Preparation method of recycled polyester tourmaline antibacterial cloud wool

Abstract

The application discloses a preparation method of regenerated polyester tourmaline antibacterial cloud wool, and relates to the technical field of cloud wool.The application is characterized in that: firstly, a silane coupling agent is used to modify tourmaline, and amino groups are introduced on the surface of the tourmaline to provide active sites for subsequent preparation of nano titanium dioxide; then, the modified tourmaline is added into a titanium dioxide sol, and nano titanium dioxide is grown on the tourmaline in situ through a sol-gel method to obtain a nano titanium dioxide / tourmaline composite carrier; then, the amino groups on the surface of the nano titanium dioxide / tourmaline composite carrier which are not involved in coordination are further activated, and the activated amino groups are allowed to react with p-xylene dicarboxaldehyde to load a Schiff base structure on the surface of the nano titanium dioxide / tourmaline composite carrier to prepare a novel antibacterial agent; the Schiff base structure is anchored on the surface of the composite carrier through a covalent bond, organic antibacterial components are immobilized, and the antibacterial performance is further improved; finally, the novel antibacterial agent is blended with regenerated polyester to prepare regenerated polyester tourmaline antibacterial cloud wool through wet spinning, so that the cloud wool has long-acting and high-efficiency antibacterial effect.

Description

Technical Field

[0001] This invention relates to the field of cloud fleece technology, specifically to a method for preparing recycled polyester tourmaline antibacterial cloud fleece. Background Technology

[0002] As the global "dual carbon" goal is advanced, the textile industry is accelerating its transformation towards green and low-carbon practices. Recycled polyester has become a core alternative raw material for the industry because it can effectively save petroleum resources and reduce waste pollution.

[0003] Furthermore, with increasing health awareness, the antibacterial properties of textiles, which come into close contact with the human body, are receiving more and more attention. In daily use, fleece fabrics, due to their loose fiber structure and large surface area, easily absorb sweat, dander, and other organic matter, providing a breeding ground for bacteria (such as Staphylococcus aureus and Escherichia coli), fungi, and other microorganisms. This can lead to odors, mildew, and even skin allergies and infections, especially in humid or sweaty environments. Fleece, with its lightweight, warmth, and softness, is widely used in home textiles, clothing linings, and infant products. However, without effective antibacterial properties, its lifespan is shortened, and the user experience and health safety are directly affected. Therefore, developing antibacterial fleece that combines the excellent performance of fleece with reliable antibacterial capabilities has become an urgent market demand. Summary of the Invention

[0004] The purpose of this invention is to provide a method for preparing recycled polyester tourmaline antibacterial cloud fleece, so as to solve the problems existing in the prior art.

[0005] To solve the above-mentioned technical problems, the present invention provides the following technical solution: a recycled polyester tourmaline antibacterial cloud wool, wherein the recycled polyester tourmaline antibacterial cloud wool is obtained by extruding a novel antibacterial agent and recycled polyester chips into a screw extruder to obtain a mixed masterbatch, and then by wet spinning.

[0006] The novel antibacterial agent is prepared by growing nano-titanium dioxide in situ on the surface of modified tourmaline to obtain a nano-titanium dioxide / tourmaline composite carrier, and then reacting it with terephthalaldehyde to load a Schiff base structure.

[0007] Furthermore, the modified tourmaline is prepared by modifying tourmaline with KH550 silane coupling agent.

[0008] Furthermore, the tourmaline is either iron tourmaline or lithium tourmaline.

[0009] Furthermore, a method for preparing recycled polyester tourmaline antibacterial cloud-like fleece includes the following preparation steps:

[0010] (1) Mix activated tourmaline and anhydrous ethanol at a solid-liquid ratio of 1:2, add 0.01 to 0.05 times the mass of activated tourmaline KH550, add ammonia dropwise under stirring until the pH is 9 to 10, react at 50 to 60°C for 4 hours, centrifuge, wash, and vacuum dry at 60°C for 4 to 6 hours to obtain modified tourmaline;

[0011] (2) The modified tourmaline and titanium dioxide sol were mixed at a solid-liquid ratio of 1:10~15, ultrasonically dispersed for 30 min, stirred at room temperature for 1~2 h, heated in a water bath at 60℃ for 1~1.5 h, centrifuged to separate the solid, washed, dried, and placed in a muffle furnace to calcine at 400℃ for 1.5~3 h to obtain nano titanium dioxide / tourmaline composite carrier;

[0012] (3) Mix nano-titanium dioxide / tourmaline composite carrier, terephthalaldehyde and ethanol, add acetic acid dropwise, adjust the pH to 5~6, heat the reaction in a water bath at 50~60℃ for 1~2h, filter, wash and dry to obtain a new antibacterial agent;

[0013] (4) Mix recycled polyester, novel antibacterial agent and mixed aqueous solution in a mass ratio of 1:0.05~0.10:6~8, stir at 25~30℃ for 30 minutes, and then wet spin through a cloud-spun spinneret to obtain hollow shaped fibers. After shaping, bundling, rapid stretching and three-dimensional crimping, the recycled polyester tourmaline antibacterial cloud-spun fibers are heat-set to obtain recycled polyester tourmaline antibacterial cloud-spun fibers.

[0014] Furthermore, in step (1), the activated tourmaline is prepared by mixing tourmaline and 1 mol / L hydrochloric acid at a solid-liquid ratio of 1:5, stirring and refluxing at 80°C for 1-2 hours, filtering, washing with deionized water until neutral, adding it to anhydrous ethanol at a solid-liquid ratio of 1:2, sonicating for 30 minutes, and vacuum drying at 60°C for 2-4 hours.

[0015] Further, the preparation method of titanium dioxide sol in step (2) is as follows: 1) using anhydrous ethanol as solvent, glacial acetic acid as catalyst, tetrabutyl titanate as precursor, the mass fraction of tetrabutyl titanate in the solution is 20%~35%, mix to form a solution, hydrolyze at 50~60℃ for 6h, then age for 12h, and extract the solvent under reduced pressure at 60~80℃ to obtain nano titanium dioxide dry gel; 2) use deionized water to prepare the above nano titanium dioxide dry gel into nano titanium dioxide sol with a concentration of 20~50wt%.

[0016] Furthermore, in step (3), the mass ratio of nano-titanium dioxide / tourmaline composite carrier, terephthalaldehyde and ethanol is 1:0.2~0.6:20~25.

[0017] Furthermore, in step (3), the nano-titanium dioxide / tourmaline composite carrier needs to be placed in 0.1 mol / L dilute hydrochloric acid and ultrasonically activated at 300W for 20~30 min to activate the surface amino groups.

[0018] Furthermore, in step (4), the recycled polyester is obtained by crushing, washing and vacuum drying waste polyethylene terephthalate to obtain polyester fragments with a moisture content of 80 ppm.

[0019] Furthermore, the mixed aqueous solution in step (4) contains 12% N,N-dimethylformamide and 16% sulfuric acid by mass.

[0020] Furthermore, the process parameters for wet spinning in step (4) are as follows: the conveying speed is 0.59~0.61mL / min, the outer diameter of the spinneret hole on the spinneret plate is 1.0~1.3mm, and the inner diameter is 0.6~0.8mm. The spinning solution is spun through the hollow profile on the cloud spinneret plate to obtain hollow profile fibers.

[0021] Furthermore, the heat setting temperature is 150~165℃, and the time is 20~25min.

[0022] Compared with the prior art, the beneficial effects achieved by the present invention are:

[0023] This invention prepares a novel antibacterial agent and blends it with recycled polyester, then uses wet spinning to produce cloud-like fibers, thereby achieving a long-lasting and highly effective antibacterial effect.

[0024] First, tourmaline is modified with a silane coupling agent to introduce amino groups on its surface, providing active sites for the subsequent preparation of nano-titanium dioxide. Then, the modified tourmaline is added to a titanium dioxide sol, and nano-titanium dioxide is grown in situ on the tourmaline using the sol-gel method to obtain a nano-titanium dioxide / tourmaline composite carrier, forming a tightly bonded core-shell structure, avoiding the shedding problem caused by traditional physical mixing. The silane chains of the amino groups create steric hindrance, inhibiting the aggregation of titanium dioxide particles. Furthermore, the crystal structure of tourmaline can release far-infrared rays and negative ions at room temperature, while nano-titanium dioxide, under visible or ultraviolet light irradiation, can generate reactive oxygen species through photogenerated electron-hole pairs, thus achieving anti-oxidation. The antibacterial effect is enhanced by synergistically combining the far-infrared properties of tourmaline with the local temperature to accelerate the generation of active oxygen, further improving the antibacterial effect. Then, the uncoordinated amino groups on the surface are further activated, reacting with terephthalaldehyde to load Schiff base structures onto the surface of a nano-titanium dioxide / tourmaline composite carrier to prepare a novel antibacterial agent. The Schiff base structure is covalently anchored on the surface of the composite carrier, achieving the immobilization of organic antibacterial components and further improving antibacterial performance. Compared with physical adsorption, it is more wash-resistant and prolongs antibacterial durability. Finally, the novel antibacterial agent is blended with recycled polyester and wet-spun to prepare recycled polyester tourmaline antibacterial cloud wool, giving the cloud wool a long-lasting and highly effective antibacterial effect. Detailed Implementation

[0025] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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 of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0026] To more clearly illustrate the method provided by the present invention, the following embodiments are provided in detail. The test methods for various indicators of the recycled polyester tourmaline antibacterial cloud fleece produced in the following embodiments are as follows:

[0027] Antibacterial properties: 1. Recycled polyester tourmaline antibacterial fleece prepared in the same mass as the examples and comparative examples was tested according to GB / T20944.3-2008 "Evaluation of antibacterial properties of textiles - Part 3: Vibration method". The bacteria used for testing were: Escherichia coli ATCC11229 and Staphylococcus aureus ATCC6538.

[0028] 2. Recycled polyester tourmaline antibacterial fleece of the same mass as those prepared in the examples and comparative examples was subjected to standard washing according to the washing method of the washing fastness tester in GB / T20944.1-2007. The antibacterial properties of the samples were tested after 50 washes. The bacteria used for testing were: Escherichia coli ATCC11229 and Staphylococcus aureus ATCC6538.

[0029] Example 1: A method for preparing recycled polyester tourmaline antibacterial cloud fleece, comprising the following preparation steps:

[0030] (1) Activated tourmaline and anhydrous ethanol were mixed at a solid-liquid ratio of 1:2. KH550 was added at a mass of 0.01 times that of activated tourmaline. Ammonia was added dropwise under stirring until the pH was 9. The mixture was reacted at 50°C for 4 hours, centrifuged, washed, and vacuum dried at 60°C for 4 hours to obtain modified tourmaline. The activated tourmaline was prepared by mixing iron tourmaline with a particle size of 300 nm and 1 mol / L hydrochloric acid at a solid-liquid ratio of 1:5, stirring and refluxing at 80°C for 1 hour, filtering, washing with deionized water until neutral, and then adding it to anhydrous ethanol at a solid-liquid ratio of 1:2. The mixture was sonicated for 30 minutes and vacuum dried at 60°C for 2 hours.

[0031] (2) The modified tourmaline and titanium dioxide sol were mixed at a solid-liquid ratio of 1:10, ultrasonically dispersed for 30 min, stirred at room temperature for 1 h, heated in a water bath at 60 °C for 1 h, centrifuged to separate the solid, washed, vacuum dried at 80 °C for 4 h, and placed in a muffle furnace to calcine at 400 °C for 1.5 h with a program temperature increase of 2 °C / min to obtain nano-titanium dioxide / tourmaline composite carrier; the preparation method of the titanium dioxide sol is as follows: 1) using anhydrous ethanol as solvent, glacial acetic acid as catalyst, tetrabutyl titanate as precursor, the mass fraction of tetrabutyl titanate in the solution is 20%, mixed to form a solution, hydrolyzed at 50 °C for 6 h, then aged for 12 h, and the solvent was extracted under reduced pressure at 60 °C to obtain nano-titanium dioxide dry gel; 2) the above nano-titanium dioxide dry gel was prepared into nano-titanium dioxide sol with a concentration of 20 wt% using deionized water;

[0032] (3) Mix nano-titanium dioxide / tourmaline composite carrier, terephthalaldehyde and ethanol, add acetic acid dropwise, adjust pH to 5, heat in a water bath at 50℃ for 1 h, filter, vacuum dry at 60℃ for 6 h, and dry to obtain a novel antibacterial agent; the mass ratio of nano-titanium dioxide / tourmaline composite carrier, terephthalaldehyde and ethanol is 1:0.2:20; the nano-titanium dioxide / tourmaline composite carrier needs to be placed in 0.1 mol / L dilute hydrochloric acid and ultrasonically activated at 300W for 20 min;

[0033] (4) Recycled polyester, novel antibacterial agent and mixed aqueous solution are mixed at a mass ratio of 1:0.05:6 and stirred at 25°C for 30 min. Then, hollow shaped fibers are obtained by wet spinning through a cloud-like spinneret. After being shaped, bundled in separate barrels, rapidly stretched and three-dimensionally crimped, recycled polyester tourmaline antibacterial cloud-like fibers are obtained by heat setting. The recycled polyester is waste polyethylene terephthalate that has been crushed, washed and vacuum dried to obtain polyester fragments with a water content of 80 ppm. The mixed aqueous solution contains 12% N,N-dimethylformamide and 16% sulfuric acid by mass. The wet spinning process parameters are: conveying speed of 0.59 mL / min, outer diameter of spinneret hole of 1.0 mm and inner diameter of 0.6 mm, the spinning solution is spun through a cloud-like spinneret to obtain hollow shaped fibers. The heat setting temperature is 150°C and the time is 20 min.

[0034] Example 2; A method for preparing recycled polyester tourmaline antibacterial cloud fleece, comprising the following preparation steps:

[0035] (1) Activated tourmaline and anhydrous ethanol were mixed at a solid-liquid ratio of 1:2. KH550 was added at a mass of 0.02 times that of activated tourmaline. Ammonia was added dropwise under stirring until the pH was 9. The mixture was reacted at 52°C for 4 hours, centrifuged, washed, and vacuum dried at 60°C for 4 hours to obtain modified tourmaline. The activated tourmaline was prepared by mixing lithium tourmaline with a particle size of 300 nm and 1 mol / L hydrochloric acid at a solid-liquid ratio of 1:5, stirring and refluxing at 80°C for 1 hour, filtering, washing with deionized water until neutral, and then adding it to anhydrous ethanol at a solid-liquid ratio of 1:2. The mixture was sonicated for 30 minutes and vacuum dried at 60°C for 2.5 hours.

[0036] (2) The modified tourmaline and titanium dioxide sol were mixed at a solid-liquid ratio of 1:11, ultrasonically dispersed for 30 min, stirred at room temperature for 1.5 h, heated in a water bath at 60 °C for 1 h, centrifuged to separate the solid, washed, vacuum dried at 80 °C for 4 h, and placed in a muffle furnace to calcine at 400 °C for 2 h with a program temperature increase of 2 °C / min to obtain nano-titanium dioxide / tourmaline composite carrier; the preparation method of the titanium dioxide sol is as follows: 1) using anhydrous ethanol as solvent, glacial acetic acid as catalyst, tetrabutyl titanate as precursor, the mass fraction of tetrabutyl titanate in the solution is 25%, mixed to form a solution, hydrolyzed at 52 °C for 6 h, then aged for 12 h, and the solvent was extracted under reduced pressure at 65 °C to obtain nano-titanium dioxide dry gel; 2) the above nano-titanium dioxide dry gel was prepared into nano-titanium dioxide sol with a concentration of 30 wt% using deionized water;

[0037] (3) Mix nano-titanium dioxide / tourmaline composite carrier, terephthalaldehyde and ethanol, add acetic acid dropwise, adjust pH to 5, heat in a water bath at 52℃ for 1.5h, filter, vacuum dry at 60℃ for 6h, and dry to obtain a novel antibacterial agent; the mass ratio of nano-titanium dioxide / tourmaline composite carrier, terephthalaldehyde and ethanol is 1:0.3:21; the nano-titanium dioxide / tourmaline composite carrier needs to be placed in 0.1mol / L dilute hydrochloric acid and ultrasonically activated at 300W for 25min;

[0038] (4) Recycled polyester, novel antibacterial agent and mixed aqueous solution are mixed at a mass ratio of 1:0.06:6 and stirred at 25°C for 30 min. Then, hollow shaped fibers are obtained by wet spinning through a cloud-like spinneret. After being shaped, bundled in separate barrels, rapidly stretched and three-dimensionally crimped, recycled polyester tourmaline antibacterial cloud-like fibers are obtained by heat setting. The recycled polyester is waste polyethylene terephthalate that has been crushed, washed and vacuum dried to obtain polyester fragments with a water content of 80 ppm. The mixed aqueous solution contains 12% N,N-dimethylformamide and 16% sulfuric acid by mass. The wet spinning process parameters are: conveying speed of 0.59 mL / min, outer diameter of spinneret hole of 1.1 mm and inner diameter of 0.6 mm, the spinning solution is spun through a cloud-like spinneret to obtain hollow shaped fibers. The heat setting temperature is 155°C and the time is 22 min.

[0039] Example 3; A method for preparing recycled polyester tourmaline antibacterial cloud fleece, comprising the following preparation steps:

[0040] (1) Activated tourmaline and anhydrous ethanol were mixed at a solid-liquid ratio of 1:2. KH550 was added at a mass of 0.03 times that of activated tourmaline. Ammonia was added dropwise under stirring until the pH was 10. The mixture was reacted at 55°C for 4 hours, centrifuged, washed, and vacuum dried at 60°C for 5 hours to obtain modified tourmaline. The activated tourmaline was prepared by mixing iron tourmaline with a particle size of 300 nm and 1 mol / L hydrochloric acid at a solid-liquid ratio of 1:5, stirring and refluxing at 80°C for 1.5 hours, filtering, washing with deionized water until neutral, and then adding it to anhydrous ethanol at a solid-liquid ratio of 1:2. The mixture was sonicated for 30 minutes and vacuum dried at 60°C for 3 hours.

[0041] (2) The modified tourmaline and titanium dioxide sol were mixed at a solid-liquid ratio of 1:13, ultrasonically dispersed for 30 min, stirred at room temperature for 1.5 h, heated in a water bath at 60 °C for 1.5 h, centrifuged to separate the solid, washed, vacuum dried at 80 °C for 4 h, and placed in a muffle furnace to calcine at 400 °C for 2 h with a program temperature increase of 2 °C / min to obtain nano-titanium dioxide / tourmaline composite carrier; the preparation method of the titanium dioxide sol is as follows: 1) using anhydrous ethanol as solvent, glacial acetic acid as catalyst, tetrabutyl titanate as precursor, the mass fraction of tetrabutyl titanate in the solution is 30%, mixed to form a solution, hydrolyzed at 55 °C for 6 h, then aged for 12 h, and the solvent was extracted under reduced pressure at 70 °C to obtain nano-titanium dioxide dry gel; 2) the above nano-titanium dioxide dry gel was prepared into nano-titanium dioxide sol with a concentration of 35 wt% using deionized water;

[0042] (3) Mix nano-titanium dioxide / tourmaline composite carrier, terephthalaldehyde and ethanol, add acetic acid dropwise, adjust pH to 6, heat in a water bath at 55℃ for 1.5h, filter, vacuum dry at 60℃ for 6h, and dry to obtain a novel antibacterial agent; the mass ratio of nano-titanium dioxide / tourmaline composite carrier, terephthalaldehyde and ethanol is 1:0.4:23; the nano-titanium dioxide / tourmaline composite carrier needs to be placed in 0.1mol / L dilute hydrochloric acid and ultrasonically activated at 300W for 25min to activate the surface amino groups;

[0043] (4) Recycled polyester, novel antibacterial agent and mixed aqueous solution are mixed at a mass ratio of 1:0.08:7 and stirred at 30℃ for 30 min. Then, hollow shaped fibers are obtained by wet spinning through a cloud-like spinneret. After being shaped, bundled in separate barrels, rapidly stretched and three-dimensionally crimped, recycled polyester tourmaline antibacterial cloud-like fibers are obtained by heat setting. The recycled polyester is waste polyethylene terephthalate that has been crushed, washed and vacuum dried to obtain polyester fragments with a water content of 80 ppm. The mixed aqueous solution contains 12% N,N-dimethylformamide and 16% sulfuric acid by mass. The wet spinning process parameters are: conveying speed of 0.60 mL / min, outer diameter of spinneret hole of 1.2 mm and inner diameter of 0.7 mm, the spinning solution is spun through a cloud-like spinneret to obtain hollow shaped fibers. The heat setting temperature is 160℃ and the time is 25 min.

[0044] Example 4; A method for preparing recycled polyester tourmaline antibacterial cloud fleece, comprising the following preparation steps:

[0045] (1) Activated tourmaline and anhydrous ethanol were mixed at a solid-liquid ratio of 1:2. KH550 was added at a mass of 0.04 times that of activated tourmaline. Ammonia was added dropwise under stirring until the pH was 10. The mixture was reacted at 58°C for 4 hours, centrifuged, washed, and vacuum dried at 60°C for 5 hours to obtain modified tourmaline. The activated tourmaline was prepared by mixing lithium tourmaline with a particle size of 300 nm and 1 mol / L hydrochloric acid at a solid-liquid ratio of 1:5, stirring and refluxing at 80°C for 1.5 hours, filtering, washing with deionized water until neutral, and then adding it to anhydrous ethanol at a solid-liquid ratio of 1:2. The mixture was sonicated for 30 minutes and vacuum dried at 60°C for 3 hours.

[0046] (2) The modified tourmaline and titanium dioxide sol were mixed at a solid-liquid ratio of 1:14, ultrasonically dispersed for 30 min, stirred at room temperature for 2 h, heated in a water bath at 60 °C for 1.5 h, centrifuged to separate the solid, washed, vacuum dried at 80 °C for 4 h, and placed in a muffle furnace to calcine at 400 °C for 2.5 h with a program temperature increase of 2 °C / min to obtain nano-titanium dioxide / tourmaline composite carrier; the preparation method of the titanium dioxide sol is as follows: 1) using anhydrous ethanol as solvent, glacial acetic acid as catalyst, tetrabutyl titanate as precursor, the mass fraction of tetrabutyl titanate in the solution is 30%, mixed to form a solution, hydrolyzed at 55 °C for 6 h, then aged for 12 h, and the solvent was extracted under reduced pressure at 75 °C to obtain nano-titanium dioxide dry gel; 2) the above nano-titanium dioxide dry gel was prepared into a nano-titanium dioxide sol with a concentration of 40 wt% using deionized water;

[0047] (3) Mix nano-titanium dioxide / tourmaline composite carrier, terephthalaldehyde and ethanol, add acetic acid dropwise, adjust pH to 6, heat in a water bath at 55℃ for 2h, filter, vacuum dry at 60℃ for 6h, and dry to obtain a novel antibacterial agent; the mass ratio of nano-titanium dioxide / tourmaline composite carrier, terephthalaldehyde and ethanol is 1:0.5:25; the nano-titanium dioxide / tourmaline composite carrier needs to be placed in 0.1mol / L dilute hydrochloric acid and ultrasonically activated at 300W for 25min to activate the surface amino groups;

[0048] (4) Recycled polyester, novel antibacterial agent and mixed aqueous solution are mixed at a mass ratio of 1:0.08:7 and stirred at 30℃ for 30 min. Then, hollow shaped fibers are obtained by wet spinning through a cloud-like spinneret. After being shaped, bundled in separate barrels, rapidly stretched and three-dimensionally crimped, recycled polyester tourmaline antibacterial cloud-like fibers are obtained by heat setting. The recycled polyester is waste polyethylene terephthalate that has been crushed, washed and vacuum dried to obtain polyester fragments with a water content of 80 ppm. The mixed aqueous solution contains 12% N,N-dimethylformamide and 16% sulfuric acid by mass. The wet spinning process parameters are: conveying speed of 0.61 mL / min, outer diameter of spinneret hole of 1.3 mm and inner diameter of 0.8 mm, the spinning solution is spun through a cloud-like spinneret to obtain hollow shaped fibers. The heat setting temperature is 160℃ and the time is 20 min.

[0049] Example 5; A method for preparing recycled polyester tourmaline antibacterial cloud fleece, comprising the following preparation steps:

[0050] (1) Activated tourmaline and anhydrous ethanol were mixed at a solid-liquid ratio of 1:2. KH550 was added at a mass of 0.05 times that of activated tourmaline. Ammonia was added dropwise under stirring until the pH was 10. The mixture was reacted at 60°C for 4 hours, centrifuged, washed, and vacuum dried at 60°C for 6 hours to obtain modified tourmaline. The activated tourmaline was prepared by mixing 300 nm iron tourmaline and 1 mol / L hydrochloric acid at a solid-liquid ratio of 1:5, stirring and refluxing at 80°C for 2 hours, filtering, washing with deionized water until neutral, and then adding it to anhydrous ethanol at a solid-liquid ratio of 1:2. The mixture was sonicated for 30 minutes and vacuum dried at 60°C for 4 hours.

[0051] (2) The modified tourmaline and titanium dioxide sol were mixed at a solid-liquid ratio of 1:15, ultrasonically dispersed for 30 min, stirred at room temperature for 2 h, heated in a water bath at 60 °C for 1.5 h, centrifuged to separate the solid, washed, vacuum dried at 80 °C for 4 h, and placed in a muffle furnace to calcine at 400 °C for 3 h with a program temperature increase of 2 °C / min to obtain nano titanium dioxide / tourmaline composite carrier; the preparation method of the titanium dioxide sol is as follows: 1) using anhydrous ethanol as solvent, glacial acetic acid as catalyst, tetrabutyl titanate as precursor, the mass fraction of tetrabutyl titanate in the solution is 35%, mixed to form a solution, hydrolyzed at 60 °C for 6 h, then aged for 12 h, and the solvent was extracted under reduced pressure at 80 °C to obtain nano titanium dioxide dry gel; 2) the above nano titanium dioxide dry gel was prepared into a nano titanium dioxide sol with a concentration of 50 wt% using deionized water;

[0052] (3) Mix nano-titanium dioxide / tourmaline composite carrier, terephthalaldehyde and ethanol, add acetic acid dropwise, adjust pH to 6, heat in a water bath at 60℃ for 2h, filter, vacuum dry at 60℃ for 6h, and dry to obtain a novel antibacterial agent; the mass ratio of nano-titanium dioxide / tourmaline composite carrier, terephthalaldehyde and ethanol is 1:0.6:25; the nano-titanium dioxide / tourmaline composite carrier needs to be placed in 0.1mol / L dilute hydrochloric acid and ultrasonically activated at 300W for 30min to activate the surface amino groups;

[0053] (4) Recycled polyester, novel antibacterial agent and mixed aqueous solution are mixed at a mass ratio of 1:0.10:8 and stirred at 30℃ for 30 min. Then, hollow shaped fibers are obtained by wet spinning through a cloud-like spinneret. After being shaped, bundled in separate barrels, rapidly stretched and three-dimensionally crimped, recycled polyester tourmaline antibacterial cloud-like fibers are obtained by heat setting. The recycled polyester is waste polyethylene terephthalate that has been crushed, washed and vacuum dried to obtain polyester fragments with a water content of 80 ppm. The mixed aqueous solution contains 12% N,N-dimethylformamide and 16% sulfuric acid by mass. The wet spinning process parameters are: conveying speed of 0.61 mL / min, outer diameter of spinneret hole of 1.3 mm and inner diameter of 0.8 mm, the spinning solution is spun through a cloud-like spinneret to obtain hollow shaped fibers. The heat setting temperature is 165℃ and the time is 25 min.

[0054] Comparative Example 1

[0055] The difference between Comparative Example 1 and Example 3 is that step (1) is omitted, and the modified tourmaline in step (2) is replaced with activated tourmaline; the remaining steps are the same as in Example 3.

[0056] Comparative Example 2

[0057] The difference between Comparative Example 2 and Example 3 is that step (2) is omitted, and the nano-titanium dioxide / tourmaline composite carrier in step (3) is replaced with modified tourmaline; the remaining steps are the same as in Example 3.

[0058] Comparative Example 3

[0059] The difference between Comparative Example 3 and Example 3 is that step (3) is omitted, and the novel antibacterial agent in step (4) is replaced with a nano-titanium dioxide / tourmaline composite carrier; the remaining steps are the same as in Example 3.

[0060] Example of effect

[0061] Table 1 below shows the performance analysis results of the recycled polyester tourmaline antibacterial cloud fleece produced using Examples 1 to 5 and Comparative Examples 1 to 3 of the present invention.

[0062] Table 1

[0063]

[0064] Furthermore, after 50 washes, the overall antibacterial performance of Examples 1-5 of this invention against Staphylococcus aureus and Escherichia coli reached over 95%, achieving the highest level AAA grade in the Chinese textile antibacterial industry standard.

[0065] A comparison of the experimental data from Example 3 and Comparative Examples 1-3 reveals that this invention first modifies tourmaline with a silane coupling agent, introducing amino groups on its surface to provide active sites for the subsequent preparation of nano-titanium dioxide. Then, the modified tourmaline is added to a titanium dioxide sol, and nano-titanium dioxide is grown in situ on the tourmaline using the sol-gel method to obtain a nano-titanium dioxide / tourmaline composite carrier, forming a tightly bonded core-shell structure, avoiding the shedding problem caused by traditional physical mixing. The silane chains of the amino groups create steric hindrance, inhibiting the aggregation of titanium dioxide particles. Furthermore, the crystal structure of tourmaline can release far-infrared rays and negative ions at room temperature, while nano-titanium dioxide can generate photoelectrons under visible or ultraviolet light irradiation. Hole pairs generate reactive oxygen species to achieve antibacterial effects. Synergistically with the far-infrared radiation of tourmaline, the generation of reactive oxygen species is accelerated by increasing local temperature, further enhancing the antibacterial effect. Then, uncoordinated amino groups on the surface are further activated, reacting with terephthalaldehyde to load Schiff base structures onto the surface of a nano-titanium dioxide / tourmaline composite carrier to prepare a novel antibacterial agent. The Schiff base structure is covalently anchored on the composite carrier surface, achieving the immobilization of organic antibacterial components and further improving antibacterial performance. Compared to physical adsorption, it is more wash-resistant and prolongs antibacterial durability. Finally, the novel antibacterial agent is blended with recycled polyester, and recycled polyester tourmaline antibacterial cloud wool is prepared through wet spinning, giving the cloud wool a long-lasting and highly effective antibacterial effect.

[0066] It will be apparent to those skilled in the art that the present invention is not limited to the details of the exemplary embodiments described above, and that the invention can be implemented in other specific forms without departing from its spirit or essential characteristics. Therefore, the embodiments should be considered in all respects as exemplary and non-limiting, and the scope of the invention is defined by the appended claims rather than the foregoing description. Thus, all variations falling within the meaning and scope of equivalents of the claims are intended to be included within the present invention. No markings in the claims should be construed as limiting the scope of the claims.

Claims

1. A recycled polyester tourmaline antibacterial cloud-like fabric, characterized in that, The recycled polyester tourmaline antibacterial cloud wool is produced by extruding a novel antibacterial agent and recycled polyester chips into a screw extruder to obtain a mixed masterbatch, which is then produced by wet spinning. The novel antibacterial agent is prepared by growing nano-titanium dioxide in situ on the surface of modified tourmaline to obtain a nano-titanium dioxide / tourmaline composite carrier, and then reacting it with terephthalaldehyde to load a Schiff base structure. The preparation process of the novel antibacterial agent includes the following steps: (1) Mix activated tourmaline and anhydrous ethanol at a solid-liquid ratio of 1:2, add 0.01 to 0.05 times the mass of activated tourmaline KH550, add ammonia dropwise under stirring until the pH is 9 to 10, react at 50 to 60°C for 4 hours, centrifuge, wash, and vacuum dry at 60°C for 4 to 6 hours to obtain modified tourmaline; (2) The modified tourmaline and titanium dioxide sol were mixed at a solid-liquid ratio of 1:10~15, ultrasonically dispersed for 30 min, stirred at room temperature for 1~2 h, heated in a water bath at 60℃ for 1~1.5 h, centrifuged to separate the solid, washed, dried, and placed in a muffle furnace to calcine at 400℃ for 1.5~3 h to obtain nano titanium dioxide / tourmaline composite carrier; (3) Mix nano-titanium dioxide / tourmaline composite carrier, terephthalaldehyde and ethanol, add acetic acid dropwise, adjust the pH to 5~6, heat the reaction in a water bath at 50~60℃ for 1~2h, filter, wash and dry to obtain a new antibacterial agent; The nano-titanium dioxide / tourmaline composite carrier needs to be placed in 0.1 mol / L dilute hydrochloric acid and ultrasonically activated at 300W for 20-30 minutes to activate the surface amino groups.

2. The recycled polyester tourmaline antibacterial cloud fleece according to claim 1, characterized in that, The tourmaline is either iron tourmaline or lithium tourmaline.

3. A method for preparing the recycled polyester tourmaline antibacterial cloud-like fleece as described in claim 1, characterized in that, The preparation steps include: mixing recycled polyester, a novel antibacterial agent, and a mixed aqueous solution at a mass ratio of 1:0.05~0.10:6~8, stirring at 25~30℃ for 30 minutes, and then wet spinning through a cloud-like spinneret to obtain hollow profiled fibers. After being shaped, bundled in separate drums, rapidly drawn, and fully formed in three-dimensional crimping, the recycled polyester tourmaline antibacterial cloud-like fibers are heat-set to obtain recycled polyester tourmaline antibacterial cloud-like fibers. The mixed aqueous solution contains 12% N,N-dimethylformamide and 16% sulfuric acid by mass.

4. The preparation method according to claim 3, characterized in that, In step (1), the activated tourmaline is prepared by mixing tourmaline and 1 mol / L hydrochloric acid at a solid-liquid ratio of 1:5, stirring and refluxing at 80°C for 1-2 hours, filtering, washing with deionized water until neutral, adding it to anhydrous ethanol at a solid-liquid ratio of 1:2, sonicating for 30 minutes, and vacuum drying at 60°C for 2-4 hours.

5. The preparation method according to claim 3, characterized in that, The preparation method of titanium dioxide sol in step (2) is as follows: 1) using anhydrous ethanol as solvent, glacial acetic acid as catalyst, and tetrabutyl titanate as precursor, with a mass fraction of 20%~35% in the solution, the mixture is mixed to form a solution, hydrolyzed at 50~60℃ for 6h, then aged for 12h, and the solvent is extracted under reduced pressure at 60~80℃ to obtain nano titanium dioxide dry gel; 2) using deionized water to prepare the above nano titanium dioxide dry gel into nano titanium dioxide sol with a concentration of 20~50wt%.

6. The preparation method according to claim 3, characterized in that, In step (3), the mass ratio of nano-titanium dioxide / tourmaline composite carrier, terephthalaldehyde and ethanol is 1:0.2~0.6:20~25.

7. The preparation method according to claim 3, characterized in that, The process parameters for wet spinning are as follows: the conveying speed is 0.59~0.61mL / min, the outer diameter of the spinneret hole on the spinneret is 1.0~1.3mm, and the inner diameter is 0.6~0.8mm. The spinning solution is spun through a hollow profile on the cloud spinneret to obtain hollow profile fibers.

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