. It can be uniformly dispersed in the polyester matrix in the front-end polymerization stage, avoiding spinning failures and performance fluctuations caused by agent agglomeration. The non-dissolving design ensures the antibacterial and detoxifying effect is long-lasting and improves the washability of polyester fibers.

[0020] (2) This invention introduces modified halloysite nanotubes as the second functional component through the “zinc-based-modified biomineral” system, which forms a multi-synergistic effect of “catalytic detoxification-adsorption enhancement-contact sterilization-physical wear resistance” with the zinc-based composite antibacterial and detoxifying agent. The resulting polyester fiber has excellent antibacterial and antiviral properties as well as wear resistance. It can achieve an antibacterial rate of >99.9% against Escherichia coli and Staphylococcus aureus, a detoxification rate of >99.9% against formaldehyde and other harmful substances, and also has a level 0 anti-mildew performance, which solves the problem of the lack of single antibacterial and detoxification capabilities in the existing technology. Detailed Implementation

[0021] To further illustrate the technical means and effects of the present invention in achieving its intended purpose, the following detailed description of the specific implementation methods, structures, features, and effects of the present invention, in conjunction with embodiments, is provided below.

[0022] It should be noted that in the following examples and comparative examples, 3-isocyanate propyltriethoxysilane was purchased from Shanghai Maclean Biochemical Technology Co., Ltd., product number: T819132; terephthalic acid was purchased from Shanghai Haohong Biomedical Technology Co., Ltd., product number: 1014521; trimethyl phosphate was purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., product number: T104024; halloysite nanotubes were purchased from Shanghai E-En Chemical Technology Co., Ltd., product number: R096336. Unless otherwise specified, the present invention does not specifically limit the source of other raw materials used. Products prepared by commercially available products or conventional preparation methods well known to those skilled in the art can be used. Experimental methods without specific conditions are all conventional methods and conditions well known in the art.

[0023] The preparation process of the zinc-based active ingredient is as follows: Prepare 100 mL of 0.1 mol / L zinc chloride aqueous solution and 100 mL of 0.4 mol / L sodium hydroxide aqueous solution. Add 7.32 g of Zn powder to the zinc chloride solution, heat to 90℃, add the prepared sodium hydroxide solution, stir for 20 min, centrifuge and filter the precipitate, and dry at 100℃ to obtain the zinc-based active ingredient.

[0024] Example 1 A zinc-based composite antibacterial and detoxifying adjuvant with a solid content of 0.15%, using ethylene glycol as the polyol medium, and a zinc-based active ingredient to ethylene glycol mass ratio of 1:4, with a particle size of 150nm.

[0025] Halloysite nanotubes were dispersed in 2 mol / L dilute hydrochloric acid and stirred at 70°C for 2–4 h. After filtration and washing until neutral, the nanotubes were dried in a vacuum oven at 60°C for 12 h to obtain activated halloysite nanotubes. 13 parts by mass of tannic acid, 5 parts by mass of 3-isocyanate propyltriethoxysilane, and 0.2 parts by mass of dibutyltin dilaurate were added to anhydrous N,N-dimethylformamide and stirred at 55°C for 15 h under nitrogen protection. After stirring, the mixture was rotary evaporated to obtain pretreated tannic acid. Halloysite nanotubes and pretreated tannic acid were mixed in an ethanol / water solvent with a volume ratio of 95:5. 0.1 mol / L acetic acid was added to adjust the pH of the solution to 4–5, and the mixture was stirred at 60°C for 8 h. The mass ratio of the pretreated tannic acid to halloysite nanotubes was 1:2 to obtain the modified halloysite nanotubes.

[0026] S1. Preparation of zinc core copolyester chips: According to the weight proportions, 100 parts of terephthalic acid and 33 parts of ethylene glycol were added to the reactor. Under a nitrogen atmosphere, the mixture was stirred evenly at a speed of 200 r / min. Then, 0.04 parts of antimony trioxide, 0.02 parts of trimethyl phosphate, 0.05 parts of antioxidant 168 and 0.2 parts of zinc-based composite antibacterial and detoxifying agent were added sequentially. The stirring speed was maintained and the mixture was stirred for 25 min. After mixing, the mixture was esterified at 250℃ and 0.25 MPa for 3 h. Then, the temperature was raised to 280℃ and the vacuum degree was ≤100 Pa for condensation for 5 h to obtain zinc core copolyester resin. S2. Slice preparation: Zinc-core copolyester resin is extruded through an extruder, cooled to room temperature in a cooling water bath, and then cut into polyester chips by a pelletizer. The moisture content of the chips is ≤0.02%. S3, spinning: Polyester chips were fed into a dryer and dried at 130°C for 5 hours. Modified halloysite nanotubes were then premixed with the polyester chips and heated to 285°C to melt. The mixture was then extruded through a spinneret on a spinning machine. After cooling, stretching, crimping, and cutting processes, polyester staple fibers were prepared to obtain the synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber fabric. The stretching ratio was 4 times, the crimp count was 10 crimps / 10cm, the spinneret orifice diameter was 0.3mm, the cooling air temperature was 23°C, the air velocity was 0.8m / s, and the mass percentage of modified halloysite nanotubes in the fiber was 1.0%.

[0027] Example 2 Zinc-based composite antibacterial and detoxifying adjuvant: solid content 0.1%, polyol medium is propylene glycol, zinc-based active ingredient to propylene glycol mass ratio 1:3, particle size 120nm.

[0028] Halloysite nanotubes were dispersed in 2 mol / L dilute hydrochloric acid and stirred at 70°C for 1 h. After filtration and washing until neutral, the nanotubes were dried in a vacuum oven at 60°C for 12 h to obtain activated halloysite nanotubes. 10 parts by mass of tannic acid, 3 parts by mass of 3-isocyanate propyltriethoxysilane, and 0.1 parts by mass of dibutyltin dilaurate were added to anhydrous N,N-dimethylformamide and stirred at 50°C for 10 h under nitrogen protection. After stirring, the mixture was rotary evaporated to obtain pretreated tannic acid. Halloysite nanotubes and pretreated tannic acid were mixed in an ethanol / water solvent with a volume ratio of 95:5. 0.1 mol / L acetic acid was added to adjust the pH of the solution to 4-5, and the mixture was stirred at 60°C for 8 h. The mass ratio of the pretreated tannic acid to halloysite nanotubes was 1:1.5 to obtain the modified halloysite nanotubes.

[0029] S1. Preparation of zinc core copolyester chips: According to the weight ratio, 100 parts of terephthalic acid and 30 parts of ethylene glycol were added to the reactor. Under a nitrogen atmosphere, the mixture was stirred at a speed of 200 r / min until homogeneous. Then, 0.02 parts of antimony trioxide, 0.01 parts of trimethyl phosphate, 0.03 parts of antioxidant 168 and 0.1 parts of zinc-based composite antibacterial and detoxifying agent were added sequentially. The stirring speed was maintained and the mixture was stirred for 20 min. After mixing, the mixture was esterified at 240℃ and 0.2 MPa for 3 h. Then, the temperature was raised to 275℃ and the vacuum degree was ≤100 Pa for condensation for 4 h to obtain zinc core copolyester resin. S2. Slice preparation: Zinc-core copolyester resin is extruded through an extruder, cooled to room temperature in a cooling water bath, and then cut into polyester chips by a pelletizer. The moisture content of the chips is ≤0.02%. S3, spinning: Polyester chips were fed into a dryer and dried at 130°C for 5 hours. Modified halloysite nanotubes were then premixed with the polyester chips and heated to 285°C to melt. The mixture was then extruded through a spinneret on a spinning machine. After cooling, stretching, crimping, and cutting processes, polyester staple fibers were prepared to obtain the synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber fabric. The stretching ratio was 3.5 times, the crimp count was 8 crimps / 10cm, the spinneret orifice diameter was 0.2mm, the cooling air temperature was 20°C, the air velocity was 0.5m / s, and the mass percentage of modified halloysite nanotubes in the fiber was 0.5%.

[0030] Example 3 Zinc-based composite antibacterial and detoxifying adjuvant: solid content 0.3%, polyol medium is ethylene glycol-glycerol in a mass ratio of 2:1, zinc-based active ingredient to compound medium in a mass ratio of 1:5, particle size 180nm.

[0031] Halloysite nanotubes were dispersed in 2 mol / L dilute hydrochloric acid and stirred at 70°C for 3 h. After filtration and washing until neutral, the nanotubes were dried in a vacuum oven at 60°C for 12 h to obtain activated halloysite nanotubes. 15 parts by mass of tannic acid, 6 parts by mass of 3-isocyanate propyltriethoxysilane, and 0.3 parts by mass of dibutyltin dilaurate were added to anhydrous N,N-dimethylformamide and stirred at 60°C for 16 h under nitrogen protection. After stirring, the mixture was rotary evaporated to obtain pretreated tannic acid. Halloysite nanotubes and pretreated tannic acid were mixed in an ethanol / water solvent with a volume ratio of 95:5. 0.1 mol / L acetic acid was added to adjust the pH of the solution to 4-5, and the mixture was stirred at 65°C for 10 h. The mass ratio of the pretreated tannic acid to halloysite nanotubes was 1:3 to obtain the modified halloysite nanotubes.

[0032] S1. Preparation of zinc core copolyester chips: According to the weight proportions, 100 parts of terephthalic acid and 35 parts of ethylene glycol were added to the reactor. Under a nitrogen atmosphere, the mixture was stirred evenly at a speed of 200 r / min. Then, 0.05 parts of antimony trioxide, 0.03 parts of trimethyl phosphate, 0.06 parts of antioxidant 168 and 0.3 parts of zinc-based composite antibacterial and detoxifying agent were added sequentially. The stirring speed was maintained and the mixture was stirred for 30 min. After mixing, the mixture was esterified at 260℃ and 0.3 MPa for 4 h. Then, the temperature was raised to 285℃ and the vacuum degree was ≤100 Pa for condensation for 6 h to obtain zinc core copolyester resin. S2. Slice preparation: Zinc-core copolyester resin is extruded through an extruder, cooled to room temperature in a cooling water bath, and then cut into polyester chips by a pelletizer. The moisture content of the chips is ≤0.02%. S3, spinning: Polyester chips were fed into a dryer and dried at 140°C for 6 hours. Modified halloysite nanotubes were then premixed with the polyester chips and heated to 290°C to melt. The mixture was then extruded through a spinneret on a spinning machine. After cooling, stretching, crimping, and cutting processes, polyester staple fibers were prepared to obtain the synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber fabric. The stretching ratio was 4.5 times, the crimp count was 12 crimps / 10cm, the spinneret orifice diameter was 0.4mm, the cooling air temperature was 25°C, the air velocity was 1.0m / s, and the mass percentage of modified halloysite nanotubes in the fiber was 2.0%.

[0033] Comparative Example 1 Using the existing blending spinning method, nano zinc oxide (particle size 150nm) was mixed with polyester chips at a content of 1.5% and melt-spun. Other processes were the same as in Example 1 to prepare polyester fibers.

[0034] Comparative Example 2 This is basically the same as Example 1, except that in this comparative example, tannic acid and halloysite nanotubes are directly physically mixed to obtain modified halloysite nanotubes.

[0035] Comparative Example 3 This is basically the same as Example 1, except that the halloysite nanotubes in this comparative example were not modified.

[0036] Comparative Example 4 This is basically the same as Example 1, except that no modified halloysite nanotubes were added in this comparative example.

[0037] Performance testing: 1. Antibacterial properties: Referring to GB / T 20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Shaking method", the bacterial strains were Escherichia coli ATCC25922 and Staphylococcus aureus ATCC6538. The test results are shown in Table 1 below: Table 1 2. Abrasion resistance: Refer to GB / T 21196.2-2007; 3. Antiviral activity: Detection method: ISO 21702:2019, using influenza A virus H1N1 (A / PR / 8 / 34) as the test virus and MDCK cells as the host for detection. The test results are shown in Table 2. Table 2 Based on the above data, it can be seen that the polyester fiber prepared by the present invention has excellent antibacterial and detoxifying effects, and also has excellent wear resistance.

[0038] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber, characterized in that, The polyester fiber is obtained by melt spinning of zinc core copolyester component and modified halloysite nanotubes; the zinc core copolyester is obtained by in-situ polymerization of the polyester by adding zinc-based composite antibacterial and detoxifying agent during the esterification polycondensation process of polyester; the modified halloysite nanotubes are obtained by modification with silane coupling agent and tannic acid. The zinc-based composite antibacterial and detoxifying adjuvant is a stable sol system formed with zinc-based active ingredients as the core and polyols as the dispersion medium, and its content in the zinc core copolyester component is 0.1~0.3%. The preparation process of the zinc-based active ingredient is as follows: Prepare 100 mL of 0.1 mol / L zinc chloride aqueous solution and 100 mL of 0.4 mol / L sodium hydroxide aqueous solution. Add 7.32 g of Zn powder to the zinc chloride solution, heat to 90℃, add the prepared sodium hydroxide solution, stir for 20 min, centrifuge and filter the precipitate, and dry at 100℃ to obtain the zinc-based active ingredient. The preparation process of the modified halloysite nanotubes is as follows: S21, Pretreated halloysite nanotubes: Halloysite nanotubes were dispersed in dilute hydrochloric acid with a concentration of 1-3 mol / L, stirred at 60-80℃ for 2-4 h, filtered and washed until neutral, and dried in a vacuum oven at 60℃ for 12 h to obtain activated halloysite nanotubes. S22. According to the mass fraction, 10-15 parts of tannic acid, 3-6 parts of 3-isocyanate propyltriethoxysilane, and 0.1-0.3 parts of dibutyltin dilaurate are added to anhydrous N,N-dimethylformamide. Under nitrogen protection, the mixture is stirred at 50-60°C for 10-16 hours. After stirring, the pretreated tannic acid is obtained by rotary evaporation. S23, Covalent grafting: Halloysite nanotubes and pretreated tannic acid were mixed in an ethanol / water solvent with a volume ratio of 95:

5. The pH of the solution was adjusted to 4-5 by adding 0.1 mol / L acetic acid. The mixture was stirred at 55-65°C for 6-10 h. The mass ratio of the pretreated tannic acid to halloysite nanotubes was 1:(1.5-3) to obtain the modified halloysite nanotubes.

2. The synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber according to claim 1, characterized in that, The zinc-based composite antibacterial and detoxifying adjuvant has a particle size of 100-200 nm, and the polyol dispersion medium is one or more of ethylene glycol, propylene glycol and glycerin, with a mass ratio of polyol dispersion medium to zinc-based active ingredient of (3-5):

1.

3. A method for preparing synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber as described in any one of claims 1-2, characterized in that, Includes the following steps: S1. Preparation of zinc core copolyester chips: According to the weight proportions, 100 parts of terephthalic acid and 30-35 parts of ethylene glycol are added to the reactor. Under a nitrogen atmosphere, the mixture is stirred at a speed of 150-200 r / min until homogeneous. Then, the additives and zinc-based composite antibacterial and detoxifying additives are added in sequence. The stirring speed is maintained and the mixture is stirred for 20-30 min. After stirring and mixing, the zinc core copolyester resin is obtained through esterification and polycondensation. S2. Slice preparation: Zinc-core copolyester resin is extruded through an extruder, cooled to room temperature in a cooling water bath, and then cut into polyester chips by a pelletizer. The moisture content of the chips is ≤0.02%. S3, spinning: Polyester chips are fed into a dryer and dried at 120-140°C for 4-6 hours. Modified halloysite nanotubes are then premixed with the polyester chips and heated to 280-290°C to melt. The mixture is then extruded through a spinneret of a spinning machine and subjected to cooling, stretching, crimping, and cutting processes to obtain polyester fiber filaments, thus producing the synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber.

4. The method for preparing synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber according to claim 3, characterized in that, In step S1, the auxiliary agent is a catalyst, a heat stabilizer, and an antioxidant. The catalyst is antimony trioxide or antimony glycolate, and the amount of catalyst added is 0.02~0.05 parts. The heat stabilizer is trimethyl phosphate, and the amount added is 0.01~0.03 parts. The antioxidant is a phosphite compound, and the amount added is 0.03~0.06 parts.

5. The method for preparing synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber according to claim 3, characterized in that, In step S1, the esterification conditions are: 240~260℃, 0.2~0.3MPa, and 3~4h.

6. The method for preparing synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber according to claim 3, characterized in that, In step S1, the conditions for polycondensation are: 275~285℃, vacuum degree ≤100Pa, and time 4~6h.

7. The method for preparing synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber according to claim 3, characterized in that, In step S3, the stretching ratio is 3.5 to 4.5 times, and the number of curls is 8 to 12 per 10 cm.

8. The method for preparing synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber according to claim 3, characterized in that, In step S3, the spinneret has an aperture of 0.2~0.4mm, a cooling air temperature of 20~25℃, and a wind speed of 0.5~1.0m / s.

9. The method for preparing synergistically modified antibacterial, detoxifying, and wear-resistant polyester fiber according to claim 3, characterized in that, In step S3, the modified halloysite nanotubes account for 0.5-2.0% of the mass percentage in the fiber.

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