Antibacterial polyester fiber and preparation method thereof

Abstract

The invention relates to the field of polyester fiber materials, and particularly discloses an antibacterial polyester fiber and a preparation method thereof.The method comprises the following steps that S1, PET fibers are coated with an isolation transition layer, S1-1, the PET fibers are cleaned and then mixed with a silane coupling agent for a reaction, and pretreated fibers are obtained; s1-2, mixing the pretreated fiber with a monomer mixture, a fluorine-containing monomer, styrene and a cross-linking agent, adding an initiator, and carrying out a heating reaction to obtain a fiber intermediate product; and S2, coating the fiber intermediate product with an antibacterial enhancement layer to obtain the antibacterial polyester fiber. The antibacterial reinforcing agent in the antibacterial reinforcing layer can generate active oxygen under illumination to provide antibacterial performance, the antibacterial performance has a long-term effect, and meanwhile, the antibacterial reinforcing agent can enhance the bonding strength, the abrasive resistance and the mechanical property of the antibacterial reinforcing layer.

Description

Technical Field

[0001] The present invention relates to the field of polyester fiber materials, and particularly to an antibacterial polyester fiber and a preparation method thereof. Background Art

[0002] Polyester fiber, namely polyethylene terephthalate fiber, abbreviated as PET fiber, commonly known as "polyester", is a synthetic fiber made by chemical polycondensation of organic dibasic acids and diols. Polyester fiber has many advantages, such as high breaking strength and elastic modulus, moderate resilience, excellent heat setting effect, good wear resistance, and stable chemical properties. It is widely used in many fields, and as a textile raw material, it has extensive applications in fields such as home textiles and industrial textiles, such as home textiles like clothing and curtains, and vehicle textiles used in trains and cars.

[0003] However, traditional polyester fibers do not have antibacterial functions, and the growth of bacteria will cause harm to the health of users. Especially for textiles used in public transportation (such as seat cushions, curtains, bed sheets, etc. on trains), the problem of bacterial growth is more serious.

[0004] Adding antibacterial agents is an effective means to endow polyester fibers with antibacterial properties. Common methods include adding antibacterial agents to the raw material components of polyester fibers. For example, a preparation method of a long-acting antibacterial polyester fiber disclosed in patent CN111020734B, a method for preparing copper oxide antibacterial fibers disclosed in patent CN105401245B, etc. This method has the following problems: the antibacterial modified components dispersed inside the fibers cannot play an antibacterial role during application and will have an adverse impact on the basic properties of the fibers such as strength. In addition, some traditional metal particles / ions can endow polyester with high antibacterial effects and good durability through melt blending spinning, but there will be toxicity problems caused by heavy metal accumulation.

[0005] Another method is to form an antibacterial coating or film layer on the surface of polyester fibers. For example, the production method of antibacterial polyester fibers disclosed in patent CN115961377B, which applies an emulsion of fiber oil agent containing antibacterial guanidine salt to the surface of the nascent fiber, but it is difficult to provide long-term antibacterial performance.

[0006] Patent CN118422487A discloses a photosensitive antibacterial polyester fiber fabric and its preparation method. Based on the aPDI effect of fluorescence resonance energy transfer (FRET), with bismuth vanadate as the donor and curcumin as the acceptor, the fluorescence emitted by bismuth vanadate under visible light excitation matches the absorption wavelength of curcumin. Through fluorescence resonance energy transfer, the natural plant-derived photosensitizer curcumin is excited to generate a high yield of singlet oxygen, achieving efficient and long-lasting sterilization. However, it has the following problems: (1) It uses singlet oxygen with strong oxidizing properties to provide antibacterial performance, but singlet oxygen can damage the mechanical properties of polyester fibers: Singlet oxygen reacts with double bonds or other active sites in polyester molecules to generate free radicals, and these free radicals further initiate chain reactions, resulting in the breakage, crosslinking, or formation of new chemical bonds in the polyester main chain, thereby destroying the structure and properties of polyester. (2) It is difficult to achieve long-lasting antibacterial performance.

[0007] Therefore, it is necessary to improve the existing technology to provide a more reliable solution. Summary of the Invention

[0008] The technical problem to be solved by the present invention is to provide an antibacterial polyester fiber and its preparation method in view of the above deficiencies in the prior art.

[0009] To solve the above technical problems, the technical solution adopted by the present invention is: A preparation method of an antibacterial polyester fiber, comprising the following steps:

[0010] S1. Coating an isolation transition layer on the PET fiber:

[0011] S1-1. After washing the PET fiber, it is mixed and reacted with a silane coupling agent to obtain a pretreated fiber;

[0012] S1-2. The pretreated fiber is mixed with a monomer mixture, a fluorinated monomer, styrene, and a crosslinking agent, and after adding an initiator, it is heated and reacted to obtain an intermediate fiber product;

[0013] S2. Coating an antibacterial enhancement layer on the intermediate fiber product:

[0014] S2-1. The antibacterial enhancer is mixed and reacted with a silane coupling agent to obtain a modified antibacterial enhancer;

[0015] S2-2. The intermediate fiber product, the modified antibacterial enhancer are mixed with a monomer mixture and a crosslinking agent, and after adding an initiator, it is heated and reacted to obtain an antibacterial polyester fiber;

[0016] The antibacterial enhancer is prepared by the following method:

[0017] 1-1) Prepare rare earth cerium-doped mesoporous silica:

[0018] 1-2) Mix T3C2Tx MXene is treated with acid and then added to an aqueous solution of ammonium dihydrogen phosphate for reaction to obtain pretreated T3C2T x MXene;

[0019] 1-3) Rare earth cerium-doped mesoporous silica, octanohydroxamic acid, pretreated T3C2T x MXene and ethylenediamine are mixed and subjected to hydrothermal reaction to obtain an antibacterial enhancer.

[0020] Preferably, the monomer mixture is a mixture of acrylic acid, 2-hydroxyethyl methacrylate, and 2-hydroxyethyl 2-methyl-2-propenoate phosphate.

[0021] Preferably, the fluorinated monomer is one or more of trifluoroethyl methacrylate, 1H,1H,2H,2H-perfluorooctyl methacrylate, perfluoromethyl ethyl acrylate, and 2-perfluorododecylethyl methacrylate. More preferably, the fluorinated monomer is 2-perfluorododecylethyl methacrylate.

[0022] Preferably, the crosslinking agent is divinylbenzene.

[0023] Preferably, the preparation method of the antibacterial polyester fiber includes the following steps:

[0024] S1. Coating an isolation transition layer on the PET fiber:

[0025] S1-1. The PET fiber is washed and then impregnated in ethanesulfonic acid, taken out and mixed with the silane coupling agent KH-570, and reacted under heating to obtain a pretreated fiber;

[0026] S1-2. The pretreated fiber is mixed with acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl 2-methyl-2-propenoate phosphate, 2-perfluorododecylethyl methacrylate, styrene, and divinylbenzene in acetone, and benzoyl peroxide is added and then reacted under heating to obtain a fiber intermediate;

[0027] S2. Coating an antibacterial enhancement layer on the fiber intermediate:

[0028] S2-1. The antibacterial enhancer is mixed and reacted with the silane coupling agent KH-570 to obtain a modified antibacterial enhancer;

[0029] S2-2. The fiber intermediate, the modified antibacterial enhancer are mixed with acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl 2-methyl-2-propenoate phosphate, and divinylbenzene, and benzoyl peroxide is added and then reacted under heating to obtain the antibacterial polyester fiber.

[0030] Further preferably, the preparation method of the antibacterial polyester fiber includes the following steps:

[0031] S1. Coating an isolation transition layer on PET fibers:

[0032] S1-1. Wash the PET fibers successively with deionized water and ethanol, then immerse them in ethanesulfonic acid. After taking them out, mix them with the silane coupling agent KH-570 and stir and react at 50-70 °C for 12-36 h to obtain pretreated fibers; wherein, the mass ratio of KH-570 to PET fibers is 1:1 to 4:1;

[0033] S1-2. Mix the pretreated fibers, acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl 2-methyl-2-propenoate phosphate, 2-perfluorododecylethyl methacrylate, styrene, and divinylbenzene in acetone, add benzoyl peroxide, and heat and react at 60-75 °C for 6-24 h to obtain fiber intermediate products;

[0034] S2. Coating an antibacterial enhancement layer on the fiber intermediate products:

[0035] S2-1. Mix the antibacterial enhancer with the silane coupling agent KH-570 and stir and react at 70-90 °C for 6-24 h to obtain a modified antibacterial enhancer; wherein, the mass ratio of KH-570 to the antibacterial enhancer is 1:1 to 2:1;

[0036] S2-2. Mix the fiber intermediate products, the modified antibacterial enhancer, acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl 2-methyl-2-propenoate phosphate, and divinylbenzene in ethanol, add benzoyl peroxide, and heat and react at 55-70 °C for 6-24 h to obtain antibacterial polyester fibers.

[0037] Preferably, in step S1-2, the mass ratio of the pretreated fibers: acrylic acid: 2-hydroxyethyl methacrylate: 2-hydroxyethyl 2-methyl-2-propenoate phosphate: 2-perfluorododecylethyl methacrylate: styrene: divinylbenzene: benzoyl peroxide is 1:0.5-2:1-2.5:0.4-2:0.35-2:0.5-2:0.2-0.5:0.01-0.1;

[0038] In step S2-2, the mass ratio of the fiber intermediate products: the modified antibacterial enhancer: acrylic acid: 2-hydroxyethyl methacrylate: 2-hydroxyethyl 2-methyl-2-propenoate phosphate: divinylbenzene: benzoyl peroxide is 1:0.2-1:1-2.5:0.5-2:1.5-3:0.2-1:0.01-0.1.

[0039] More preferably, the preparation method of the antibacterial polyester fibers comprises the following steps:

[0040] S1. Coating an isolation transition layer on PET fibers:

[0041] S1-1. Wash 2.5 - 10 g of PET fibers successively with deionized water and ethanol, then immerse them in 5 - 15 wt% ethanesulfonic acid for 5 - 30 min. After taking them out, add them to 100 - 400 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:1, and ultrasonicate for 15 - 60 min. Add 1.25 - 5 g of silane coupling agent KH-570, stir and react at 50 - 70 °C for 12 - 36 h, centrifuge and filter. Wash the solid product with ethanol and then vacuum dry at 60 - 90 °C for 6 - 24 h to obtain pretreated fibers;

[0042] S1-2. Take 2.5 - 10 g of pretreated fibers and add them to 150 - 600 mL of acetone. Ultrasonically disperse them under a nitrogen atmosphere for 15 - 60 min, then add 2.5 - 10 g of acrylic acid, 3.5 - 14 g of 2-hydroxyethyl methacrylate, 2.5 - 9 g of 2-hydroxyethyl phosphate 2-methyl-2-propenoate, 1.75 - 7 g of 2-perfluorododecylethyl methacrylate, 2.5 - 10 g of styrene, 0.75 - 3 g of divinylbenzene. Stir under nitrogen protection for 15 - 60 min. While stirring, add 2 - 10 mL of acetone containing 0.025 - 0.1 g of benzoyl peroxide to the obtained mixture, stir and react at 60 - 68 °C for 2 - 8 h. Add 5 - 20 mL of acetone containing 0.05 - 0.2 g of benzoyl peroxide, raise the temperature to 70 - 75 °C, and continue to react for 4 - 16 h. Cool to room temperature, filter by suction. Wash the solid product successively with acetone and ethanol, and vacuum dry at 50 - 70 °C for 6 - 24 h to obtain fiber intermediate products;

[0043] S2. Coating an antibacterial reinforcing layer on the fiber intermediate products:

[0044] S2-1. Mix 1 - 4 g of antibacterial enhancer with 0.75 - 3 g of silane coupling agent KH-570 in 50 - 200 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:1, stir and react at 70 - 90 °C for 6 - 24 h, filter. Wash the solid product with deionized water and then vacuum dry at 60 - 80 °C for 6 - 24 h to obtain modified antibacterial enhancer;

[0045] S2-2. Take 2.5 - 10 fiber intermediates and 1 - 4 g of modified antibacterial enhancer, add them to 75 - 300 mL of ethanol, ultrasonically disperse for 15 - 60 min under nitrogen, then add 3.75 - 15 g of acrylic acid, 5 - 20 g of 2 - hydroxyethyl methacrylate, 3 - 12 g of 2 - hydroxyethyl 2 - methyl - 2 - acrylate phosphate, and 0.75 - 3 g of divinylbenzene. Stir for 15 - 60 min under nitrogen protection, and dropwise add 2 - 10 mL of acetone containing 0.025 - 0.1 g of benzoyl peroxide while stirring. Stir and react at 50 - 65 °C for 2 - 8 h, add 5 - 20 mL of acetone containing 0.05 - 0.2 g of benzoyl peroxide, raise the temperature to 65 - 70 °C, and continue to react for 4 - 16 h. Cool to room temperature, filter by suction, wash the solid product with acetone and ethanol successively, and dry in vacuum at 50 - 70 °C for 6 - 24 h to obtain antibacterial polyester fibers.

[0046] Preferably, the antibacterial enhancer is prepared by the following method:

[0047] 1 - 1) Preparation of rare - earth cerium - doped mesoporous silica:

[0048] Add hexadecylamine, cerium nitrate, mesitylene, and deionized water to n - pentanol, disperse, then add tetraethyl orthosilicate, and then dropwise add ammonia water. Stir and react, filter, wash, and dry the product, and then calcine to obtain rare - earth cerium - doped mesoporous silica;

[0049] 1 - 2) Load MXene quantum dots on the rare - earth cerium - doped mesoporous silica;

[0050] Add the T3C2T x MXene treated with a mixed acid composed of nitric acid and sulfuric acid to an aqueous solution of ammonium dihydrogen phosphate, stir and react, centrifuge and filter, wash to obtain the pretreated T3C2T x MXene;

[0051] 1 - 3) Mix rare - earth cerium - doped mesoporous silica, octanohydroxamic acid, pretreated T3C2T x MXene, and ethylenediamine in deionized water, ultrasonically disperse, transfer to a reaction kettle, carry out hydrothermal reaction under heating, filter, wash, and dry to obtain the antibacterial enhancer.

[0052] More preferably, the antibacterial enhancer is prepared by the following method:

[0053] 1 - 1) Preparation of rare - earth cerium - doped mesoporous silica:

[0054] Add 0.75 - 3 g of hexadecylamine, 0.25 - 1 g of cerium nitrate, 0.2 - 0.8 g of mesitylene, and 60 - 240 mL of deionized water to 75 - 300 n - pentanol, ultrasonically disperse for 5 - 30 min, then add 4.5 - 20 mL of tetraethyl orthosilicate, and then dropwise add 5 - 20 mL of ammonia water with a mass concentration of 5 - 20%. Stir and react at 20 - 30 °C for 12 - 48 h. After filtering the product, wash it with deionized water, dry it at 50 - 70 °C for 4 - 16 h, and then calcine it at 500 - 600 °C for 3 - 10 h to obtain rare - earth cerium - doped mesoporous silica;

[0055] 1 - 2) Load MXene quantum dots on the rare - earth cerium - doped mesoporous silica;

[0056] Add 0.5 - 2 g of T3C2T x MXene to a mixed acid containing 25 - 100 mL of 65 wt% concentrated nitric acid and 25 - 100 mL of 95 wt% concentrated sulfuric acid, react at 90 - 100 °C for 4 - 16 h, filter after cooling to room temperature, wash with deionized water until neutral, and then add it to 50 - 200 mL of an aqueous solution of ammonium dihydrogen phosphate with a mass concentration of 2.5 - 10%. Stir at room temperature for 6 - 24 h, centrifuge and filter, wash to obtain pretreated T3C2T x MXene;

[0057] 1 - 3) Take 1.25 - 5 g of rare - earth cerium - doped mesoporous silica and 0.5 - 2 g of octanoyl hydroxamic acid, add them to 100 - 400 mL of deionized water, ultrasonically disperse for 15 - 60 min, and then add the pretreated T3C2T x MXene and 0.05 - 0.3 g of ethylenediamine, ultrasonically disperse for 30 - 90 min. Transfer the obtained mixture to a stainless - steel autoclave, react at 120 - 150 °C for 6 - 24 h, cool to room temperature, centrifuge and filter. Wash the solid product with deionized water and ethanol in sequence, vacuum - dry at 70 - 90 °C for 6 - 24 h, and grind to obtain an antibacterial enhancer.

[0058] The present invention also provides an antibacterial polyester fiber, which includes a PET fiber as the core, an isolation transition layer coated on the core, and an antibacterial enhancement layer coated on the isolation transition layer; the antibacterial polyester fiber is prepared by the method described above.

[0059] The antibacterial polyester fiber prepared by the present invention has a structure with a PET fiber as the core and an isolation transition layer and an antibacterial enhancement layer as double - coating layers. The antibacterial enhancement layer in it can at least provide long - term antibacterial performance by generating reactive oxygen species under light through the contained antibacterial enhancer, and at the same time can also enhance the bonding strength, wear resistance, and mechanical properties of the antibacterial enhancement layer; the isolation transition layer can isolate the reactive oxygen species (such as singlet oxygen) generated in the antibacterial enhancement layer1 O2), preventing reactive oxygen species from entering the core and accelerating the aging and degradation of the core, thus damaging the mechanical properties of the core. At the same time, the double coating layer structure has an improvement effect on the mechanical properties, scratch resistance, etc. of PET fibers.

[0060] Preparation process of antibacterial polyester fiber:

[0061] 1. First, clean PET fibers (polyester fibers, i.e., polyethylene terephthalate fibers), impregnate and activate them with ethanesulfonic acid, then modify the surface with silane coupling agent KH-570 to achieve vinyl modification and obtain pretreated fibers; then perform a coating treatment: use acrylic acid, 2-hydroxyethyl methacrylate, 2-perfluorododecylethyl methacrylate, 2-hydroxyethyl phosphate 2-methyl-2-acrylate, and styrene as mixed monomers, divinylbenzene as a crosslinking agent, and benzoyl peroxide as an initiator. Through in-situ polymerization, form an isolation transition layer on the surface of the pretreated fibers to obtain fiber intermediates.

[0062] Among them, the double bonds contained in the silane coupling agent KH-570 (methacryloxy-functional silane) used to modify the surface of the pretreated fibers can participate in the polymerization reaction process (Sun Guisheng, Zu Jianhua, Liu Xinwen, etc. Research on the surface modification of nano-silica and radiation-induced grafting of GMA [J]. Journal of Radiation Research and Radiation Processing, 2007, 25(5):275-278. DOI:10.3969 / j.issn.1000-3436.2007.05.005.), thus promoting the formation of the isolation transition layer coating film on the surface of the pretreated fibers.

[0063] Among them, acrylic acid and 2-hydroxyethyl methacrylate, as the main acrylic monomers for film formation, can form a polyacrylate-based coating film layer with high weather resistance, transparency, and excellent mechanical properties.

[0064] Among them, 2-hydroxyethyl phosphate 2-methyl-2-acrylate (alias: 2-hydroxyethyl methacrylate phosphate) is used as a functional monomer. Its molecular structure protects double bonds and hydroxyl groups and has reactivity. Its double bonds can participate in the polymerization reaction, enabling it to be uniformly doped into the isolation transition layer, effectively enhancing the adhesion and denseness of the film layer, improving the barrier effect. At the same time, 2-hydroxyethyl phosphate 2-methyl-2-acrylate can improve the flame retardancy (Lai Xuejun, Yan Lu, Li Hongqiang, etc. Preparation and properties of 2-hydroxyethyl methacrylate phosphate californium salt and bicyclic cage phosphate synergistic flame retardant PP / EPDM thermoplastic elastomer [J]. Guangdong Rubber, 2017(8):7. DOI:10.ssss / j.cn.44-1271(TQ).2017.8.000.)), and its addition can improve the flame retardancy of the prepared antibacterial polyester fiber products.

[0065] Among them, the addition of the fluorine-containing monomer 2-perfluorododecylethyl methacrylate can introduce perfluoroalkyl groups onto the polyacrylate polymer chain, which can further improve the barrier ability of the isolation transition layer, especially the barrier ability to reactive oxygen, and at the same time can also improve the compactness, stability and durability of the coating layer. In the isolation transition layer formed by the fluorinated acrylate polymer, the perfluoro groups are located on the side chains of the polymer. During the film-forming process, the perfluoroalkyl groups will accumulate at the polymer interface and stretch outwards. Since the perfluoro side chains tend to face outwards, they form a "shielding protection" for the main chain and internal molecules, and for singlet oxygen 1 such as O2 also has good barrier effects. Secondly, the fluorine atom radius is slightly larger than that of the hydrogen atom, but smaller than that of other elements' atoms, and can tightly wrap the carbon-carbon main chain, thereby improving the stability and durability of the polymer, enabling the isolation transition layer to withstand the attack of reactive oxygen generated in the antibacterial enhancement layer and protecting the PET fiber core in the inner layer.

[0066] Among them, styrene is used as a doping monomer. The double bonds it contains can participate in the polymerization reaction to form polystyrene by doping, which can improve the film-forming performance and film-forming strength, and can also improve the flexibility and impact resistance of the film layer. In addition, it can also enhance the weather resistance of the film layer.

[0067] Among them, divinylbenzene can be used as a crosslinking agent to improve the film-forming strength and bonding performance.

[0068] 2. Then, a secondary coating treatment is carried out: acrylic acid, 2-hydroxyethyl methacrylate, and 2-hydroxyethyl 2-methyl-2-propenoate phosphate are used as mixed monomers, divinylbenzene is used as a crosslinking agent, benzoyl peroxide is used as an initiator, and a modified bacteriostatic agent modified by a silane coupling agent KH-570 is used as a component providing antibacterial activity enhancement. An antibacterial enhancement layer is formed by in-situ polymerization on the surface of the isolation transition layer of the fiber intermediate product to obtain the final antibacterial polyester fiber. In this process, the modification of KH-570 introduces double bonds that can participate in the polymerization reaction on the surface of the modified bacteriostatic agent, so that the modified bacteriostatic agent can be evenly dispersed in the polymer system to participate in film formation, and can improve the interfacial connection strength, forming an antibacterial enhancement layer with uniform distribution of the modified bacteriostatic agent.

[0069] Acrylic acid, 2-hydroxyethyl methacrylate, and 2-hydroxyethyl 2-methyl-2-propenoate phosphate are used as film-forming monomers, and divinylbenzene is used as a crosslinking agent. Their functions are similar to those in the isolation transition layer, and finally an antibacterial enhancement layer with excellent antibacterial performance and good mechanical properties is formed on the surface of the isolation transition layer.

[0070] In the present invention, the modified bacteriostatic agent as the activity enhancement component can not only provide long-term antibacterial performance, but also enhance the bonding strength, wear resistance and mechanical properties of the film layer. Its preparation process and action mechanism are as follows:

[0071] (1) First, using hexadecylamine as a template agent, mesitylene as a pore-expanding agent, and cerium nitrate as a doping component, rare-earth cerium-doped mesoporous silica was synthesized by the soft-template method. It has a rich pore structure. As a pore-expanding agent, mesitylene can increase the pore diameter and promote the formation of a three-dimensional pore structure, creating favorable conditions for using it as a carrier to load MXene quantum dots.

[0072] (2) After treating the T3C2T x MXene material with a mixed acid and then performing an intercalation treatment with ammonium dihydrogen phosphate, the pretreated T3C2T x MXene was obtained. Then, the pretreated T3C2T x MXene was blended with ethylenediamine, octanohydroxamic acid, and rare-earth cerium-doped mesoporous silica, and phosphorus- and nitrogen-doped MXene quantum dots were in-situ synthesized on the rare-earth cerium-doped mesoporous silica through a one-pot hydrothermal reaction to obtain an antibacterial enhancer.

[0073] Among them, on the one hand, rare-earth cerium-doped mesoporous silica itself can serve as an enhancing component of the antibacterial enhancing layer, which can improve the wear resistance, adhesion strength, and stability of the film layer (Bao Yan, Li Miao, Ma Jianzhong, et al. Effect of hollow SiO2 microspheres on the properties of polyacrylate films [J]. Journal of Functional Materials, 2016, 47(7):6. DOI: 10.3969 / j.issn.1001 - 9731.2016.07.005.). On the other hand, in the present invention, rare-earth cerium-doped mesoporous silica also serves as a carrier. With its rich pore structure, it can achieve a large amount and uniform loading of MXene quantum dots during the in-situ hydrothermal synthesis of MXene quantum dots. And during use, the antibacterial enhancer dispersed in the antibacterial enhancing layer can provide a slow-release effect on MXene quantum dots and the reactive oxygen species generated by them through the mesoporous structure of silica, providing long-term antibacterial performance: the MXene quantum dots in the mesoporous structure can slowly release into the antibacterial enhancing layer system during long-term use, exerting their long-term antibacterial performance and avoiding the aggregation of MXene quantum dots in the antibacterial enhancing layer system; similarly, the reactive oxygen species generated by the MXene quantum dots in the mesoporous structure under light can also slowly and continuously release into the antibacterial enhancing layer system.

[0074] Among them, during the high-temperature calcination of mesoporous silica doped with cerium, nano-CeO2 will be formed, which can improve the strength and thermal stability of mesoporous silica, reduce the collapse of the pore structure during high-temperature calcination, and ensure the porosity of mesoporous silica; on the other hand, rare earth Ce has a high affinity for oxygen. In the antibacterial enhancer system, rare earth Ce can efficiently capture oxygen-containing substances (such as oxygen) entering the system, thereby promoting MXene quantum dots to use oxygen-containing substances to produce active oxygen under light, thereby improving the efficiency of active oxygen generation;

[0075] Among them, the main function of MXene quantum dots loaded on rare earth cerium-doped mesoporous silica is to provide antibacterial properties. Its antibacterial mechanism is mainly as follows: (1) MXene quantum dots The surface of MXene quantum dots is rich in oxygen vacancies. These oxygen vacancies can serve as active sites to promote the adsorption and activation of oxygen molecules. They use oxygen in the air to efficiently produce reactive oxygen species (ROS) under light, such as singlet oxygen and hydroxyl radicals. These reactive oxygen species can oxidize biological macromolecules in bacterial cells, such as DNA, proteins and lipids, leading to cell damage and death. (2) MXene quantum dots can enter the bacterial cell membrane or adsorb on it, destroying the integrity of the membrane, leading to leakage of cell contents and cell death.

[0076] Among them, octanoylhydroxamic acid as a precursor substance has excellent antibacterial properties, and its doping can improve the antibacterial properties of the prepared MXene quantum dots. At the same time, octanoylhydroxamic acid can introduce the doping element N into the MXene quantum dots, which can effectively regulate the charge distribution, promote electron transfer, and improve the efficiency of generating active oxygen under light.

[0077] Among them, T3C2T was treated with ammonium dihydrogen phosphate x MXene is intercalated to introduce P. The doping of P in MXene quantum dots can reduce the bandgap width of MXene quantum dots, increase the width of their absorption spectrum, provide more photogenerated electrons and photogenerated holes, and thus improve the efficiency of generating active oxygen under light.

[0078] The beneficial effects of the present invention are:

[0079] The present invention provides an antibacterial polyester fiber with a double coating structure, which has a PET fiber as a core, an isolation transition layer as an inner coating layer, and an antibacterial reinforcement layer as an outer coating layer;

[0080] The antibacterial enhancer in the antibacterial enhancement layer can generate active oxygen under light to provide antibacterial performance, and the antibacterial performance is long-lasting. At the same time, the antibacterial enhancer can also enhance the bonding strength, wear resistance and mechanical properties of the antibacterial enhancement layer.

[0081] Among them, the isolation transition layer can isolate the reactive oxygen generated in the antibacterial enhancement layer, prevent the reactive oxygen from entering the core body and accelerating the aging and degradation of the core body, so as to damage the mechanical properties of the core body. At the same time, the coating of the isolation transition layer and the antibacterial enhancement layer can also improve the mechanical properties and scratch resistance of the PET fiber.

[0082] In the present invention, the compounding of the functional monomer 2-hydroxyethyl phosphate 2-methyl-2-acrylate, the fluorine-containing monomer 2-perfluorododecylethyl methacrylate, the doping monomer styrene and the acrylic monomer endows the prepared isolation transition layer with excellent bonding strength, density, durability and stability, which can ensure its barrier ability, thus being able to cope with the attack of the reactive oxygen generated in the antibacterial enhancement layer and protect the PET fiber core body in the inner layer. Therefore, the goal of providing antibacterial ability through reactive oxygen while avoiding the destruction of the fiber body structure by reactive oxygen is achieved.

[0083] In the present invention, the modified bacteriostatic agent constructs a loading system through rare earth cerium-doped mesoporous silica and phosphorus and nitrogen-doped MXene quantum dots, realizing the uniform distribution of MXene quantum dots in the antibacterial enhancement layer system. At the same time, it can also exhibit long-lasting and stable antibacterial properties, and can simultaneously improve the bonding strength, wear resistance and mechanical properties of the antibacterial enhancement layer. BRIEF DESCRIPTION OF THE DRAWINGS

[0084] Figure 1 Test results of singlet oxygen generation performance of antibacterial enhancers AP1-AP4;

[0085] Figure 2 Test results of antibacterial performance of antibacterial enhancers AP1-AP4;

[0086] Figure 3 Infrared spectrum of antibacterial enhancer AP1;

[0087] Figure 4 Test results of antibacterial performance of antibacterial polyester fiber;

[0088] Figure 5 Test results of breaking strength of antibacterial polyester fiber;

[0089] Figure 6 Test results of breaking strength retention rate of antibacterial polyester fiber after light exposure. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0090] The following further describes the present invention in detail with reference to the embodiments, so that those skilled in the art can implement it according to the description in the specification.

[0091] It should be understood that the terms such as "having", "comprising" and "including" used herein do not exclude the presence or addition of one or more other elements or their combinations.

[0092] Unless otherwise specified, the test methods used in the following examples are all conventional methods. Unless otherwise specified, the materials, reagents, etc. used in the following examples are all commercially available. For those not specified with specific conditions in the following examples, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. For those reagents or instruments without indicating the manufacturer, they are all conventional products that can be obtained by purchasing in the market.

[0093] 1. The sources of the main raw materials involved are as follows:

[0094] Polyester chip, model CB-602, relative viscosity 0.8 dl / g, acid value 35 mg KOH / g, Far Eastern New Century Corporation (Shanghai);

[0095] Ti3AlC2, 800 mesh, Suzhou Kefa New Material Technology Co., Ltd.;

[0096] Ethanesulfonic acid, Nanjing Chemical Reagent Co., Ltd.;

[0097] Silane coupling agent KH-570, Nanjing Chemical Reagent Co., Ltd.;

[0098] Acrylic acid, Nanjing Chemical Reagent Co., Ltd.;

[0099] 2-Hydroxyethyl methacrylate, Jiangsu Runfeng Synthetic Technology Co., Ltd.;

[0100] 2-Hydroxyethyl 2-methyl-2-propenoate phosphate, Nantong Runfeng Petrochemical Co., Ltd.;

[0101] 2-Perfluorododecylethyl methacrylate, CAS No.: 6014-75-1, Shaanxi Didu New Material Co., Ltd.

[0102] Styrene, Jiangsu Runfeng Synthetic Technology Co., Ltd.;

[0103] Divinylbenzene, Jiangsu Runfeng Synthetic Technology Co., Ltd.;

[0104] Hexadecylamine, Jiangsu Runfeng Synthetic Technology Co., Ltd.;

[0105] Mesitylene, Nanjing Chemical Reagent Co., Ltd.;

[0106] Tetraethyl orthosilicate, Nanjing Chemical Reagent Co., Ltd.;

[0107] Ammonium dihydrogen phosphate, Nanjing Chemical Reagent Co., Ltd.;

[0108] Octanoyl hydroxamic acid, Nantong Shenglun Chemical Technology Co., Ltd.

[0109] 2. PET fiber can be commercially available or homemade. In the present invention, the conventional method is used to make homemade PET fiber for use in the following examples and comparative examples. The preparation method is as follows:

[0110] The polyester chips were dried at 90°C for 8 hours, and then added into a melt spinning machine for melt spinning, winding, stretching, and air cooling to obtain polyester fibers; wherein the spinning temperature was 270°C, the winding rate was 1000m / mim, the stretching ratio was 2.5 times, and the stretching rate was 800m / mim.

[0111] 3. T3C2T x MXene can be commercially available or homemade. In the present invention, conventional methods are used to make T3C2T x MXene is used in the following examples and comparative examples, and the preparation method is as follows:

[0112] 2 g Ti3AlC2 powder was added to 45 mL 35 wt% HF solution and stirred at room temperature for 48 h. The product was centrifuged and washed with deionized water until the pH of the supernatant was > 6.5. It was then vacuum dried at 70 °C for 24 h to obtain T3C2T x MXene.

[0113] 4. Prepare a series of antibacterial enhancers in advance for use in subsequent examples and comparative examples.

[0114] 4-1. Antibacterial enhancer AP1

[0115] It is prepared by the following method:

[0116] 1-1) Preparation of rare earth cerium doped mesoporous silica:

[0117] 1.5 g of hexadecylamine, 0.5 g of cerium nitrate, 0.4 g of mesitylene, and 120 mL of deionized water were added to 150 ml of n-pentanol, and ultrasonically dispersed for 15 min. Then, 9.5 mL of tetraethyl orthosilicate was added, and then 10 mL of 10% ammonia water was added dropwise. The mixture was stirred and reacted at 25 ° C for 24 h. The product was filtered and washed with deionized water, dried at 60 ° C for 8 h, and then calcined at 550 ° C for 5 h to obtain rare earth cerium doped mesoporous silica.

[0118] 1-2) Loading MXene quantum dots on rare earth cerium-doped mesoporous silica:

[0119] 1g T3C2T xMXene was added to a mixed acid containing 50 mL of 65 wt% concentrated nitric acid and 50 mL of 95 wt% concentrated sulfuric acid, and the reaction was carried out at 100 °C for 8 h. After cooling to room temperature, it was filtered, washed with deionized water until neutral, and then added to 100 mL of an aqueous ammonium dihydrogen phosphate solution with a mass concentration of 5%. It was stirred at room temperature for 12 h, centrifuged, filtered, and washed to obtain pretreated T3C2T x MXene;

[0120] 1-3) Take 2.5 g of rare earth cerium-doped mesoporous silica and 1 g of octanohydroxamic acid, add them to 200 mL of deionized water, ultrasonically disperse for 30 min, and then add the pretreated T3C2T prepared in step 1-2 x MXene, 0.15 g of ethylenediamine, ultrasonically disperse for 45 min. The obtained mixture was transferred to a stainless steel autoclave and reacted at 140 °C for 12 h. After cooling to room temperature, it was centrifuged and filtered. The solid product was washed successively with deionized water and ethanol, vacuum dried at 80 °C for 12 h, and ground to obtain an antibacterial enhancer, denoted as antibacterial enhancer AP1.

[0121] 4-2. Antibacterial enhancer AP2

[0122] It is prepared by the following method:

[0123] 1-1) Preparation of mesoporous silica:

[0124] Add 1.5 g of hexadecylamine, 0.4 g of mesitylene, and 120 mL of deionized water to 150 n-pentanol, ultrasonically disperse for 15 min, then add 9.5 mL of tetraethyl orthosilicate, and then dropwise add 10 mL of ammonia water with a mass concentration of 10%. Stir and react at 25 °C for 24 h. After the product is filtered, it is washed with deionized water and dried at 60 °C for 8 h and then calcined at 550 °C for 5 h to obtain mesoporous silica;

[0125] 1-2) Loading MXene quantum dots on mesoporous silica;

[0126] Add 1 g of T3C2T x MXene to a mixed acid containing 50 mL of 65 wt% concentrated nitric acid and 50 mL of 95 wt% concentrated sulfuric acid, and the reaction is carried out at 100 °C for 8 h. After cooling to room temperature, it is filtered, washed with deionized water until neutral, and then added to 100 mL of an aqueous ammonium dihydrogen phosphate solution with a mass concentration of 5%. It is stirred at room temperature for 12 h, centrifuged, filtered, and washed to obtain pretreated T3C2T x MXene;

[0127] 1-3) Take 2.5 g of mesoporous silica and 1 g of octanohydroxamic acid, add them to 200 mL of deionized water, ultrasonically disperse for 30 min, and then add the pretreated T3C2T prepared in step 1-2x MXene, 0.15 g of ethylenediamine were ultrasonically dispersed for 45 min. The obtained mixture was transferred to a stainless-steel autoclave and reacted at 140 °C for 12 h. After cooling to room temperature, it was centrifuged and filtered. The solid product was washed successively with deionized water and ethanol, vacuum-dried at 80 °C for 12 h, and ground to obtain an antibacterial enhancer, denoted as antibacterial enhancer AP2.

[0128] 4-3. Antibacterial enhancer AP3

[0129] It was prepared by the following method:

[0130] 1-1) Prepare rare-earth cerium-doped mesoporous silica by the same method as AP1:

[0131] 1-2) Load MXene quantum dots on the rare-earth cerium-doped mesoporous silica by the same method as AP1;

[0132] 1-3) Take 2.5 g of rare-earth cerium-doped mesoporous silica and add it to 200 mL of deionized water, ultrasonically disperse for 30 min, and then add the pretreated T3C2T prepared in step 1-2) x MXene, 0.15 g of ethylenediamine were ultrasonically dispersed for 45 min. The obtained mixture was transferred to a stainless-steel autoclave and reacted at 140 °C for 12 h. After cooling to room temperature, it was centrifuged and filtered. The solid product was washed successively with deionized water and ethanol, vacuum-dried at 80 °C for 12 h, and ground to obtain an antibacterial enhancer, denoted as antibacterial enhancer AP3.

[0133] 4-4. Antibacterial enhancer AP4

[0134] It was prepared by the following method:

[0135] 1-1) Prepare rare-earth cerium-doped mesoporous silica by the same method as AP1:

[0136] 1-2) Load MXene quantum dots on the rare-earth cerium-doped mesoporous silica;

[0137] Add 1 g of T3C2T x MXene to a mixed acid containing 50 mL of 65 wt% concentrated nitric acid and 50 mL of 95 wt% concentrated sulfuric acid, react at 100 °C for 8 h, filter after cooling to room temperature, wash with deionized water until neutral, and centrifuge to obtain pretreated T3C2T x MXene;

[0138] 1-3) Take 2.5 g of rare-earth cerium-doped mesoporous silica, 1 g of octanoyl hydroxamic acid and add them to 200 mL of deionized water, ultrasonically disperse for 30 min, and then add the pretreated T3C2T prepared in step 1-2) xMXene, 0.15 g of ethylenediamine were ultrasonically dispersed for 45 min. The obtained mixture was transferred to a stainless-steel autoclave and reacted at 140 °C for 12 h. After cooling to room temperature, it was centrifuged and filtered. The solid product was washed successively with deionized water and ethanol, vacuum-dried at 80 °C for 12 h, and ground to obtain an antibacterial enhancer, denoted as antibacterial enhancer AP4.

[0139] Example 1

[0140] An antibacterial polyester fiber includes a PET fiber as the core, an isolation transition layer coated on the core, and an antibacterial enhancement layer coated on the isolation transition layer. Its preparation method includes the following steps:

[0141] S1. Coating an isolation transition layer on the PET fiber:

[0142] S1-1. Pretreatment of the PET fiber:

[0143] Take 5 g of PET fiber and add it to deionized water, ultrasonically clean it at 70 °C for 30 min, then add it to ethanol and ultrasonically clean it at 50 °C for 30 min. After taking it out, immerse it in ethane sulfonic acid with a mass concentration of 8% for 15 min and then take it out. Then add it to 200 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:1, ultrasonically for 30 min, add 2.5 g of silane coupling agent KH-570, stir and react at 60 °C for 24 h, centrifuge and filter. The solid product is washed with ethanol and then vacuum-dried at 70 °C for 12 h to obtain pretreated fiber.

[0144] S1-2. Primary in-situ coating treatment;

[0145] Take 5 g of pretreated fiber and add it to 300 mL of acetone, ultrasonically disperse it under nitrogen for 30 min, then add 5 g of acrylic acid, 7 g of 2-hydroxyethyl methacrylate, 4.5 g of 2-hydroxyethyl phosphate 2-methyl-2-acrylate, 3.5 g of 2-perfluorododecylethyl methacrylate, 5 g of styrene, and 1.5 g of divinylbenzene. Stir for 30 min under nitrogen protection. While stirring, add 5 mL of acetone containing 0.05 g of benzoyl peroxide dropwise to the obtained mixture, stir and react at 65 °C for 4 h, add 10 mL of acetone containing 0.1 g of benzoyl peroxide, raise the temperature to 72 °C, and continue to react for 8 h. After cooling to room temperature, filter by suction. The solid product is washed successively with acetone and ethanol, vacuum-dried at 60 °C for 12 h, and an isolation transition layer is coated on the surface of the pretreated fiber to obtain a fiber intermediate product.

[0146] S2. Coating an antibacterial enhancement layer on the fiber intermediate product:

[0147] S2-1. Take 2 g of antibacterial enhancer AP1 and add it to 100 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:1. Ultrasonically disperse for 30 min, then add 1.5 g of silane coupling agent KH-570, and stir and react at 85 °C for 12 h. Filter, wash the solid product with deionized water, and then vacuum dry at 70 °C for 12 h to obtain a surface-modified antibacterial enhancer;

[0148] S2-2. Secondary in-situ coating treatment: Take 5 g of fiber intermediate product and 2 g of surface-modified bacteriostatic agent and add them to 150 mL of ethanol. Ultrasonically disperse for 30 min under nitrogen gas, then add 7.5 g of acrylic acid, 6 g of 2-hydroxyethyl phosphate 2-methyl-2-acrylate, 10 g of 2-hydroxyethyl methacrylate, and 1.5 g of divinylbenzene. Stir for 30 min under nitrogen protection, and dropwise add 5 mL of acetone containing 0.05 g of benzoyl peroxide while stirring. Stir and react at 60 °C for 4 h, add 10 mL of acetone containing 0.1 g of benzoyl peroxide, raise the temperature to 70 °C, and continue to react for 8 h. Cool to room temperature, filter by suction, wash the solid product with acetone and ethanol in sequence, and vacuum dry at 60 °C for 12 h to form an antibacterial enhancement layer on the surface of the isolation transition layer of the fiber intermediate product, obtaining antibacterial polyester fiber.

[0149] Example 2

[0150] An antibacterial polyester fiber, comprising a PET fiber as the core, an isolation transition layer coated on the core, and an antibacterial enhancement layer coated on the isolation transition layer. Its preparation method includes the following steps:

[0151] S1. Coat an isolation transition layer on the PET fiber:

[0152] S1-1. Pretreatment of PET fiber:

[0153] Take 5 g of PET fiber and add it to deionized water. Ultrasonically clean at 70 °C for 30 min, then add it to ethanol and ultrasonically clean at 50 °C for 30 min. Take it out and immerse it in ethane sulfonic acid with a mass concentration of 8% for 15 min and then take it out. Then add it to 200 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:1, ultrasonically for 30 min, add 2.5 g of silane coupling agent KH-570, stir and react at 60 °C for 24 h, centrifuge and filter, wash the solid product with ethanol, and then vacuum dry at 70 °C for 12 h to obtain a pretreated fiber;

[0154] S1-2. Primary in-situ coating treatment;

[0155] Take 5 g of pretreated fibers, add them to 300 mL of acetone, and ultrasonically disperse them for 30 min under a nitrogen atmosphere. Then add 5 g of acrylic acid, 7 g of 2-hydroxyethyl methacrylate, 4.0 g of 2-hydroxyethyl phosphate 2-methyl-2-propenoate, 4.0 g of 2-perfluorododecylethyl methacrylate, 5 g of styrene, and 1.5 g of divinylbenzene. Stir for 30 min under nitrogen protection. While stirring, add 5 mL of acetone containing 0.05 g of benzoyl peroxide dropwise to the resulting mixture. Stir and react at 65 °C for 4 h. Add 10 mL of acetone containing 0.1 g of benzoyl peroxide, raise the temperature to 72 °C, and continue to react for 8 h. Cool to room temperature, filter by suction. Wash the solid product successively with acetone and ethanol, and dry it in vacuo at 60 °C for 12 h to form an isolation transition layer on the surface of the pretreated fibers, obtaining an intermediate fiber product;

[0156] S2. Coating an antibacterial enhancement layer on the intermediate fiber product:

[0157] S2-1. Take 2 g of antibacterial enhancer AP1, add it to 100 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:1, ultrasonically disperse it for 30 min, then add 1.5 g of silane coupling agent KH-570, stir and react at 85 °C for 12 h, filter. Wash the solid product with deionized water and then dry it in vacuo at 70 °C for 12 h to obtain a surface-modified antibacterial enhancer;

[0158] S2-2. Secondary in-situ coating treatment: Take 5 g of the intermediate fiber product and 1.8 g of the surface-modified antibacterial agent, add them to 150 mL of ethanol, ultrasonically disperse them for 30 min under a nitrogen atmosphere, then add 7.0 g of acrylic acid, 6 g of 2-hydroxyethyl phosphate 2-methyl-2-propenoate, 9 g of 2-hydroxyethyl methacrylate, and 1.5 g of divinylbenzene. Stir for 30 min under nitrogen protection. While stirring, add 5 mL of acetone containing 0.05 g of benzoyl peroxide dropwise, stir and react at 60 °C for 4 h. Add 10 mL of acetone containing 0.1 g of benzoyl peroxide, raise the temperature to 70 °C, and continue to react for 8 h. Cool to room temperature, filter by suction. Wash the solid product successively with acetone and ethanol, and dry it in vacuo at 60 °C for 12 h to form an antibacterial enhancement layer on the surface of the isolation transition layer of the intermediate fiber product, obtaining the antibacterial polyester fiber.

[0159] Example 3

[0160] An antibacterial polyester fiber, comprising a PET fiber as the core, an isolation transition layer coated on the core, and an antibacterial enhancement layer coated on the isolation transition layer. Its preparation method includes the following steps:

[0161] S1. Coating an isolation transition layer on the PET fiber:

[0162] S1-1. Pretreatment of PET fiber:

[0163] Take 5 g of PET fibers, add them to deionized water, and ultrasonically clean them at 70 °C for 30 min. Then add them to ethanol and ultrasonically clean them at 50 °C for 30 min. After taking them out, add them to ethane sulfonic acid with a mass concentration of 8% and impregnate for 15 min, then take them out. Then add them to 200 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:1, ultrasonically treat for 30 min, add 2.0 g of silane coupling agent KH-570, stir and react at 60 °C for 24 h, centrifuge and filter. Wash the solid product with ethanol and then vacuum dry at 70 °C for 12 h to obtain pretreated fibers;

[0164] S1-2, primary in-situ coating treatment;

[0165] Take 5 g of pretreated fibers and add them to 300 mL of acetone. Ultrasonically disperse them under nitrogen for 30 min. Then add 5 g of acrylic acid, 7.5 g of 2-hydroxyethyl methacrylate, 4.0 g of 2-hydroxyethyl 2-methyl-2-propenoate phosphate, 3.0 g of 2-perfluorododecylethyl methacrylate, 5.5 g of styrene, and 1.5 g of divinylbenzene. Stir under nitrogen protection for 30 min. While stirring, add 5 mL of acetone containing 0.05 g of benzoyl peroxide to the obtained mixture. Stir and react at 65 °C for 4 h. Add 10 mL of acetone containing 0.1 g of benzoyl peroxide, raise the temperature to 72 °C, and continue to react for 8 h. Cool to room temperature, filter by suction. Wash the solid product with acetone and ethanol in sequence, and vacuum dry at 60 °C for 12 h to form an isolation transition layer on the surface of the pretreated fibers to obtain fiber intermediates;

[0166] S2. Coating an antibacterial enhancement layer on the fiber intermediates:

[0167] S2-1. Take 2 g of antibacterial enhancer AP1 and add it to 100 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:1. Ultrasonically disperse it for 30 min. Then add 1.2 g of silane coupling agent KH-570. Stir and react at 85 °C for 12 h. Filter. Wash the solid product with deionized water and then vacuum dry at 70 °C for 12 h to obtain a surface-modified antibacterial enhancer;

[0168] S2-2. Secondary in-situ coating treatment: Take 5 g of the intermediate fiber product and 2 g of the surface-modified antibacterial agent, add them to 150 mL of ethanol, ultrasonically disperse for 30 min under nitrogen, then add 7.5 g of acrylic acid, 5.5 g of 2-hydroxyethyl phosphate 2-methyl-2-propenoate, 12 g of 2-hydroxyethyl methacrylate, and 1.5 g of divinylbenzene. Stir for 30 min under nitrogen protection, dropwise add 5 mL of acetone containing 0.05 g of benzoyl peroxide while stirring, stir and react at 60 °C for 4 h, add 10 mL of acetone containing 0.1 g of benzoyl peroxide, raise the temperature to 70 °C, and continue to react for 8 h. Cool to room temperature, filter by suction, wash the solid product successively with acetone and ethanol, and dry in vacuum at 60 °C for 12 h to form an antibacterial enhancement layer on the surface of the isolation transition layer of the intermediate fiber product, obtaining antibacterial polyester fiber.

[0169] Comparative Example 1

[0170] The difference between this example and Example 1 is only that: in step S2-2, the surface-modified antibacterial agent is not added.

[0171] Comparative Example 2

[0172] An antibacterial polyester fiber includes a PET fiber as the core, an isolation transition layer coated on the core, and an antibacterial enhancement layer coated on the isolation transition layer. Its preparation method includes the following steps:

[0173] S1. Coating an isolation transition layer on the PET fiber:

[0174] S1-1. Pretreatment of PET fiber:

[0175] Take 5 g of PET fiber and add it to deionized water, ultrasonically clean at 70 °C for 30 min, then add it to ethanol, ultrasonically clean at 50 °C for 30 min, take it out and immerse it in ethane sulfonic acid with a mass concentration of 8% for 15 min and then take it out, and then add it to 200 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:1, ultrasonically for 30 min, add 2.5 g of silane coupling agent KH-570, stir and react at 60 °C for 24 h, centrifuge and filter, wash the solid product with ethanol and then dry in vacuum at 70 °C for 12 h to obtain pretreated fiber;

[0176] S2. Coating an antibacterial enhancement layer on the pretreated fiber:

[0177] S2-1. Take 2 g of antibacterial enhancer AP1 and add it to 100 mL of an ethanol aqueous solution composed of ethanol and deionized water in a volume ratio of 1:1, ultrasonically disperse for 30 min, then add 1.5 g of silane coupling agent KH-570, stir and react at 85 °C for 12 h, filter, wash the solid product with deionized water and then dry in vacuum at 70 °C for 12 h to obtain a surface-modified antibacterial enhancer;

[0178] S2-2. Take 5 g of pretreated fiber and 2 g of surface-modified antibacterial agent, add them to 150 mL of ethanol, disperse ultrasonically for 30 min under nitrogen, then add 7.5 g of acrylic acid, 6 g of 2-hydroxyethyl methacrylate phosphate, 10 g of 2-hydroxyethyl methacrylate, and 1.5 g of divinylbenzene. Stir for 30 min under nitrogen protection, dropwise add 5 mL of acetone containing 0.05 g of benzoyl peroxide under stirring, stir and react at 60 °C for 4 h, supplement 10 mL of acetone containing 0.1 g of benzoyl peroxide, raise the temperature to 70 °C, continue to react for 8 h, cool to room temperature, filter by suction, wash the solid product successively with acetone and ethanol, and dry in vacuum at 60 °C for 12 h to form an antibacterial enhancement layer on the surface of the pretreated fiber, obtaining antibacterial polyester fiber.

[0179] Comparative Example 3

[0180] The difference between this example and Example 1 is only that: 2-hydroxyethyl methacrylate phosphate is not added in step S1-2.

[0181] Comparative Example 4

[0182] The difference between this example and Example 1 is only that: 2-perfluorododecylethyl methacrylate is not added in step S1-2.

[0183] Comparative Example 5

[0184] The difference between this example and Example 1 is only that: styrene is not added in step S1-2.

[0185] I. Performance test of antibacterial enhancer

[0186] (1) Singlet oxygen generation performance

[0187] Add each antibacterial enhancer (AP1-AP4) to deionized water, stir for 30 min in an air environment to prepare a dispersion with a concentration of 1 mg / mL, and use a singlet oxygen fluorescence probe (SOSG, Shanghai Beyotime Biotechnology Co., Ltd., model S0067) to measure it under light (504 nm, 0.5 W / cm 2Ability to generate ROS (stir the dispersion in an air environment for 30 min every 1 h). SOSG is a probe highly selective for singlet oxygen. Before reacting with singlet oxygen, SOSG itself has weak blue fluorescence. After reacting with singlet oxygen, the generated SOSG endoperoxide (SOSG-EP) emits green fluorescence similar to that of Fluorescein, with a maximum excitation wavelength of 504 nm and a maximum emission wavelength of 525 nm. The ability to generate singlet oxygen is judged by detecting the intensity of the emission light at 525 nm. The greater the intensity of the emission light, the stronger the ability to generate singlet oxygen.

[0188] Among them, No Light represents a blank control example, in which the antibacterial enhancer AP1 cannot generate ROS.

[0189] The test results are as Figure 1 shown. It can be seen from the test results that under no light, the antibacterial enhancer AP1 cannot generate ROS. When there is light, the antibacterial enhancers AP1 - AP4 can all generate reactive oxygen species, and the generation of reactive oxygen species has the characteristic of long-term effectiveness. At the same time, by comparison, it can be seen that the ability of the antibacterial enhancer AP1 to generate reactive oxygen species under light is stronger than that of AP2 - AP4.

[0190] (2) Antibacterial performance

[0191] Add 10 mg of the antibacterial enhancer to 20 mL of phosphate buffer, mix it with 1×10 4 CFU / mL Escherichia coli (ATCC25922) bacterial solution to obtain a bacterial solution mixture. Pipette 100 μL of the bacterial solution mixture onto a plate and culture it at 37 °C for 24 h. During this period, irradiate it with a fluorescent lamp (50 W) for 30 min every 1 h, and calculate the inhibition rate. Among them, No Light represents a blank control example, which uses the antibacterial enhancer AP1 for testing, but there is no light during the culture process.

[0192] Table 1

[0193]

[0194] The test results are as shown in Table 1 below and Figure 2 shown. It can be seen from the test results that when there is no light, the antibacterial enhancer AP1 shows certain antibacterial performance, but it is significantly worse than the situation under light. The antibacterial performance of the antibacterial enhancer AP1 is stronger than that of AP2 - AP4.

[0195] 3. Refer to Figure 3, is the infrared spectrum of the antibacterial enhancer AP1 prepared above. The characteristic peaks of Si-O and Ce-O are from rare-earth cerium-doped mesoporous silica, indicating the successful doping of cerium. The characteristic peaks of Ti-O, Ti-C, etc. are from MXene quantum dots loaded on rare-earth cerium-doped mesoporous silica, indicating the successful synthesis of the antibacterial enhancer AP1.

[0196] II. Performance Testing of Antibacterial Polyester Fibers

[0197] 1. Antibacterial Performance

[0198] Initial antibacterial performance: According to GB / T 20944.3-2008 "Evaluation of Antibacterial Properties of Textiles - Part 3: Oscillation Method", the antibacterial rate of the prepared antibacterial polyester fibers against Escherichia coli ATCC 25922 was measured by the shaking flask method to characterize its initial antibacterial performance. During the mixed culture of bacteria and fiber samples, every 1h, it was irradiated with a fluorescent lamp (50W) for 30min, and the total culture time was 18h.

[0199] Long-term antibacterial performance: The antibacterial polyester fibers were washed and dried to complete one washing, and repeated several times. According to the above method, the antibacterial rates under different repeated washing times were tested.

[0200] Among them, No Light represents the blank control example, and there is no light during the mixed culture of bacteria and fiber samples.

[0201] The test results are shown in Table 2 and Figure 4 as follows:

[0202] Table 2

[0203]

[0204] It can be seen from the test results that Example 1 has long-term antibacterial performance. Comparing with Comparative Example 1 shows that the antibacterial performance mainly comes from the antibacterial enhancer. Comparing with the blank control example shows that the antibacterial performance of the polyester fibers in Example 1 under light has been significantly improved.

[0205] 2. Mechanical Properties

[0206] Initial breaking strength: Refer to the standard "GB / T 14344-2022 Test Method for Tensile Properties of Chemical Fibers - Filament Yarns" to measure the breaking strength of polyester fibers.

[0207] Breaking strength after light irradiation: The polyester fibers were irradiated with a fluorescent lamp. The distance between the fluorescent lamp and the sample was 20cm, the power was 50W, and the irradiation time was 120h. Then, according to the above standard, the breaking strength of the polyester fibers was measured again, and the breaking strength retention rate was calculated. The breaking strength retention rate = (breaking strength after light irradiation / initial breaking strength) × 100%.

[0208] The test results are shown in Table 3 and Figure 5 and Figure 6 as follows:

[0209] Table 3

[0210]

[0211] It can be seen from the test results that the antibacterial polyester fibers prepared in Examples 1-3 have high breaking strength and little strength loss after light treatment; in Comparative Example 2, there is no isolation transition layer, and the reactive oxygen generated by the antibacterial enhancer in the antibacterial enhancement layer under light will attack the internal PET fibers, resulting in a significant and rapid decrease in its breaking strength. In Comparative Examples 3-5, the retention rates of the breaking strength all decreased to varying degrees, indicating that 2-hydroxyethyl phosphate 2-methyl-2-acrylate, 2-perfluorododecylethyl methacrylate, and styrene monomer in the isolation transition layer can cooperate with each other to enhance the barrier performance of the coating film.

[0212] Although the embodiments of the present invention have been disclosed as above, it is not limited to the applications listed in the specification and embodiments. It can be fully applied to various fields suitable for the present invention. For those familiar with the field, additional modifications can be easily made. Therefore, without departing from the general concept defined by the claims and the equivalent scope, the present invention is not limited to specific details.

Claims

1. A preparation method of an antibacterial polyester fiber, characterized in that, It includes the following steps: S1. Coating an isolation transition layer on the PET fiber: S1-1. After cleaning the PET fiber, mix it with a silane coupling agent and react to obtain pretreated fiber; S1-2. Mix the pretreated fiber with a monomer mixture, a fluorine-containing monomer, styrene and a crosslinking agent, add an initiator and then heat and react to obtain an intermediate fiber product; S2. Coating an antibacterial enhancement layer on the intermediate fiber product: S2-1. Mix an antibacterial enhancer with a silane coupling agent and react to obtain a modified antibacterial enhancer; S2-2. Mix the intermediate fiber product, the modified antibacterial enhancer with a monomer mixture and a crosslinking agent, add an initiator and then heat and react to obtain antibacterial polyester fiber; The antibacterial enhancer is prepared by the following method: 1-1) Prepare rare earth cerium-doped mesoporous silica: 1-2) Add T3C2T x After treating MXene with acid, add it to an aqueous solution of ammonium dihydrogen phosphate for reaction to obtain pretreated T3C2T x MXene; 1-3) Mix rare earth cerium-doped mesoporous silica, octanohydroxamic acid, pretreated T3C2T x MXene, and ethylenediamine, and then carry out a hydrothermal reaction to obtain an antibacterial enhancer.

2. The preparation method of the antibacterial polyester fiber according to claim 1, characterized in that, Wherein, The monomer mixture is a mixture of acrylic acid, 2-hydroxyethyl methacrylate and 2-hydroxyethyl 2-methyl-2-propenoate phosphate.

3. The preparation method of the antibacterial polyester fiber according to claim 2, characterized in that, The fluorine-containing monomer is one or more of trifluoroethyl methacrylate, 1H,1H,2H,2H-perfluorooctyl methacrylate, perfluoromethyl ethyl acrylate, 2-perfluorododecylethyl methacrylate.

4. The preparation method of the antibacterial polyester fiber according to claim 3, characterized in that, The fluorine-containing monomer is 2-perfluorododecylethyl methacrylate, and the crosslinking agent is divinylbenzene.

5. The preparation method of the antibacterial polyester fiber according to claim 4, characterized in that, It includes the following steps: S1. Coating an isolation transition layer on the PET fiber: S1-1. After cleaning the PET fiber, immerse it in ethanesulfonic acid, take it out and mix it with the silane coupling agent KH-570, and react under heating to obtain pretreated fiber; S1-2. Mix the pretreated fiber with acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl 2-methyl-2-propenoate phosphate, 2-perfluorododecylethyl methacrylate, styrene and divinylbenzene in acetone, add benzoyl peroxide and then heat and react to obtain an intermediate fiber product; S2. Coating an antibacterial enhancement layer on the intermediate fiber product: S2-1. Mix an antibacterial enhancer with the silane coupling agent KH-570 and react to obtain a modified antibacterial enhancer; S2-2. Mix the intermediate fiber product, the modified antibacterial enhancer with acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl 2-methyl-2-propenoate phosphate and divinylbenzene, add benzoyl peroxide and then heat and react to obtain antibacterial polyester fiber.

6. The preparation method of the antibacterial polyester fiber according to claim 5, characterized in that, It includes the following steps: S1. Coating an isolation transition layer on the PET fiber: S1-1. After sequentially cleaning the PET fiber with deionized water and ethanol, immerse it in ethanesulfonic acid, take it out and mix it with the silane coupling agent KH-570, and stir and react at 50-70 °C for 12-36 h to obtain pretreated fiber; wherein, the mass ratio of KH-570 to PET fiber is 1:1~4:1; S1-2. Mix the pretreated fiber with acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl 2-methyl-2-propenoate phosphate, 2-perfluorododecylethyl methacrylate, styrene and divinylbenzene in acetone, add benzoyl peroxide and then heat and react at 60-75 °C for 6-24 h to obtain an intermediate fiber product; S2. Coating an antibacterial enhancement layer on the intermediate fiber product: S2-1. Mix the antibacterial enhancer with silane coupling agent KH-570 and stir and react at 70-90 °C for 6-24 h to obtain a modified antibacterial enhancer; wherein, the mass ratio of KH-570 to antibacterial enhancer is 1:1 to 2:1; S2-2. Mix the fiber intermediate product, modified antibacterial enhancer, acrylic acid, 2-hydroxyethyl methacrylate, 2-hydroxyethyl 2-methyl-2-propenoate phosphate, and divinylbenzene in ethanol, add benzoyl peroxide, and heat and react at 55-70 °C for 6-24 h to obtain antibacterial polyester fiber.

7. The preparation method of the antibacterial polyester fiber according to claim 6, characterized in that, In step S1-2, the mass ratio of pretreated fiber: acrylic acid: 2-hydroxyethyl methacrylate: 2-hydroxyethyl 2-methyl-2-propenoate phosphate: 2-perfluorododecylethyl methacrylate: styrene: divinylbenzene: benzoyl peroxide is 1:0.5-2:1-2.5:0.4-2:0.35-2:0.5-2:0.2-0.5:0.01-0.1; In step S2-2, the mass ratio of fiber intermediate product: modified antibacterial enhancer: acrylic acid: 2-hydroxyethyl methacrylate: 2-hydroxyethyl 2-methyl-2-propenoate phosphate: divinylbenzene: benzoyl peroxide is 1:0.2-1:1-2.5:0.5-2:1.5-3:0.2-1:0.01-0.

1.

8. The preparation method of the antibacterial polyester fiber according to claim 4, characterized in that, The antibacterial enhancer is prepared by the following method: 1-1) Prepare rare earth cerium-doped mesoporous silica: Add hexadecylamine, cerium nitrate, mesitylene, and deionized water to n-pentanol, disperse, add tetraethyl orthosilicate, then dropwise add ammonia water, stir and react, filter, wash, dry the product, and calcine to obtain rare earth cerium-doped mesoporous silica; 1-2) Load MXene quantum dots on the rare earth cerium-doped mesoporous silica; T3C2T x After treating MXene with a mixed acid composed of nitric acid and sulfuric acid, it is added to an aqueous solution of ammonium dihydrogen phosphate and stirred for reaction, followed by centrifugal filtration and washing to obtain pretreated T3C2T x MXene; 1-3) Mix rare earth cerium-doped mesoporous silica, octanohydroxamic acid, pretreated T3C2T x MXene, and ethylenediamine in deionized water, transfer it to a reaction kettle after ultrasonic dispersion, carry out hydrothermal reaction under heating, filter, wash, and dry to obtain an antibacterial enhancer.

9. The preparation method of the antibacterial polyester fiber according to claim 8, characterized in that, The antibacterial enhancer is prepared by the following method: 1-1) Prepare rare earth cerium-doped mesoporous silica: Add 0.75-3 g of hexadecylamine, 0.25-1 g of cerium nitrate, 0.2-0.8 g of mesitylene, and 60-240 mL of deionized water to 75-300 n-pentanol, ultrasonically disperse for 5-30 min, then add 4.5-20 mL of tetraethyl orthosilicate, and then dropwise add 5-20 mL of ammonia water with a mass concentration of 5-20%. Stir and react at 20-30 °C for 12-48 h. Filter the product and wash it with deionized water. Dry it at 50-70 °C for 4-16 h and then calcine it at 500-600 °C for 3-10 h to obtain rare earth cerium-doped mesoporous silica; 1-2) Load MXene quantum dots on the rare earth cerium-doped mesoporous silica; Add 0.5 - 2 g of T3C2T x MXene to a mixed acid containing 25 - 100 mL of 65 wt% concentrated nitric acid and 25 - 100 mL of 95 wt% concentrated sulfuric acid, react at 90 - 100 °C for 4 - 16 h, filter after cooling to room temperature, wash with deionized water until neutral, and then add it to 50 - 200 mL of an aqueous solution of ammonium dihydrogen phosphate with a mass concentration of 2.5 - 10%, stir at room temperature for 6 - 24 h, centrifuge, filter, and wash to obtain pretreated T3C2T x MXene; 1-3) Take 1.25 - 5 g of rare earth cerium-doped mesoporous silica and 0.5 - 2 g of octanohydroxamic acid, add them to 100 - 400 mL of deionized water, ultrasonically disperse for 15 - 60 min, and then add the pretreated T3C2T MXene prepared in step 1-2), 0.05 - 0.3 g of ethylenediamine, ultrasonically disperse for 30 - 90 min. Transfer the obtained mixture to a stainless steel autoclave, react at 120 - 150 °C for 6 - 24 h, cool to room temperature, centrifuge and filter. Wash the solid product successively with deionized water and ethanol, vacuum dry at 70 - 90 °C for 6 - 24 h, and grind to obtain an antibacterial enhancer. x ​ 10. An antibacterial polyester fiber, characterized in that, It includes a PET fiber as the core, an isolation transition layer coated on the core, and an antibacterial enhancement layer coated on the isolation transition layer; the antibacterial polyester fiber is prepared by the method described in any one of claims 1-9.

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