Antibacterial and warm fabric fiber and preparation method thereof

Abstract

This invention discloses an antibacterial and warm fabric fiber and its preparation method, belonging to the field of fabric fiber processing technology. It addresses the technical problem that the mechanical strength, antibacterial properties, and warming properties of fabric fibers in existing technologies need further improvement. Specifically, it includes the following steps: In an inert gas atmosphere, terephthalic acid, ethylene glycol, PEG-400, sodium 3,5-bis(2-hydroxyethoxycarbonyl)benzenesulfonate, and a catalyst are mixed and stirred. This invention introduces quaternary ammonium salt-containing gel-based particles, silicon-titanium coupled activated epoxy graphene, and azodicarbonamide into a composite polyester matrix, constructing numerous closed and semi-closed air cavities within the hollow fiber. This not only effectively improves the mechanical and antibacterial properties of the fabric fiber material but also enhances the warmth retention and far-infrared emission properties of the fabric fiber, giving the fabric excellent heat storage and feedback capabilities and wearing comfort.

Description

Technical Field

[0001] This invention relates to the field of fabric fiber processing technology, specifically to an antibacterial and warm fabric fiber and its preparation method. Background Technology

[0002] With the improvement of people's living standards and the enhancement of health awareness, textiles are not only required to have good comfort and appearance performance, but also to have a variety of functions, such as warmth, antibacterial properties, and far-infrared radiation. Traditional thermal insulation fiber materials mainly improve thermal performance through hollow structure, composite spinning, or the addition of thermally conductive fillers.

[0003] Current antibacterial fibers typically rely on coating the fiber surface or incorporating inorganic antibacterial agents into the polymer to improve the antibacterial properties of the material. However, these antibacterial agents have drawbacks such as easy migration and loss, poor washability, and degradation of antibacterial performance after long-term use.

[0004] Meanwhile, single antibacterial components often have poor compatibility with polymer matrices, which can easily lead to uneven dispersion during spinning, thus affecting the mechanical properties of the fiber and the overall quality of the fabric. Although traditional polyester fibers have good mechanical properties and heat resistance, they have high thermal conductivity and poor moisture absorption, resulting in limited wearing comfort and warmth. If the insulation effect is improved only through hollow design, the mechanical strength and molding stability of the fiber will be affected. The mechanical strength, antibacterial properties, and warmth retention of the fabric fibers need to be further improved. Summary of the Invention

[0005] The purpose of this invention is to provide an antibacterial and warm fabric fiber and its preparation method, in order to solve the technical problem that the mechanical strength, antibacterial properties and warmness retention properties of fabric fibers in the prior art need to be further improved.

[0006] The objective of this invention can be achieved through the following technical solution: a method for preparing antibacterial and warm fabric fibers, comprising the following steps:

[0007] S1. Under an inert gas atmosphere, terephthalic acid, ethylene glycol, PEG-400, sodium 3,5-bis(2-hydroxyethoxycarbonyl)benzenesulfonate and catalyst are mixed and stirred. The reaction system temperature is raised to 220-240℃ and kept at this temperature for 2-3 hours. The reaction system temperature is then raised to 260-280℃, and the reaction system is evacuated to a negative pressure of 100-180 Pa. The reaction is then kept at this temperature and pressure for 60-80 minutes. 2-(perfluorooctyl)ethyl isocyanate is added to the reaction system, and the reaction is kept at this temperature for 30-50 minutes. After post-treatment, the composite polyester is obtained.

[0008] The synthesis reaction mechanism of composite polyester is as follows:

[0009] Under high temperature and high vacuum conditions, the catalyst promotes the esterification condensation of the carboxyl group at the end of terephthalic acid with the hydroxyl group at the end of ethylene glycol, PEG-400, or sodium 3,5-bis(2-hydroxyethoxycarbonyl)benzenesulfonate molecules. The generated water (byproduct) is removed by vacuum extraction, and the equilibrium is continuously pushed towards the condensation direction, resulting in a rapid increase in the degree of polymerization and the formation of a high molecular weight copolyester chain. In the later stage of polycondensation, 2-(perfluorooctyl)ethyl isocyanate is added. The isocyanate group on the 2-(perfluorooctyl)ethyl isocyanate molecule undergoes an addition reaction with the residual hydroxyl or carboxyl group at the end of the polyester chain, covalently attaching the fluorocarbon segment to the end of the polyester molecule, achieving fluorination end-capping, and preparing a composite polyester.

[0010] S2. The composite polyester, gel-based particles, epoxy activated graphene, azodicarbonamide and auxiliary additives are added to a twin-screw extruder and melt-mixed to obtain the skin layer melt; polyvinylpyrrolidone is heated to melt to obtain the core layer melt, wherein the epoxy activated graphene is KH-560 coated and modified supported graphene.

[0011] S3. The molten cortex and molten core are transported to the melt spinning machine by a metering pump. The melt is spun to form spun fibers with the molten core as the core and the molten cortex as the shell. After hot stretching, the fibers are further processed to obtain antibacterial and warm fabric fibers.

[0012] The synthesis reaction mechanism of antibacterial and warm fabric fibers is as follows:

[0013] During the preparation of the skin layer melt, high temperature promotes the uniform mixing of composite polyester, gel-based particles, epoxy-activated graphene, and azodicarbonamide. The composite polyester, as the main resin, melts to form a continuous phase. The gel-based particles and epoxy-activated graphene are dispersed under the shear force of the screw. The epoxy groups on the epoxy-activated graphene react with the hydroxyl / carboxyl groups on the composite polyester or gel-based particles to form a three-phase chemically bonded interfacial network. Azodicarbonamide, as a chemical foaming agent, decomposes at high temperature to release gas, which is then used for subsequent fiber processing. Microporization provides a latent gas source; polyvinylpyrrolidone in the core melt acts as a soluble sacrificial layer, serving as the core material during spinning. The two are connected via a coaxial spinneret, forming a "core-skin coaxial melt flow." The sheath melt viscosity is slightly higher than the core melt, stabilizing the core and resulting in a sheath-core structure fiber. During cooling, the gas released from the decomposition of azodicarbonamide forms micropores, creating closed or semi-closed microbubbles in the sheath. Simultaneously, graphene and tourmaline components are stretched and oriented along the spinning direction, forming thermally conductive and infrared-reflective channels. Boiling water causes the core to dissolve and escape, leaving a hollow structure. At the same time, high-temperature water promotes the release of residual ADCA gas within the sheath, stabilizing the pores and yielding a finished fiber product with a hollow and microporous sheath, resulting in an antibacterial and warm fabric fiber.

[0014] Further, in step S1, the molar ratio of terephthalic acid, ethylene glycol, PEG-400, sodium 3,5-bis(2-hydroxyethoxycarbonyl)benzenesulfonate, and 2-(perfluorooctyl)ethyl isocyanate is 10:2.5:2.2:4:0.8, the catalyst is antimony trioxide, and the amount of catalyst used is 0.01 times the weight of terephthalic acid. The post-treatment includes: after the reaction is completed, the material is discharged while hot, the reactants are cooled and solidified, sliced, and then transferred to a drying oven at a temperature of 95-105℃ to dry until the moisture content is less than 5ppm, to obtain the composite polyester.

[0015] Further, in step S2, the weight ratio of the composite polyester, gel-based particles, epoxy activated graphene, azodicarbonamide, and auxiliary additives is 70-80:15-18:10-12:3.2-3.5:3-5. The auxiliary additives include internal lubricant, dispersant, antioxidant, light stabilizer, and heat stabilizer. The internal lubricant is ethylene bis-stearamide, the dispersant is stearate, the antioxidant is any one of antioxidant 1010, antioxidant 168, and antioxidant 1076, the light stabilizer is any one of UV-531 and UV-328, and the heat stabilizer is triphenyl phosphate. The temperature of the twin-screw extruder is 230°C in zone I, 240°C in zone II, 240°C in zone III, and 245°C in zone IV, and the melt mixing time is 30 seconds.

[0016] Further, in step S3, the flow rate ratio of the sheath melt and the core melt is 5:2, the temperature of the melt spinning chamber is 260-280℃, side blowing is used for cooling, the side blowing temperature is 25-26℃, the humidity is 40-50%, the hot stretching temperature is 160-180℃, and the stretching ratio is 1.3-1.5 times. The reprocessing includes: cutting the hot-stretched spun fibers into short segments, placing them in boiling purified water, keeping them warm for 50-60 minutes, taking the fibers out of the solution, washing them three times with anhydrous ethanol, and then placing them in a drying oven at a temperature of 70-80℃ to dry to constant weight to obtain fabric fibers.

[0017] Furthermore, the preparation method of gel-based particles is as follows: methyltriethoxysilane, dimethyldiethoxysilane, and trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride are added to a dispersion and stirred at room temperature for 120-150 min. Porous silica and urea are added to the reaction system, the temperature of the reaction system is raised to 75-85℃, stirred for 40-50 min, allowed to stand for 3-4 h, and then post-treated to obtain gel-based particles.

[0018] The synthesis reaction mechanism of gel-based particles is as follows:

[0019] During the reaction, methyltriethoxysilane and dimethyldiethoxysilane generate triol and diol-type silanols, respectively. Trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride hydrolyzes into silanols containing quaternary ammonium side groups. After the addition of porous silica, the hydrolyzed silanols condense and anchor on the surface of the porous silica. The addition of urea and the subsequent heating promote the gradual thermal decomposition of urea, causing the pH of the system to slowly shift from acidic to neutral or even slightly alkaline. The slow increase in pH triggers and accelerates the condensation reaction between silanols, which is beneficial for obtaining small and narrowly distributed particles. The silica support provides heterogeneous nucleation sites and also serves as a framework that is coated / interpenetrated by the organosilicon network, resulting in a hybrid nanogel of "organically modified Si-O-Si network / SiO2". Under negative pressure and heating, low-boiling substances are removed by vacuum evaporation, and the removal of condensation byproducts promotes the continued formation and solidification of Si-O-Si bonds, resulting in gel-based particles.

[0020] Furthermore, the ratio of methyltriethoxysilane, dimethyldiethoxysilane, trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, dispersion, porous silica, and urea is 5g:8g:3g:50mL:2.5-2.8g:1.6g. The dispersion is composed of deionized water, isopropanol, acetic acid, hexadecyltrimethylammonium bromide, and PEG-800 in a ratio of 10mL:2mL:1g:0.3-0.6g:0.8-1g. The post-treatment includes: after the reaction is complete, the reaction system is kept at 75-85℃, and the negative pressure is reduced to -0.1MPa. Under stirring, low-boiling substances are removed by vacuum evaporation. The solid is washed with purified water until neutral and then dried. The filter cake is transferred to a drying oven at 75-85℃ and dried to constant weight. It is then pulverized to obtain gel-based particles with a particle size of 40-60nm.

[0021] Furthermore, epoxy-activated graphene is obtained through the following steps:

[0022] A1. Mix nano-tourmaline powder, nano-zirconium carbide, graphene oxide, and ethanol solution, and ultrasonically disperse for 30-50 min. Add silicon-titanium modifier to the reaction system, react at room temperature for 4-6 h, and then perform post-treatment to obtain supported graphene.

[0023] The synthesis reaction mechanism of supported graphene is as follows:

[0024] Ultrasonication promotes the uniform dispersion of nano-tourmaline powder, nano-zirconium carbide, and graphene oxide. Acetic acid in the ethanol solution provides weakly acidic conditions, allowing the silicon-titanium modifier to slowly hydrolyze in the ethanol solution, generating silanol / titanium alcohol. The surface of graphene oxide contains abundant carboxyl, hydroxyl, and epoxy groups, and the surfaces of tourmaline powder and zirconium carbide also have hydroxyl groups or oxide layers. The generated silanol / titanium alcohol condenses with these surface hydroxyl groups, forming chemical bonds on the surface of graphene oxide sheets and inorganic particles, allowing tourmaline and zirconium carbide to firmly adhere to the graphene surface, thus preparing loaded graphene.

[0025] A2. Mix the supported graphene, KH-560, and anhydrous ethanol, and ultrasonically disperse for 30-50 minutes. Raise the temperature of the reaction system to 50-60℃, add alkaline solution to the reaction system, and keep the reaction at this temperature for 60-80 minutes. After post-treatment, epoxy-activated graphene is obtained.

[0026] The synthesis reaction mechanism of epoxy-activated graphene is as follows:

[0027] The supported graphene and KH-560 were uniformly dispersed in ethanol by ultrasound. Then, the siloxane bonds on the KH-560 molecules were hydrolyzed to form silanols, which chemically bonded to the surface of the supported graphene, forming epoxy groups on the surface of the supported graphene, thus preparing epoxy-activated graphene.

[0028] Further, in step A1, the ratio of the nano-tourmaline powder, nano-zirconium carbide, graphene oxide, ethanol solution, and silicon-titanium modifier is 2.8-3.2g:2.1-2.5g:5g:100mL:2.3-2.5g. The ethanol solution is composed of deionized water, anhydrous ethanol, and acetic acid in a ratio of 7mL:15mL:2g. The silicon-titanium modifier is composed of tetraethyl orthosilicate and tetrabutyl titanate in a weight ratio of 3:1.8-2.0. The post-treatment includes: after the reaction is complete, filtration is performed, the filter cake is washed three times with purified water and then dried, the filter cake is transferred to a drying oven at a temperature of 70-80℃, dried to constant weight, and pulverized to obtain supported graphene.

[0029] Further, in step A2, the ratio of the loaded graphene, KH-560, anhydrous ethanol, and alkaline solution is 10g:2.6-2.8g:100mL:10mL, and the alkaline solution is a 0.8-1mol / L sodium hydroxide solution. The post-treatment includes: after the reaction is complete, the temperature of the reaction system is lowered to room temperature, filtered, the filter cake is washed with purified water until neutral, dried, and the filter cake is transferred to a drying oven at a temperature of 60-70℃ and dried to constant weight to obtain epoxy activated graphene.

[0030] This invention also proposes an antibacterial and warm-keeping fabric fiber, which is prepared using the aforementioned method for preparing an antibacterial and warm-keeping fabric fiber.

[0031] The present invention has the following beneficial effects:

[0032] 1. This invention uses terephthalic acid / ethylene glycol as a backbone, introduces PEG-400 flexible segments and sodium 3,5-bis(2-hydroxyethoxycarbonyl)benzenesulfonate ionic groups, and grafts 2-(perfluorooctyl)ethyl isocyanate at the end of polycondensation to form fluorocarbon chain end caps, constructing a functionalized matrix with flexibility, polarity, and tunable surface energy. This provides a high-affinity, high-anchoring interface platform for gel-based particles and epoxy-activated graphene, significantly improving the dispersion uniformity and interfacial bonding strength of gel-based particles and epoxy-activated graphene particles, inhibiting aggregation and migration loss. Without increasing spinning complexity, it achieves efficient exposure and durability of far-infrared emission and antibacterial functions in the fiber skin. The introduced azodicarbonamide forms micropores in the skin layer, and a stable hollow core layer is obtained by dissolving polyvinylpyrrolidone in the "skin / core" structure. A large number of closed and semi-closed air cavities are constructed in the fiber, which increases the interfacial thermal resistance and significantly reduces the heat transfer coefficient. At the same time, under the effect of interfacial reinforcement, the fiber maintains the required breaking strength and high breaking elongation, ensuring the spinning and weaving processability. The synergy between the polar groups of the composite polyester and the fluorinated segments on the skin surface has a composite antibacterial pathway of "anti-adhesion + contact sterilization", which improves the antibacterial performance of the fiber material. Meanwhile, the low polarizability of the fluorocarbon segments and the interfacial discontinuity also contribute to phonon scattering, synergistically reducing the heat transfer coefficient of the material.

[0033] 2. This invention also utilizes organosilane co-condensation, surfactant regulation, and porous silica filling to form organic-inorganic hybrid gel-based particles. The gel-based particles have a porous silica framework, with an outer layer formed by the co-condensation of methyltriethoxysilane, dimethyldiethoxysilane, and quaternary ammonium silane to create a flexible organosilicon network structure, possessing both rigidity and toughness. The surface of the gel-based particles is coated with flexible organosilane chains and polyether segments. The siloxane bonds and ether groups on the particle surface can form hydrogen bonds and polar interactions with the hydroxyl and ester groups in the composite polyester, improving interfacial bonding and avoiding the stress concentration phenomenon of traditional inorganic fillers. During stretching, the particles can move along with the polyester... Synergistic deformation of chain segments delays crack initiation and improves ductility in the early stages of fiber stretching. Meanwhile, the nanoscale size and good dispersion of particles form a "rigid-flexible" micro-network in the composite system, providing support while allowing local chain segment slippage, thereby enhancing the mechanical strength of the fiber material. The low thermal conductivity and porous structure of the gel-based particles effectively block heat flow and significantly reduce the heat transfer coefficient. In synergy with far-infrared functional fillers such as tourmaline and zirconium carbide, they enhance infrared radiation absorption and re-emission, achieving lightweight and efficient warmth retention. The fixed quaternary ammonium salt cationic groups on the particle surface endow the fiber with significant and long-lasting contact bactericidal ability.

[0034] 3. This invention also employs silicon-titanium coupling and epoxy-silane activated graphene carriers to efficiently load and stably anchor nano-tourmaline and zirconium carbide on two-dimensional sheets, resulting in epoxy-activated graphene. Loading tourmaline and zirconium carbide roughens the sheet surface and increases polarity. Combined with a coupling agent, it inhibits secondary graphene agglomeration, reduces stress concentration, and epoxy activation enhances the interfacial bonding strength and dispersibility between the graphene material and the composite polyester matrix, significantly improving stress transfer efficiency. While maintaining the hollow and microporous structure, it maintains high fracture strength and increases elongation at break by limiting necking and dissipating energy. Nano-tourmaline powder and nano-zirconium carbide loaded on graphene can generate far-infrared rays when excited by external energy. Through the superposition of the absorption-re-radiation characteristics of graphene and with the help of the multi-interface light trapping effect, the far-infrared emissivity of the fabric is improved, giving the fabric excellent heat storage and feedback capabilities and wearing comfort. The sheet structure of graphene has sharp edges, which can disrupt the structural integrity of cell membranes, causing the leakage of substances inside bacterial cells, thereby killing bacteria. The silicon-titanium modifier introduced on graphene and the surface potential effect of tourmaline work together to further improve the antibacterial properties of the fiber material. Detailed Implementation

[0035] The technical solution of the present invention will be clearly and completely described below with reference to the embodiments. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0036] In this invention, the porous silica is a commercially available material selected from Zhengzhou Songshan Boron Industry Technology Co., Ltd., with an effective component content of 99.8%, a particle size of 10-20 nm, and a specific surface area of ​​180-1220 m². 2 / g;

[0037] In this invention, the nano-tourmaline powder is 20,000 mesh white tourmaline powder, selected from Shijiazhuang Xu'ang Mineral Products Processing Co., Ltd.;

[0038] In this invention, the nano-zirconium carbide has a particle size of 50-300 nm and an effective component content of 99.99%, and is selected from Shanghai Yingfeng Ruihuang Metal Materials Co., Ltd.

[0039] In this invention, KH-560 is γ-glycidyl etheroxypropyltrimethoxysilane, CAS No. 2530-83-8;

[0040] In this invention, PEG-800 has an average molecular weight of 800 and an effective ingredient content of 99%, and is selected from Jinan Zhuoyue Chemical Technology Co., Ltd.

[0041] In this invention, PEG-400 has an average molecular weight of 400 and an effective ingredient content of 99%, and is selected from Jinan Zhuoyue Chemical Technology Co., Ltd.

[0042] In this invention, the polyvinylpyrrolidone is model PVP-K90, with an active ingredient content of 99%, and is selected from Greenlink (Jining) Chemical Technology Co., Ltd.

[0043] Example 1

[0044] This embodiment provides a method for preparing antibacterial and warm fabric fibers, which includes the following steps:

[0045] Step S1: Preparation of gel-based particles

[0046] Deionized water, isopropanol, acetic acid, hexadecyltrimethylammonium bromide, and PEG-800 were mixed evenly at a ratio of 10 mL: 2 mL: 1 g: 0.3 g: 0.8 g to obtain a dispersion.

[0047] Weigh out 20g of methyltriethoxysilane, 32g of dimethyldiethoxysilane, 12g of trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, and 200mL of dispersion and add them to a reaction flask. Stir and disperse at room temperature for 120min. Fix the reaction flask on an iron stand with mechanical stirring and add 10g of porous silica and 6.4g of urea to the reaction flask. Raise the temperature of the reaction flask to 75℃ and stir for 40min. Let it stand for 3h. Keep the reaction flask at 75℃ and apply a negative pressure to -0.1MPa. Under stirring, remove low-boiling substances by vacuum evaporation. Wash the solid with purified water until neutral and then dry it. Transfer the filter cake to a drying oven at 75℃ and dry it to constant weight. Crush the cake to obtain gel-based particles with a particle size of 40-60nm.

[0048] Step S2: Preparation of epoxy-activated graphene

[0049] Deionized water, anhydrous ethanol, and acetic acid were mixed thoroughly at a ratio of 7 mL: 15 mL: 2 g to obtain an ethanol solution.

[0050] Tetrabutyl titanate and tetrabutyl titanate were mixed evenly at a weight ratio of 3:1.8 to obtain a silicon-titanium modifier.

[0051] Weigh out 28g of nano-tourmaline powder, 21g of nano-zirconium carbide, 50g of graphene oxide, and 1000mL of ethanol solution and add them to a reaction flask. Mix and ultrasonically disperse for 30min. Fix the reaction flask on an iron stand with mechanical stirring and stir. Add 23g of silicon-titanium modifier to the reaction flask and react at room temperature for 4h. Filter and wash the filter cake three times with purified water and dry it. Transfer the filter cake to a drying oven at 70℃ and dry it to constant weight. Crush it to obtain supported graphene.

[0052] Weigh out 100g of supported graphene, 26g of KH-560, and 1000mL of anhydrous ethanol and add them to a reaction flask. Disperse the mixture by sonication for 30min. Raise the temperature of the reaction flask to 50℃ and add 100mL of 0.8mol / L sodium hydroxide solution. Keep the mixture warm for 60min. Lower the temperature of the reaction flask to room temperature and filter. Wash the filter cake with purified water until neutral and then dry it. Transfer the filter cake to a drying oven at 60℃ and dry it to constant weight to obtain epoxy activated graphene.

[0053] Step S3: Preparation of composite polyester

[0054] Weigh out 166.1g of terephthalic acid, 15.5g of ethylene glycol, 88g of PEG-400, 179.2g of sodium 3,5-bis(2-hydroxyethoxycarbonyl)benzenesulfonate, and 1.7g of antimony trioxide catalyst, and add them to a high-pressure reaction flask under argon protection. Stir the mixture and raise the temperature of the reaction flask to 220℃. Maintain the temperature for 2 hours. Raise the temperature of the reaction flask to 260℃, apply a negative pressure of 100Pa, and maintain the temperature and pressure for 60 minutes. Add 39.1g of 2-(perfluorooctyl)ethyl isocyanate to the reaction flask and maintain the temperature for 30 minutes. Discharge the mixture while it is still hot. After the reactants have cooled and solidified, slice them and transfer them to a drying oven at 95℃. Dry them until the moisture content is 5ppm to obtain the composite polyester.

[0055] Step S4: Prepare the skin melt and core melt

[0056] Ethylene bis-stearamide, zinc stearate, antioxidant 1010, light stabilizer UV-531, and triphenyl phosphate were mixed evenly in a weight ratio of 2:3:5:3:1 to obtain the auxiliary additive.

[0057] Weigh out the following components by weight: 70 parts of composite polyester, 15 parts of gel-based particles, 10 parts of epoxy activated graphene, 3.2 parts of azodicarbonamide, and 3 parts of auxiliary additives. Add these components to a twin-screw extruder. Set the temperature of zone I of the twin-screw extruder to 230℃, zone II to 240℃, zone III to 240℃, and zone IV to 245℃. Melt and mix for 30 seconds to obtain the skin melt.

[0058] Polyvinylpyrrolidone is heated to melt to obtain the core layer melt.

[0059] Step S5: Prepare antibacterial and warm fabric fibers

[0060] The molten sheath and molten core are pumped into a melt spinning machine at a chamber temperature of 260°C using a metering pump at a flow rate ratio of 5:2. Melt spinning is then performed using side-blowing cooling at a temperature of 25°C and a humidity of 40%, forming spun fibers with the molten core as the core and the molten sheath as the shell. The spun fibers are then hot-stretched at a ratio of 1.3 at a temperature of 160°C. The hot-stretched fibers are then cut into short segments and placed in boiling purified water for 50 minutes. The fibers are then removed from the solution, washed three times with anhydrous ethanol, and finally placed in a drying oven at 70°C to dry to constant weight, yielding antibacterial and warm fabric fibers.

[0061] Example 2

[0062] This embodiment provides a method for preparing antibacterial and warm fabric fibers, which includes the following steps:

[0063] Step S1: Preparation of gel-based particles

[0064] Deionized water, isopropanol, acetic acid, hexadecyltrimethylammonium bromide, and PEG-800 were mixed evenly at a ratio of 10 mL: 2 mL: 1 g: 0.45 g: 0.9 g to obtain a dispersion.

[0065] Weigh out 20g of methyltriethoxysilane, 32g of dimethyldiethoxysilane, 12g of trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, and 200mL of dispersion and add them to a reaction flask. Stir and disperse at room temperature for 135min. Fix the reaction flask on an iron stand with mechanical stirring and add 10.6g of porous silica and 6.4g of urea to the reaction flask. Raise the temperature of the reaction flask to 80℃ and stir for 45min. Let it stand for 3.5h. Keep the reaction flask at 80℃ and apply a negative pressure to -0.1MPa. Under stirring, remove low-boiling substances by vacuum evaporation. Wash the solid with purified water until neutral and then dry it. Transfer the filter cake to a drying oven at 80℃ and dry it to constant weight. Crush the cake to obtain gel-based particles with a particle size of 40-60nm.

[0066] Step S2: Preparation of epoxy-activated graphene

[0067] Deionized water, anhydrous ethanol, and acetic acid were mixed thoroughly at a ratio of 7 mL: 15 mL: 2 g to obtain an ethanol solution.

[0068] Tetrabutyl titanate and tetrabutyl titanate were mixed evenly at a weight ratio of 3:1.9 to obtain a silicon-titanium modifier.

[0069] Weigh out 30g of nano-tourmaline powder, 23g of nano-zirconium carbide, 50g of graphene oxide, and 1000mL of ethanol solution and add them to a reaction flask. Mix and ultrasonically disperse for 40min. Fix the reaction flask on an iron stand with mechanical stirring and stir. Add 24g of silicon-titanium modifier to the reaction flask and react at room temperature for 5h. Filter and wash the filter cake three times with purified water and dry it. Transfer the filter cake to a drying oven at 75℃ and dry it to constant weight. Crush it to obtain supported graphene.

[0070] Weigh out 100g of supported graphene, 27g of KH-560, and 1000mL of anhydrous ethanol and add them to a reaction flask. Disperse the mixture by sonication for 40min. Raise the temperature of the reaction flask to 55℃ and add 100mL of 0.9mol / L sodium hydroxide solution. Keep the mixture warm for 70min. Lower the temperature of the reaction flask to room temperature and filter. Wash the filter cake with purified water until neutral and then dry it. Transfer the filter cake to a drying oven at 65℃ and dry it to constant weight to obtain epoxy activated graphene.

[0071] Step S3: Preparation of composite polyester

[0072] Weigh out 166.1g of terephthalic acid, 15.5g of ethylene glycol, 88g of PEG-400, 179.2g of sodium 3,5-bis(2-hydroxyethoxycarbonyl)benzenesulfonate, and 1.7g of antimony trioxide catalyst, and add them to a high-pressure reaction flask under argon protection. Stir the mixture, raise the temperature of the reaction flask to 230℃, and maintain the temperature for 2.5h. Raise the temperature of the reaction flask to 270℃, apply a negative pressure of 140Pa, and maintain the temperature and pressure for 70min. Add 39.1g of 2-(perfluorooctyl)ethyl isocyanate to the reaction flask, and maintain the temperature for 40min. Discharge the mixture while it is still hot. After the reactants are cooled and solidified, slice them and transfer them to a drying oven at 100℃ to dry until the moisture content is 4ppm to obtain the composite polyester.

[0073] Step S4: Prepare the skin melt and core melt

[0074] Ethylene bis-stearamide, calcium stearate, antioxidant 168, light stabilizer UV-328, and triphenyl phosphate were mixed evenly in a weight ratio of 2:3:5:3:1 to obtain the auxiliary additive.

[0075] Weigh out the following components by weight: 75 parts of composite polyester, 16.5 parts of gel-based particles, 11 parts of epoxy activated graphene, 3.4 parts of azodicarbonamide, and 4 parts of auxiliary additives. Add these components to a twin-screw extruder. Set the temperature of zone I of the twin-screw extruder to 230℃, zone II to 240℃, zone III to 240℃, and zone IV to 245℃. Melt and mix for 30 seconds to obtain the skin melt.

[0076] Polyvinylpyrrolidone is heated to melt to obtain the core layer melt.

[0077] Step S5: Prepare antibacterial and warm fabric fibers

[0078] The molten sheath and molten core are pumped into a melt spinning machine at a chamber temperature of 270°C using a metering pump at a flow rate ratio of 5:2. Melt spinning is then performed, with side-blowing cooling at a temperature of 25.5°C and a humidity of 45%. This forms spun fibers with the molten core as the core and the molten sheath as the shell. The spun fibers are then hot-stretched at a ratio of 1.4 at a temperature of 170°C. The hot-stretched fibers are then cut into short segments and placed in boiling purified water for 55 minutes. The fibers are then removed from the solution, washed three times with anhydrous ethanol, and finally placed in a drying oven at 75°C to dry to constant weight, yielding antibacterial and warm fabric fibers.

[0079] Example 3

[0080] This embodiment provides a method for preparing antibacterial and warm fabric fibers, which includes the following steps:

[0081] Step S1: Preparation of gel-based particles

[0082] Deionized water, isopropanol, acetic acid, hexadecyltrimethylammonium bromide, and PEG-800 were mixed evenly at a ratio of 10 mL: 2 mL: 1 g: 0.6 g: 1 g to obtain a dispersion.

[0083] Weigh out 20g of methyltriethoxysilane, 32g of dimethyldiethoxysilane, 12g of trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, and 200mL of dispersion and add them to a reaction flask. Stir and disperse at room temperature for 150min. Fix the reaction flask on an iron stand with mechanical stirring and add 11.2g of porous silica and 6.4g of urea to the reaction flask. Raise the temperature of the reaction flask to 85℃ and stir for 50min. Let it stand for 4h. Keep the reaction flask at 85℃ and apply a negative pressure to -0.1MPa. Under stirring, remove low-boiling substances by vacuum evaporation. Wash the solid with purified water until neutral and then dry it. Transfer the filter cake to a drying oven at 85℃ and dry it to constant weight. Crush the cake to obtain gel-based particles with a particle size of 40-60nm.

[0084] Step S2: Preparation of epoxy-activated graphene

[0085] Deionized water, anhydrous ethanol, and acetic acid were mixed thoroughly at a ratio of 7 mL: 15 mL: 2 g to obtain an ethanol solution.

[0086] Tetrabutyl titanate and tetrabutyl titanate were mixed evenly at a weight ratio of 3:2.0 to obtain a silicon-titanium modifier.

[0087] Weigh out 32g of nano-tourmaline powder, 25g of nano-zirconium carbide, 50g of graphene oxide, and 1000mL of ethanol solution and add them to a reaction flask. Mix and ultrasonically disperse for 50min. Fix the reaction flask on an iron stand with mechanical stirring and stir. Add 25g of silicon-titanium modifier to the reaction flask and react at room temperature for 6h. Filter and wash the filter cake three times with purified water and dry it. Transfer the filter cake to a drying oven at 80℃ and dry it to constant weight. Crush it to obtain supported graphene.

[0088] Weigh out 100g of supported graphene, 28g of KH-560, and 1000mL of anhydrous ethanol and add them to a reaction flask. Disperse the mixture by sonication for 50min. Raise the temperature of the reaction flask to 60℃ and add 100mL of 1mol / L sodium hydroxide solution. Keep the mixture warm for 80min. Lower the temperature of the reaction flask to room temperature and filter. Wash the filter cake with purified water until neutral and then dry it. Transfer the filter cake to a drying oven at 70℃ and dry it to constant weight to obtain epoxy activated graphene.

[0089] Step S3: Preparation of composite polyester

[0090] Weigh out 166.1g of terephthalic acid, 15.5g of ethylene glycol, 88g of PEG-400, 179.2g of sodium 3,5-bis(2-hydroxyethoxycarbonyl)benzenesulfonate, and 1.7g of antimony trioxide catalyst, and add them to a high-pressure reaction flask under argon protection. Stir the mixture and raise the temperature of the reaction flask to 240℃. Maintain the temperature for 3 hours. Raise the temperature of the reaction flask to 280℃, apply a negative pressure of 180Pa, and maintain the temperature and pressure for 80 minutes. Add 39.1g of 2-(perfluorooctyl)ethyl isocyanate to the reaction flask and maintain the temperature for 50 minutes. Discharge the mixture while it is still hot. After the reactants have cooled and solidified, slice them and transfer them to a drying oven at 105℃. Dry them until the moisture content is 3ppm to obtain the composite polyester.

[0091] Step S4: Prepare the skin melt and core melt

[0092] Ethylene bis-stearamide, barium stearate, antioxidant 1076, light stabilizer UV-531, and triphenyl phosphate were mixed evenly in a weight ratio of 2:3:5:3:1 to obtain the auxiliary additive.

[0093] Weigh out the following components by weight: 80 parts of composite polyester, 18 parts of gel-based particles, 12 parts of epoxy activated graphene, 3.5 parts of azodicarbonamide, and 5 parts of auxiliary additives. Add these components to a twin-screw extruder. Set the temperature of zone I of the twin-screw extruder to 230℃, zone II to 240℃, zone III to 240℃, and zone IV to 245℃. Melt and mix for 30 seconds to obtain the skin melt.

[0094] Polyvinylpyrrolidone is heated to melt to obtain the core layer melt.

[0095] Step S5: Prepare antibacterial and warm fabric fibers

[0096] The molten sheath and molten core are pumped into a melt spinning machine at a chamber temperature of 280°C using a metering pump at a flow rate ratio of 5:2. Melt spinning is then performed, with side-blowing cooling at a temperature of 26°C and a humidity of 50%. This forms spun fibers with the molten core as the core and the molten sheath as the shell. The spun fibers are then hot-stretched at a rate of 1.5 at a temperature of 180°C. The hot-stretched fibers are then cut into short segments and placed in boiling purified water for 60 minutes. The fibers are then removed from the solution, washed three times with anhydrous ethanol, and finally placed in a drying oven at 80°C to dry to a constant weight, yielding antibacterial and warm fabric fibers.

[0097] Comparative Example 1

[0098] The difference between this comparative example and Example 3 is that trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride was not added in step S1.

[0099] Comparative Example 2

[0100] The difference between this comparative example and Example 3 is that no titanium-silicon modifier was added in step S2.

[0101] Comparative Example 3

[0102] The difference between this comparative example and Example 3 is that nano-tourmaline powder and nano-zirconium carbide were not added in step S2.

[0103] Comparative Example 4

[0104] The difference between this comparative example and Example 3 is that 2-(perfluorooctyl)ethyl isocyanate was not added in step S3.

[0105] Comparative Example 5

[0106] The difference between this comparative example and Example 3 is that azodicarbonamide was not added to the skin melt in step S4.

[0107] Performance testing:

[0108] The breaking strength, breaking elongation, and antibacterial rate of the antibacterial and warm fabric fiber samples prepared in Examples 1-3 and Comparative Examples 1-5 were determined according to standard FZ / T 52035-2014 "Antibacterial Polyester Staple Fiber".

[0109] Using the antibacterial and warm fabric fibers prepared in Examples 1-3 and Comparative Examples 1-5 as raw materials, the fabrics were spun into fibers with a thickness of 0.3 mm and a density of 105 g / m³. 2 The fabric was used as a sample to measure the heat transfer coefficient and far-infrared emissivity of the sample.

[0110] The heat transfer coefficient was determined in accordance with the standard GB / T 35762-2017 "Test Methods for Heat Transfer Properties of Textiles - Plate Method";

[0111] The far-infrared emissivity was measured in accordance with the standard GB / T 30127-2013 "Test and Evaluation of Far-Infrared Performance of Textiles". The specific test data are shown in Table 1 below.

[0112] Table 1 - Performance Test Data of Samples

[0113]

[0114] Data Analysis:

[0115] Comparative analysis of the data in Table 1 shows that the antibacterial and warm fabric fiber sample prepared by this invention has a breaking strength of 3.6 cN / dtex, a breaking elongation of 38%, an antibacterial rate of 99.7% against Staphylococcus aureus, and an antibacterial rate of 99.5% against Escherichia coli. The heat transfer coefficient of the fabric sample prepared from the fabric fiber reaches 0.032 W / (m·K), and the far-infrared emissivity reaches 0.93. All performance test data are superior to the comparative example. This indicates that this invention prepares a foamed skin melt by introducing quaternary ammonium salt-containing gel-based particles, silicon-titanium coupled activated epoxy graphene, and azodicarbonamide into the composite polyester matrix, and combines it with the polyvinylpyrrolidone core layer to construct a large number of closed and semi-closed air cavities within the hollow fiber. This not only effectively improves the mechanical and antibacterial properties of the fabric fiber material, but also improves the warmth retention and far-infrared emissivity of the fabric fiber, giving the fabric excellent heat storage and feedback capabilities and wearing comfort.

[0116] The preferred embodiments of the present invention disclosed above are merely illustrative of the invention. These preferred embodiments do not exhaustively describe all details, nor do they limit the invention to specific implementations. Clearly, many modifications and variations can be made based on the content of this specification. This specification selects and specifically describes these embodiments to better explain the principles and practical applications of the invention, thereby enabling those skilled in the art to better understand and utilize the invention. The invention is limited only by the claims and their full scope and equivalents.

Claims

1. A method of preparing a bacteria-inhibiting, warmth-retaining fabric fiber, characterized by, Includes the following steps: S1. Under an inert gas atmosphere, terephthalic acid, ethylene glycol, PEG-400, sodium 3,5-bis(2-hydroxyethoxycarbonyl)benzenesulfonate and catalyst are mixed and stirred. The reaction system temperature is raised to 220-240℃ and kept at this temperature for 2-3 hours. The reaction system temperature is then raised to 260-280℃, and the reaction system is evacuated to a negative pressure of 100-180 Pa and kept at this temperature and pressure for 60-80 minutes. 2-(perfluorooctyl)ethyl isocyanate is added to the reaction system, and the reaction is kept at this temperature for 30-50 minutes. After post-treatment, a composite polyester is obtained. The molar ratio of terephthalic acid, ethylene glycol, PEG-400, sodium 3,5-bis(2-hydroxyethoxycarbonyl)benzenesulfonate, and 2-(perfluorooctyl)ethyl isocyanate is 10:2.5:2.2:4:0.

8. The catalyst is antimony trioxide, and the amount of catalyst used is 0.01 times the weight of terephthalic acid. S2. The composite polyester, gel-based particles, epoxy-activated graphene, azodicarbonamide, and auxiliary additives are added to a twin-screw extruder and melt-mixed to obtain a skin layer melt; polyvinylpyrrolidone is heated to melt to obtain a core layer melt, wherein the epoxy-activated graphene is KH-560 coated and modified supported graphene, and the weight ratio of the composite polyester, gel-based particles, epoxy-activated graphene, azodicarbonamide, and auxiliary additives is 70-80:15-18:10-12:3.2-3.5:3-5; S3. The sheath melt and core melt are transported to the melt spinning machine by a metering pump for melt spinning to form spun fibers with the core melt as the core and the sheath melt as the shell. After hot stretching, the fibers are further processed to obtain antibacterial and warm fabric fibers. The flow rate ratio of the sheath melt to the core melt is 5:

2. The temperature of the melt spinning chamber is 260-280℃. Side blowing is used for cooling. The side blowing temperature is 25-26℃ and the humidity is 40-50%. The hot stretching temperature is 160-180℃ and the stretching ratio is 1.3-1.5 times. The preparation method of gel-based particles is as follows: methyltriethoxysilane, dimethyldiethoxysilane, and trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride are added to a dispersion and stirred at room temperature for 120-150 min. Porous silica and urea are added to the reaction system, the temperature of the reaction system is raised to 75-85℃, stirred for 40-50 min, allowed to stand for 3-4 h, and then post-treated to obtain gel-based particles. Epoxy-activated graphene is obtained through the following steps: A1. Mix nano-tourmaline powder, nano-zirconium carbide, graphene oxide, and ethanol solution, and ultrasonically disperse for 30-50 min. Add silicon-titanium modifier to the reaction system, react at room temperature for 4-6 h, and then perform post-treatment to obtain supported graphene. A2. Mix the supported graphene, KH-560, and anhydrous ethanol, and ultrasonically disperse for 30-50 minutes. Raise the temperature of the reaction system to 50-60℃, add alkaline solution to the reaction system, and keep the reaction at this temperature for 60-80 minutes. After post-treatment, epoxy-activated graphene is obtained.

2. A process for the preparation of an antibacterial and warm fabric fiber as claimed in claim 1, wherein, In step S1, the post-processing includes: after the reaction is completed, the material is discharged while hot, the reactants are cooled and solidified and then sliced, and then transferred to a drying oven at a temperature of 95-105℃ to dry until the moisture content is less than 5ppm to obtain composite polyester.

3. A process for the preparation of an antibacterial and warm fabric fiber as claimed in claim 1, wherein, In step S2, the auxiliary additives include an internal lubricant, a dispersant, an antioxidant, a light stabilizer, and a heat stabilizer. The internal lubricant is ethylene bis-stearamide, the dispersant is stearate, the antioxidant is any one of antioxidant 1010, antioxidant 168, and antioxidant 1076, the light stabilizer is any one of UV-531 and UV-328, and the heat stabilizer is triphenyl phosphate. The temperature of the twin-screw extruder is 230°C in zone I, 240°C in zone II, 240°C in zone III, and 245°C in zone IV, and the melt mixing time is 30 seconds.

4. The method for preparing an antibacterial and warm fabric fiber according to claim 1, characterized in that, In step S3, the reprocessing includes: cutting the hot-stretched spun fibers into short segments, placing them in boiling purified water, keeping them warm for 50-60 minutes, taking the fibers out of the solution, washing them three times with anhydrous ethanol, and then placing them in a drying oven at a temperature of 70-80℃ to dry to constant weight to obtain fabric fibers.

5. The method for preparing an antibacterial and warm fabric fiber according to claim 1, characterized in that, The ratio of methyltriethoxysilane, dimethyldiethoxysilane, trimethyl[3-(trimethoxysilyl)propyl]ammonium chloride, dispersion, porous silica, and urea is 5g:8g:3g:50mL:2.5-2.8g:1.6g. The dispersion is composed of deionized water, isopropanol, acetic acid, hexadecyltrimethylammonium bromide, and PEG-800 in a ratio of 10mL:2mL:1g:0.3-0.6g:0.8-1g. The post-treatment includes: after the reaction is complete, the reaction system is kept at 75-85℃, and the negative pressure is reduced to -0.1MPa. Under stirring, low-boiling substances are removed by vacuum evaporation. The solid is washed with purified water until neutral and then dried. The filter cake is transferred to a drying oven at 75-85℃ and dried to constant weight. It is then pulverized to obtain gel-based particles with a particle size of 40-60nm.

6. The method for preparing an antibacterial and warm fabric fiber according to claim 1, characterized in that, In step A1, the ratio of the nano-tourmaline powder, nano-zirconium carbide, graphene oxide, ethanol solution, and silicon-titanium modifier is 2.8-3.2g:2.1-2.5g:5g:100mL:2.3-2.5g. The ethanol solution is composed of deionized water, anhydrous ethanol, and acetic acid in a ratio of 7mL:15mL:2g. The silicon-titanium modifier is composed of tetraethyl orthosilicate and tetrabutyl titanate in a weight ratio of 3:1.8-2.

0. The post-treatment includes: after the reaction is complete, filtration is performed, the filter cake is washed three times with purified water and then dried, the filter cake is transferred to a drying oven at a temperature of 70-80℃, dried to constant weight, and pulverized to obtain supported graphene.

7. The method for preparing an antibacterial and warm fabric fiber according to claim 1, characterized in that, In step A2, the ratio of the loaded graphene, KH-560, anhydrous ethanol, and alkaline solution is 10g:2.6-2.8g:100mL:10mL, and the alkaline solution is a 0.8-1mol / L sodium hydroxide solution. The post-treatment includes: after the reaction is complete, the temperature of the reaction system is lowered to room temperature, filtered, the filter cake is washed with purified water until neutral, dried, and the filter cake is transferred to a drying oven at a temperature of 60-70℃ and dried to constant weight to obtain epoxy activated graphene.

8. A fabric fiber with antibacterial and warm properties, characterized in that, The antibacterial and warm fabric fiber is prepared using the method described in any one of claims 1-7 for preparing antibacterial and warm fabric fibers.

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