Preparation method of molybdenum disulfide and graphene modified antibacterial polyester fiber

Abstract

The application relates to the technical field of textiles and discloses a preparation method of molybdenum disulfide and graphene modified antibacterial polyester fiber, which comprises the following steps: (1) dispersing modified graphene and modified nano MoS2 powder in dihydric alcohol to prepare an antibacterial agent dispersion liquid; the surface of the modified graphene and the modified nano MoS2 powder is attached with a dispersant; (2) mixing diacid, a catalyst and the antibacterial agent dispersion liquid to perform polymerization, so as to prepare modified polyester; and (3) preparing the modified polyester into a fiber. The modified graphene and the modified nano MoS2 powder, which are attached with the dispersant on the surface, are compounded, and the in-situ polymerization method is used, so that the prepared polyester fiber can exert good antibacterial effects on escherichia coli, staphylococcus aureus and candida albicans.

Description

Technical Field

[0001] This invention relates to the field of textile technology, and in particular to a method for preparing molybdenum disulfide and graphene modified antibacterial polyester fiber. Background Technology

[0002] Ordinary polyester fibers lack antibacterial properties and are prone to bacterial growth during use. The proliferation of pathogenic bacteria such as Escherichia coli, Staphylococcus aureus, and Candida albicans can harm human health. By modifying polyester fibers with antibacterial properties, the growth and reproduction of bacteria on the fibers and fabrics can be inhibited. This process is now widely used in medical, clothing, and home furnishing fields.

[0003] Graphene, a typical two-dimensional nanomaterial, consists of a hydrophobic planar structure and hydrophilic edges. This unique structure endows it with excellent antibacterial properties, making it suitable for use as an antibacterial modifier in fabrics. Current methods primarily involve coating fabrics as a post-processing step (e.g., patent CN202010540044.9), a complex process that is not easily sustainable. While adding graphene to polyester fibers through in-situ polymerization (e.g., patent CN202011380311.7) can improve the durability of the antibacterial effect, its improvement on the fiber's antibacterial properties is limited, and it's difficult to achieve inhibition rates of over 97% against Escherichia coli, Staphylococcus aureus, and Candida albicans. Summary of the Invention

[0004] To address the aforementioned technical problem—namely, the poor antibacterial effect of existing graphene-modified polyester fibers—this invention provides a method for preparing molybdenum disulfide and graphene-modified antibacterial polyester fibers. This method combines modified graphene with a dispersant-coated surface with modified nano-MoS2 powder, and employs an in-situ polymerization method, enabling the resulting polyester fibers to exhibit good antibacterial effects against Escherichia coli, Staphylococcus aureus, and Candida albicans.

[0005] The specific technical solution of this invention is as follows:

[0006] A method for preparing molybdenum disulfide and graphene-modified antibacterial polyester fiber includes the following steps:

[0007] (1) Modified graphene and modified nano MoS2 powder are dispersed in diol to prepare an antibacterial agent dispersion; the surface of the modified graphene and modified nano MoS2 powder is coated with a dispersant.

[0008] (2) The diacid, catalyst and antibacterial agent dispersion are mixed and polymerized to obtain the modified polyester;

[0009] (3) The modified polyester is made into fibers.

[0010] Graphene can exert its antibacterial effect through physical cutting and oxidative stress pathways. Specifically: 1) Physical cutting pathway: The sharp sheets of graphene pierce the bacterial cell membrane, causing the cell contents to flow out, thereby killing the bacteria; 2) Oxidative stress pathway: After the cell membrane comes into direct contact with graphene, the transfer of charge stimulates free radical reactions, thereby destroying the bacterial membrane structure and important biomolecules, leading to the death of the bacteria.

[0011] Nano-molybdenum disulfide (MoS2) powder shares a similar layered structure with graphene, exhibiting a large specific surface area. The fewer stacked layers per nanosheet result in a larger total area including the edges, with the edges occupying a higher proportion of the surface. When nano-MoS2 powder comes into direct contact with bacteria, membrane stress is generated between the nanosheet edges and the cell membrane, causing oxidative stress in the cells and leading to their oxidative decomposition. Furthermore, the presence of a highly conductive 1T phase in the nano-MoS2 powder facilitates electron-hole pair separation, thereby increasing the production of reactive oxygen species generated by the reaction of electrons, holes, and molecules in the aqueous solution, thus enhancing the destructive effect on bacterial cells.

[0012] This invention combines graphene and nano-MoS2 powder, which work synergistically to attack bacteria at both physical and chemical levels, thus significantly enhancing the antibacterial properties of polyester fibers. Furthermore, this invention modifies the graphene and nano-MoS2 powders, attaching a dispersant to their surface and employing an in-situ polymerization method. This reduces the agglomeration of graphene and nano-MoS2 powders within the polyester fibers, ensuring optimal physical and chemical bactericidal effects and improving the antibacterial properties of the polyester fibers. This results in superior antibacterial efficacy against Escherichia coli, Staphylococcus aureus, and Candida albicans.

[0013] Preferably, in step (1), the mass ratio of the modified graphene to the modified nano MoS2 powder is 1:1 to 9.

[0014] When the ratio of graphene and nano MoS2 powder is controlled within the above range, the two can work well together to further improve the antibacterial ability of polyester fiber.

[0015] Preferably, in step (1), the dispersant includes one or more of sodium dodecylbenzenesulfonate, polyvinylpyrrolidone, hexadecyltrimethylammonium bromide, and silane coupling agents.

[0016] Preferably, in step (1), the modified graphene includes graphene, a SiO2 layer coated on the outside of the graphene, and a dispersant attached to the surface of the SiO2 layer; the modified nano MoS2 powder includes nano MoS2 powder, a SiO2 layer coated on the outside of the nano MoS2 powder, and a dispersant attached to the surface of the SiO2 layer; after step (3), the fiber is alkali washed to remove SiO2.

[0017] This invention creates voids between the graphene and nano MoS2 powder and the polyester matrix by coating the graphene and nano MoS2 powder with a SiO2 layer and removing the SiO2 by alkaline washing after the fibers are made. This facilitates direct contact between the bacterial surface and the graphene and nano MoS2 powder, thereby killing bacteria through physical and chemical means and thus giving the polyester fiber better antibacterial properties.

[0018] Preferably, the thickness of the SiO2 layer is 30~60 nm.

[0019] Preferably, the preparation method of the modified graphene and modified nano MoS2 powder includes the following steps: dissolving a silicon source in a reaction solvent to prepare a silicon source solution; dispersing graphene and nano MoS2 powder in a dispersion medium, adjusting the pH to 8-9, adding the silicon source solution dropwise under stirring and at 40-45°C to carry out a hydrolysis reaction, then adding a dispersant, stirring and compounding, separating the product to obtain modified graphene and modified nano MoS2 powder.

[0020] Furthermore, the mass ratio of the dispersant to the total mass of graphene and nano MoS2 powder is 0.5~1.5:1.

[0021] Furthermore, the mixing and compounding temperature is 70~80℃, and the time is 2~6h.

[0022] Furthermore, the mass ratio of the silicon source to the total mass of graphene and nano MoS2 powder is 15~20:1.

[0023] Furthermore, the mass-to-volume ratio of the silicon source to the reaction solvent is 1g:5~7mL; the total mass ratio of the graphene and nano MoS2 powder to the volume of the dispersion medium is 1g:200~500mL.

[0024] Furthermore, the specific process of adding the silicon source solution dropwise includes the following steps: the silicon source solution is divided into 2 to 4 batches and added dropwise, with each batch added at a rate of 0.2 to 0.3 mL / min. After each batch is added, the mixture is stirred for 10 to 20 minutes before adding the next batch. After all the batches are added, the mixture is stirred for another 10 to 30 minutes.

[0025] Preferably, the alkaline washing process for removing SiO2 includes the following steps: immersing the fiber in a 0.1~1 mol / L sodium hydroxide and / or potassium hydroxide solution and soaking it at 60~80°C for 1~2 hours.

[0026] Preferably, in step (1), the total mass of the modified graphene and modified nano MoS2 powder is 0.06~1% of the theoretical polyester yield.

[0027] The aforementioned "theoretical polyester yield" refers to the quality of polyester that can be obtained after polymerization, calculated based on the amount of diacid and the yield of diacid as 100%.

[0028] Preferably, in step (1), the diol is ethylene glycol; and in step (2), the dicarboxylic acid is terephthalic acid.

[0029] Preferably, the molar ratio of the diol in step (1) to the dicarboxylic acid in step (2) is 1:1.1~1.3.

[0030] As a preferred option, the specific process of step (3) includes the following steps: after drying the modified polyester, it is sequentially melt-extruded, spun, cooled, oiled and stretched; during the melt extrusion process, the screw temperature is 250~280℃.

[0031] Compared with the prior art, the present invention has the following advantages:

[0032] (1) The present invention combines modified graphene with a dispersant attached to its surface and modified nano MoS2 powder, and combines them with an in-situ polymerization method, so that the resulting polyester fiber can exert a good antibacterial effect against Escherichia coli, Staphylococcus aureus and Candida albicans.

[0033] (2) By coating graphene and nano MoS2 powder with a SiO2 layer, the present invention can create a gap between the graphene and nano MoS2 powder and the polyester matrix after the SiO2 is removed by alkali washing, thereby further improving the antibacterial effect of polyester fiber. Detailed Implementation

[0034] The present invention will be further described below with reference to embodiments.

[0035] General Implementation Examples

[0036] A method for preparing molybdenum disulfide and graphene-modified antibacterial polyester fiber includes the following steps:

[0037] (1) Modified graphene and modified nano MoS2 powder are dispersed in diol to prepare an antibacterial agent dispersion; the surface of the modified graphene and modified nano MoS2 powder is coated with a dispersant.

[0038] (2) The diacid, catalyst and antibacterial agent dispersion are mixed and polymerized to obtain the modified polyester;

[0039] (3) The modified polyester is made into fibers.

[0040] In one specific implementation, the mass ratio of the modified graphene and the modified nano MoS2 powder in step (1) is 1:1~9.

[0041] In one specific implementation, in step (1), the total mass of the modified graphene and modified nano MoS2 powder is 0.06~1% of the theoretical polyester yield.

[0042] In one specific embodiment, in step (1), the dispersant includes one or more of sodium dodecylbenzenesulfonate, polyvinylpyrrolidone, hexadecyltrimethylammonium bromide, and silane coupling agents.

[0043] In one specific implementation, in step (1), the modified graphene includes graphene, a SiO2 layer coated on the outside of the graphene, and a dispersant attached to the surface of the SiO2 layer; the modified nano MoS2 powder includes nano MoS2 powder, a SiO2 layer coated on the outside of the nano MoS2 powder, and a dispersant attached to the surface of the SiO2 layer; the thickness of the SiO2 layer is 30~60 nm; after step (3), the fiber is alkali washed to remove SiO2.

[0044] As one specific embodiment, the preparation method of the modified graphene and modified nano MoS2 powder includes the following steps: dissolving a silicon source in a reaction solvent to prepare a silicon source solution; dispersing graphene and nano MoS2 powder in a dispersion medium, adjusting the pH to 8-9, adding the silicon source solution dropwise under stirring and at 40-45°C to carry out a hydrolysis reaction, then adding a dispersant, and stirring and compounding at 70-80°C for 2-6 hours, then separating the product to obtain modified graphene and modified nano MoS2 powder. The mass ratio of the silicon source, the dispersant, and the total mass of graphene and nano-MoS2 powder is 15~20:0.5~1.5:1; the mass-to-volume ratio of the silicon source to the reaction solvent is 1g:5~7mL; the total mass ratio of the graphene and nano-MoS2 powder to the volume of the dispersion medium is 1g:200~500mL; the silicon source solution is added in 2~4 batches, with each batch added at a rate of 0.2~0.3mL / min. After each batch is added, the mixture is stirred for 10~20min before adding the next batch, and stirring is continued for 10~30min after all the batches are added.

[0045] As one specific embodiment, the alkaline washing process for removing SiO2 includes the following steps: immersing the fiber in a 0.1~1 mol / L sodium hydroxide and / or potassium hydroxide solution and soaking it at 60~80℃ for 1~2 hours.

[0046] In one specific implementation, in step (1), the diol is ethylene glycol; in step (2), the dicarboxylic acid is terephthalic acid.

[0047] In one specific implementation, the molar ratio of the diol in step (1) to the dicarboxylic acid in step (2) is 1:1.1~1.3.

[0048] As a specific implementation method, the specific process of step (3) includes the following steps: after drying the modified polyester, it is sequentially subjected to melt extrusion, spinning, cooling, oiling and stretching; during the melt extrusion process, the screw temperature is 250~280℃. Specific Implementation

[0050] The present invention will now be described through specific embodiments. It should be understood that these embodiments are for illustrative purposes only and are not intended to limit the scope of the invention. Variations and advantages that can be conceived by those skilled in the art without departing from the spirit and scope of the inventive concept are included in the present invention, and the scope of protection of the present invention is defined by the appended claims and any equivalents thereof.

[0051] Unless otherwise defined, all technical and scientific terms used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this disclosure pertains. Unless otherwise specified, the raw materials and equipment used in this invention are conventional in the art and can be obtained through conventional commercial means; unless otherwise specified, the methods used in this invention are conventional methods in the art.

[0052] In the following examples, the antibacterial performance test was conducted in accordance with GB / T 20944.3-2008 Evaluation of antibacterial properties of textiles - Part 3: Vibration method, and the antibacterial rate was measured after washing five times according to the washing fastness tester method in the standard.

[0053] Example 1

[0054] An antibacterial polyester fiber is prepared through the following steps:

[0055] (1) Preparation of modified graphene and modified nano-MoS2 powder:

[0056] (1.1) Mix 13 mL of tetraethyl orthosilicate and 70 mL of anhydrous ethanol to prepare a silicon source solution.

[0057] (1.2) 0.312g graphene, 0.312g nano MoS2 powder and 0.624g sodium dodecylbenzenesulfonate were added to 250mL anhydrous ethanol, ultrasonically dispersed, 12mL water was added, the pH was adjusted to 8.5 with ammonia water, and the temperature was raised to 40℃ to obtain a dispersion.

[0058] (1.3) The silicon source solution was divided into two equal batches and added dropwise at a rate of 0.2 mL / min to the dispersion at 40 °C under stirring. After each batch was added, the mixture was stirred for 10 min before adding the next batch. After all the batches were added, the mixture was stirred for another 30 min to obtain the graphene@SiO2 and MoS2@SiO2 dispersions.

[0059] (1.4) Add 0.624 g of sodium dodecylbenzenesulfonate to the graphene@SiO2 and MoS2@SiO2 dispersions obtained in step (1.3), stir at 80°C for 2 h, centrifuge, dry and cool the separated precipitate to obtain modified graphene and modified nano MoS2 powder, wherein the thickness of the SiO2 layer is 30~40 nm.

[0060] (2) Preparation of modified polyester:

[0061] The modified graphene and modified nano-MoS2 powder obtained in step (1) were added to 300g of ethylene glycol and ultrasonically dispersed. Then, they were added to a polymerization reactor along with 664g of terephthalic acid and 0.35g of antimony glycolate. The esterification reaction was carried out at 230℃ for 2h. When the esterification water reached 140mL, a vacuum was drawn, and after 1h, the vacuum was reduced to -0.1MPa. The temperature was then raised to 275℃ for a polycondensation reaction for 2h. After cooling and pelletizing, the modified polyester was obtained.

[0062] (3) Fiber preparation:

[0063] The modified polyester obtained in step (2) is vacuum dried to remove moisture, and then melt-extruded through a screw extruder. The screw temperature is 250°C in zone 1, 275°C in zone 2, and 280°C in zone 3 to obtain a melt. The spinning box temperature is 280°C, and the melt is extruded through a spinneret to form filaments. The filaments are cooled, oiled, and then stretched and shaped by hot rollers (draw ratio of 2) and wound at 3000 m / min to obtain fibers.

[0064] (4) Alkali washing:

[0065] Take the fiber obtained in step (3), immerse it in 0.5 mol / L NaOH solution, soak it at 70℃ for 1.5 h to obtain antibacterial polyester fiber.

[0066] The mechanical and antibacterial properties of the antibacterial polyester fiber prepared in this embodiment were tested as follows: the breaking strength was 3.2 cN / dtex, and the breaking elongation was 27%; the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans after washing were 99.0%, 99.4%, and 99.1%, respectively.

[0067] Example 2

[0068] An antibacterial polyester fiber is prepared through the following steps:

[0069] (1) Preparation of modified graphene and modified nano-MoS2 powder:

[0070] (1.1) Mix 80 mL of tetraethyl orthosilicate and 430 mL of anhydrous ethanol to prepare a silicon source solution.

[0071] (1.2) 1.92g graphene, 1.92g nano MoS2 powder and 3.84g sodium dodecylbenzenesulfonate were added to 1540mL anhydrous ethanol, ultrasonically dispersed, 74mL water was added, the pH was adjusted to 8.5 with ammonia water, and the temperature was raised to 40℃ to obtain a dispersion.

[0072] (1.3) The silicon source solution was divided into two equal batches and added dropwise at a rate of 0.2 mL / min to the dispersion at 40 °C under stirring. After each batch was added, the mixture was stirred for 10 min before adding the next batch. After all the batches were added, the mixture was stirred for another 30 min to obtain the graphene@SiO2 and MoS2@SiO2 dispersions.

[0073] (1.4) Add 3.84 g of sodium dodecylbenzenesulfonate to the graphene@SiO2 and MoS2@SiO2 dispersions obtained in step (1.3), stir at 80°C for 2 h, centrifuge, dry and cool the separated precipitate to obtain modified graphene and modified nano MoS2 powder, wherein the thickness of the SiO2 layer is 35~50 nm.

[0074] (2) Preparation of modified polyester:

[0075] The modified graphene and modified nano-MoS2 powder obtained in step (1) were added to 300g of ethylene glycol and ultrasonically dispersed. Then, they were added to a polymerization reactor along with 664g of terephthalic acid and 0.35g of antimony glycolate. The esterification reaction was carried out at 230℃ for 2h. When the esterification water reached 140mL, a vacuum was drawn, and after 1h, the vacuum was reduced to -0.1MPa. The temperature was then raised to 275℃ for a polycondensation reaction for 2h. After cooling and pelletizing, the modified polyester was obtained.

[0076] (3) Preparation of antibacterial polyester fibers:

[0077] The modified polyester obtained in step (2) is vacuum dried to remove moisture, and then melt-extruded through a screw extruder. The screw temperature is 250°C in zone 1, 275°C in zone 2, and 280°C in zone 3 to obtain a melt. The spinning box temperature is 280°C, and the melt is extruded through a spinneret to form filaments. The filaments are cooled, oiled, and then stretched and shaped by hot rollers (draw ratio of 2) and wound at 3000 m / min to obtain fibers.

[0078] (4) Alkali washing:

[0079] Take the fiber obtained in step (3), immerse it in 0.5 mol / L NaOH solution, soak it at 70℃ for 1.5 h to obtain antibacterial polyester fiber.

[0080] The mechanical and antibacterial properties of the antibacterial polyester fiber prepared in this embodiment were tested as follows: the breaking strength was 3.0 cN / dtex, and the breaking elongation was 26%; the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans after washing were 99.6%, 99.7%, and 99.4%, respectively.

[0081] Example 3

[0082] An antibacterial polyester fiber is prepared through the following steps:

[0083] (1) Preparation of modified graphene and modified nano-MoS2 powder:

[0084] (1.1) Mix 13 mL of tetraethyl orthosilicate and 70 mL of anhydrous ethanol to prepare a silicon source solution.

[0085] (1.2) 0.25g graphene, 0.374g nano MoS2 powder and 0.624g sodium dodecylbenzenesulfonate were added to 250mL anhydrous ethanol, ultrasonically dispersed, 12mL water was added, the pH was adjusted to 8.5 with ammonia water, and the temperature was raised to 40℃ to obtain a dispersion.

[0086] (1.3) The silicon source solution was divided into two equal batches and added dropwise at a rate of 0.2 mL / min to the dispersion at 40 °C under stirring. After each batch was added, the mixture was stirred for 10 min before adding the next batch. After all the batches were added, the mixture was stirred for another 30 min to obtain the graphene@SiO2 and MoS2@SiO2 dispersions.

[0087] (1.4) Add 0.624 g of sodium dodecylbenzenesulfonate to the graphene@SiO2 and MoS2@SiO2 dispersions obtained in step (1.3), stir at 80°C for 2 h, centrifuge, dry and cool the separated precipitate to obtain modified graphene and modified nano MoS2 powder, wherein the thickness of the SiO2 layer is 30~40 nm.

[0088] (2) Preparation of modified polyester:

[0089] The modified graphene and modified nano-MoS2 powder obtained in step (1) were added to 300g of ethylene glycol and ultrasonically dispersed. Then, they were added to a polymerization reactor along with 664g of terephthalic acid and 0.35g of antimony glycolate. The esterification reaction was carried out at 230℃ for 2h. When the esterification water reached 140mL, a vacuum was drawn, and after 1h, the vacuum was reduced to -0.1MPa. The temperature was then raised to 275℃ for a polycondensation reaction for 2h. After cooling and pelletizing, the modified polyester was obtained.

[0090] (3) Preparation of antibacterial polyester fibers:

[0091] The modified polyester obtained in step (2) is vacuum dried to remove moisture, and then melt-extruded through a screw extruder. The screw temperature is 250°C in zone 1, 275°C in zone 2, and 280°C in zone 3 to obtain a melt. The spinning box temperature is 280°C, and the melt is extruded through a spinneret to form filaments. The filaments are cooled, oiled, and then stretched and shaped by hot rollers (draw ratio of 2) and wound at 3000 m / min to obtain fibers.

[0092] (4) Alkali washing:

[0093] Take the fiber obtained in step (3), immerse it in 0.5 mol / L NaOH solution, soak it at 70℃ for 1.5 h to obtain antibacterial polyester fiber.

[0094] The mechanical and antibacterial properties of the antibacterial polyester fiber prepared in this embodiment were tested as follows: the breaking strength was 3.3 cN / dtex, and the breaking elongation was 27%; the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans after washing were 99.4%, 99.1%, and 99.1%, respectively.

[0095] Example 4

[0096] An antibacterial polyester fiber is prepared through the following steps:

[0097] (1) Preparation of modified graphene and modified nano-MoS2 powder:

[0098] (1.1) Mix 10 mL of tetraethyl orthosilicate and 50 mL of anhydrous ethanol to prepare a silicon source solution.

[0099] (1.2) 0.312g graphene, 0.312g nano MoS2 powder and 0.624g sodium dodecylbenzenesulfonate were added to 120mL anhydrous ethanol, ultrasonically dispersed, 6mL water was added, the pH was adjusted to 8.0 with ammonia water, and the temperature was raised to 45℃ to obtain a dispersion.

[0100] (1.3) The silicon source solution was divided into three equal batches and added dropwise at a rate of 0.3 mL / min to the dispersion at 45 °C with stirring. After each batch was added, the mixture was stirred for 20 min before adding the next batch. After all the batches were added, the mixture was stirred for another 10 min to obtain the graphene@SiO2 and MoS2@SiO2 dispersions.

[0101] (1.4) Add 0.312 g sodium dodecylbenzenesulfonate to the graphene@SiO2 and MoS2@SiO2 dispersions obtained in step (1.3), stir at 70°C for 3 h, centrifuge, dry and cool the separated precipitate to obtain modified graphene and modified nano MoS2 powder, wherein the thickness of the SiO2 layer is 40~50 nm.

[0102] (2) Preparation of modified polyester:

[0103] The modified graphene and modified nano-MoS2 powder obtained in step (1) were added to 300g of ethylene glycol and ultrasonically dispersed. Then, they were added to a polymerization reactor along with 664g of terephthalic acid and 0.35g of antimony glycolate. The esterification reaction was carried out at 230℃ for 2h. When the esterification water reached 140mL, a vacuum was drawn, and after 1h, the vacuum was reduced to -0.1MPa. The temperature was then raised to 275℃ for a polycondensation reaction for 2h. After cooling and pelletizing, the modified polyester was obtained.

[0104] (3) Preparation of antibacterial polyester fibers:

[0105] The modified polyester obtained in step (2) is vacuum dried to remove moisture, and then melt-extruded through a screw extruder. The screw temperature is 250°C in zone 1, 275°C in zone 2, and 280°C in zone 3 to obtain a melt. The spinning box temperature is 280°C, and the melt is extruded through a spinneret to form filaments. The filaments are cooled, oiled, and then stretched and shaped by hot rollers (draw ratio of 2) and wound at 3000 m / min to obtain fibers.

[0106] (4) Alkali washing:

[0107] Take the fiber obtained in step (3), immerse it in 0.1 mol / L NaOH solution, soak it at 80℃ for 1 h to obtain antibacterial polyester fiber.

[0108] The mechanical and antibacterial properties of the antibacterial polyester fiber prepared in this embodiment were tested as follows: the breaking strength was 3.0 cN / dtex, and the breaking elongation was 27%; the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans after washing were 99.2%, 99.5%, and 99.4%, respectively.

[0109] Example 5

[0110] An antibacterial polyester fiber is prepared through the following steps:

[0111] (1) Preparation of modified graphene and modified nano-MoS2 powder:

[0112] (1.1) Mix 30 mL of tetraethyl orthosilicate and 195 mL of anhydrous ethanol to prepare a silicon source solution.

[0113] (1.2) 0.78g graphene, 0.78g nano MoS2 powder and 1.5g sodium dodecylbenzenesulfonate were added to 720mL of water-ethanol, ultrasonically dispersed, 38mL of water was added, the pH was adjusted to 8.9 with ammonia, and the temperature was raised to 40℃ to obtain a dispersion.

[0114] (1.3) The silicon source solution was divided into three equal batches and added dropwise at a rate of 0.2 mL / min to the dispersion at 40 °C with stirring. After each batch was added, the mixture was stirred for 10 min before adding the next batch. After all the batches were added, the mixture was stirred for another 20 min to obtain the graphene@SiO2 and MoS2@SiO2 dispersions.

[0115] (1.4) Add 2.34 g of sodium dodecylbenzenesulfonate to the graphene@SiO2 and MoS2@SiO2 dispersions obtained in step (1.3), stir at 80°C for 2 h, centrifuge, dry and cool the separated precipitate to obtain modified graphene and modified nano MoS2 powder, wherein the thickness of the SiO2 layer is 45~60 nm.

[0116] (2) Preparation of modified polyester:

[0117] The modified graphene and modified nano-MoS2 powder obtained in step (1) were added to 300g of ethylene glycol and ultrasonically dispersed. Then, they were added to a polymerization reactor along with 664g of terephthalic acid and 0.35g of antimony glycolate. The esterification reaction was carried out at 230℃ for 2h. When the esterification water reached 140mL, a vacuum was drawn, and after 1h, the vacuum was reduced to -0.1MPa. The temperature was then raised to 275℃ for a polycondensation reaction for 2h. After cooling and pelletizing, the modified polyester was obtained.

[0118] (3) Preparation of antibacterial polyester fibers:

[0119] The modified polyester obtained in step (2) is vacuum dried to remove moisture, and then melt-extruded through a screw extruder. The screw temperature is 250°C in zone 1, 275°C in zone 2, and 280°C in zone 3 to obtain a melt. The spinning box temperature is 280°C, and the melt is extruded through a spinneret to form filaments. The filaments are cooled, oiled, and then stretched and shaped by hot rollers (draw ratio of 2) and wound at 3000 m / min to obtain fibers.

[0120] (4) Alkali washing:

[0121] Take the fiber obtained in step (3), immerse it in 1 mol / L NaOH solution, soak it at 60℃ for 2 hours to obtain antibacterial polyester fiber.

[0122] The mechanical and antibacterial properties of the antibacterial polyester fiber prepared in this embodiment were tested as follows: the breaking strength was 3.0 cN / dtex, and the breaking elongation was 25%; the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans after washing were 99.5%, 99.5%, and 99.3%, respectively.

[0123] Example 6

[0124] An antibacterial polyester fiber is prepared through the following steps:

[0125] (1) Preparation of modified graphene and modified nano-MoS2 powder:

[0126] 0.78g of graphene, 0.78g of nano-MoS2 powder and 2.34g of sodium dodecylbenzenesulfonate were added to 720mL of water. After stirring at 80℃ for 2h, the mixture was centrifuged, and the separated precipitate was dried and cooled to obtain modified graphene and modified nano-MoS2 powder.

[0127] (2) Preparation of modified polyester:

[0128] The modified graphene and modified nano-MoS2 powder obtained in step (1) were added to 300g of ethylene glycol and ultrasonically dispersed. Then, they were added to a polymerization reactor along with 664g of terephthalic acid and 0.35g of antimony glycolate. The esterification reaction was carried out at 230℃ for 2h. When the esterification water reached 140mL, a vacuum was drawn, and after 1h, the vacuum was reduced to -0.1MPa. The temperature was then raised to 275℃ for a polycondensation reaction for 2h. After cooling and pelletizing, the modified polyester was obtained.

[0129] (3) Preparation of antibacterial polyester fibers:

[0130] The modified polyester obtained in step (2) was vacuum dried to remove moisture, and then melt-extruded through a screw extruder. The screw temperature was 250°C in zone 1, 275°C in zone 2, and 280°C in zone 3 to obtain a melt. The spinning box temperature was 280°C, and the melt was extruded through a spinneret to form filaments. The filaments were cooled, oiled, and then stretched and shaped by hot rollers (draw ratio of 2) and wound at 3000 m / min to obtain antibacterial polyester fibers.

[0131] The mechanical and antibacterial properties of the antibacterial polyester fiber prepared in this embodiment were tested as follows: the breaking strength was 3.3 cN / dtex, and the breaking elongation was 27%; the antibacterial rates against Escherichia coli, Staphylococcus aureus, and Candida albicans after washing were 97.4%, 99.0%, and 97.9%, respectively.

[0132] Example 7

[0133] An antibacterial polyester fiber is prepared through the following steps:

[0134] (1) Preparation of modified graphene and modified nano-MoS2 powder:

[0135] (1.1) Mix 30 mL of tetraethyl orthosilicate and 195 mL of anhydrous ethanol to prepare a silicon source solution.

[0136] (1.2) 0.78g graphene, 0.78g nano MoS2 powder and 1.5g sodium dodecylbenzenesulfonate were added to 720mL of water-ethanol, ultrasonically dispersed, 38mL of water was added, the pH was adjusted to 8.9 with ammonia, and the temperature was raised to 40℃ to obtain a dispersion.

[0137] (1.3) The silicon source solution was divided into three equal batches and added dropwise at a rate of 0.2 mL / min to the dispersion at 40 °C with stirring. After each batch was added, the mixture was stirred for 10 min before adding the next batch. After all the batches were added, the mixture was stirred for another 20 min to obtain the graphene@SiO2 and MoS2@SiO2 dispersions.

[0138] (1.4) Add 2.34 g of sodium dodecylbenzenesulfonate to the graphene@SiO2 and MoS2@SiO2 dispersions obtained in step (1.3), stir at 80°C for 2 h, centrifuge, dry and cool the separated precipitate to obtain modified graphene and modified nano MoS2 powder, wherein the thickness of the SiO2 layer is 45~60 nm.

[0139] (2) Preparation of modified polyester:

[0140] The modified graphene and modified nano-MoS2 powder obtained in step (1) were added to 300g of ethylene glycol and ultrasonically dispersed. Then, they were added to a polymerization reactor along with 664g of terephthalic acid and 0.35g of antimony glycolate. The esterification reaction was carried out at 230℃ for 2h. When the esterification water reached 140mL, a vacuum was drawn, and after 1h, the vacuum was reduced to -0.1MPa. The temperature was then raised to 275℃ for a polycondensation reaction for 2h. After cooling and pelletizing, the modified polyester was obtained.

[0141] (3) Preparation of antibacterial polyester fibers:

[0142] The modified polyester obtained in step (2) was vacuum dried to remove moisture, and then melt-extruded through a screw extruder. The screw temperature was 250°C in zone 1, 275°C in zone 2, and 280°C in zone 3 to obtain a melt. The spinning box temperature was 280°C, and the melt was extruded through a spinneret to form filaments. The filaments were cooled, oiled, and then stretched and shaped by hot rollers (draw ratio of 2) and wound at 3000 m / min to obtain antibacterial polyester fibers.

[0143] The mechanical and antibacterial properties of the antibacterial polyester fiber prepared in this embodiment were tested as follows: the breaking strength was 3.1 cN / dtex, and the breaking elongation was 25%; the antibacterial rates of the fiber after washing against Escherichia coli, Staphylococcus aureus, and Candida albicans were 95.7%, 98.2%, and 96.0%, respectively.

[0144] Analysis of test results: Compared with Examples 6 and 7, the antibacterial properties of the fibers prepared in Example 5 are improved, indicating that coating the graphene and nano-MoS2 powder with a SiO2 layer and then performing alkali washing after fiber preparation can improve the antibacterial properties of polyester fibers. This is because: after the SiO2 layer is removed by alkali washing, gaps are formed between the graphene and nano-MoS2 powder and the polyester matrix, which facilitates direct contact between the bacterial surface and the graphene and nano-MoS2 powder, thereby killing bacteria through physical and chemical means.

[0145] Comparative Example 1

[0146] An antibacterial polyester fiber is prepared through the following steps:

[0147] (1) Preparation of modified graphene:

[0148] 1.56 g of graphene and 2.34 g of sodium dodecylbenzenesulfonate were added to 720 mL of water, stirred at 80 °C for 2 h, centrifuged, and the separated precipitate was dried and cooled to obtain modified graphene.

[0149] (2) Preparation of modified polyester:

[0150] The modified graphene obtained in step (1) was added to 300g of ethylene glycol and ultrasonically dispersed. Then, it was added to a polymerization reactor along with 664g of terephthalic acid and 0.35g of antimony glycolate. Esterification was carried out at 230℃ for 2 hours. When the esterification water reached 140mL, a vacuum was applied, and after 1 hour, the vacuum was reduced to -0.1MPa. The temperature was then increased to 275℃ for a polycondensation reaction for 2 hours. The mixture was then cooled and pelletized to obtain the modified polyester.

[0151] (3) Preparation of antibacterial polyester fibers:

[0152] The modified polyester obtained in step (2) was vacuum dried to remove moisture, and then melt-extruded through a screw extruder. The screw temperature was 250°C in zone 1, 275°C in zone 2, and 280°C in zone 3 to obtain a melt. The spinning box temperature was 280°C, and the melt was extruded through a spinneret to form filaments. The filaments were cooled, oiled, and then stretched and shaped by hot rollers (draw ratio of 2) and wound at 3000 m / min to obtain antibacterial polyester fibers.

[0153] The mechanical and antibacterial properties of the antibacterial polyester fiber prepared in this comparative example were tested as follows: the breaking strength was 3.5 cN / dtex, and the breaking elongation was 27%; the antibacterial rates of the fiber after washing against Escherichia coli, Staphylococcus aureus, and Candida albicans were 86.0%, 85.6%, and 80.7%, respectively.

[0154] Comparative Example 2

[0155] An antibacterial polyester fiber is prepared through the following steps:

[0156] (1) Preparation of modified nano-MoS2 powder:

[0157] 1.56 g of nano MoS2 powder and 2.34 g of sodium dodecylbenzenesulfonate were added to 720 mL of water, stirred at 80 °C for 2 h, centrifuged, and the separated precipitate was dried and cooled to obtain modified nano MoS2 powder.

[0158] (2) Preparation of modified polyester:

[0159] The modified nano-MoS2 powder obtained in step (1) was added to 300g of ethylene glycol and ultrasonically dispersed. Then, it was added to a polymerization reactor along with 664g of terephthalic acid and 0.35g of antimony glycolate. Esterification was carried out at 230℃ for 2 hours. When the esterification water reached 140mL, a vacuum was applied, and after 1 hour, the pressure was reduced to -0.1MPa. The temperature was then increased to 275℃ for a polycondensation reaction for 2 hours. The mixture was then cooled and pelletized to obtain the modified polyester.

[0160] (3) Preparation of antibacterial polyester fibers:

[0161] The modified polyester obtained in step (2) was vacuum dried to remove moisture, and then melt-extruded through a screw extruder. The screw temperature was 250°C in zone 1, 275°C in zone 2, and 280°C in zone 3 to obtain a melt. The spinning box temperature was 280°C, and the melt was extruded through a spinneret to form filaments. The filaments were cooled, oiled, and then stretched and shaped by hot rollers (draw ratio of 2) and wound at 3000 m / min to obtain antibacterial polyester fibers.

[0162] The mechanical and antibacterial properties of the antibacterial polyester fiber prepared in this embodiment were tested as follows: the breaking strength was 3.3 cN / dtex, and the breaking elongation was 27%; the antibacterial rates of the fiber after washing against Escherichia coli, Staphylococcus aureus, and Candida albicans were 90.4%, 84.0%, and 81.1%, respectively.

[0163] Test results analysis: Compared with Example 6, the fibers prepared in Comparative Examples 1 and 2 showed poorer antibacterial properties. This indicates that compared to using graphene and nano-MoS2 powder alone, using both in combination can significantly improve the antibacterial properties of polyester fibers.

[0164] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Any simple modifications, alterations, and equivalent transformations made to the above embodiments based on the technical essence of the present invention shall still fall within the protection scope of the present invention.

Claims

1. A method for preparing a molybdenum disulfide and graphene-modified antibacterial polyester fiber, characterized by, The method comprises the following steps: (1) dispersing modified graphene and modified nano-MoS2 powder in a dihydric alcohol to prepare an antibacterial agent dispersion liquid; the modified graphene comprises graphene, a SiO2 layer coated on the graphene, and a dispersant attached to the surface of the SiO2 layer; the modified nano-MoS2 powder comprises nano-MoS2 powder, a SiO2 layer coated on the nano-MoS2 powder, and a dispersant attached to the surface of the SiO2 layer; (2) mixing a dihydric acid, a catalyst, and the antibacterial agent dispersion liquid to perform polymerization to prepare a modified polyester; (3) preparing a fiber from the modified polyester; and performing alkali washing on the fiber to remove SiO2.

2. The production method according to claim 1, characterized by, In the modified graphene and modified nano-MoS2 powder of step (1), the mass ratio of graphene to nano-MoS2 powder is 1:1-9.

3. The production method according to claim 1, characterized by, In step (1), the dispersant comprises one or more of sodium dodecyl benzene sulfonate, polyvinylpyrrolidone, cetyltrimethylammonium bromide, and a silane coupling agent.

4. The production method according to claim 1, characterized by, The thickness of the SiO2 layer is 30-60 nm.

5. The preparation method according to claim 1, characterized in that, The preparation method of the modified graphene and modified nano-MoS2 powder comprises the following steps: dissolving a silicon source into a reaction solvent to prepare a silicon source solution; dispersing graphene and nano-MoS2 powder into a dispersion medium, adjusting the pH to 8-9, adding the silicon source solution drop by drop under stirring and at 40-45℃ to perform a hydrolysis reaction, then adding a dispersant, and after stirring and compounding, separating the product to obtain the modified graphene and modified nano-MoS2 powder.

6. The production method according to claim 5, wherein The mass ratio of the dispersant to the total mass of graphene and nano-MoS2 powder is 0.5-1.5:

1.

7. The preparation method according to claim 5, characterized in that, The temperature of the stirring and compounding is 70-80℃, and the time is 2-6 h.

8. The method of claim 1, wherein, In the modified graphene and modified nano-MoS2 powder of step (1), the total mass of graphene and nano-MoS2 powder is 0.06-1% of the theoretical polyester yield.

9. The method of claim 1, wherein, In step (1), the dihydric alcohol is ethylene glycol; and in step (2), the dihydric acid is terephthalic acid.